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172 results on '"Andrei Y. Khodakov"'

1. Photocatalytic dihydroxylation of light olefins to glycols by water

Author: Chunyang Dong, Yinghao Wang, Ziqi Deng, Wenchao Wang, Maya Marinova, Karima Ben Tayeb, Jean-Charles Morin, Melanie Dubois, Martine Trentesaux, Yury G. Kolyagin, My Nghe Tran, Vlad Martin-Diaconescu, Olga Safonova, Jeremie Zaffran, Andrei Y. Khodakov, and Vitaly V. Ordomsky
Subjects: Science
Abstract: Abstract Aliphatic diols such as ethylene and propylene glycol are the key products in the chemical industry for manufacturing polymers. The synthesis of these molecules usually implies sequential processes, including epoxidation of olefins using hydrogen peroxide or oxygen with subsequent hydrolysis to glycols. Direct hydroxylation of olefins by cheap and green oxidants is an economically attractive and environmentally friendly route for the synthesis of diols. Here, we report a photocatalytic reaction for the dihydroxylation of ethylene and propylene to their glycols at room temperature using water as the oxidant. The photocatalyst contains Pd clusters stabilized by sub-nanometric polyoxometalate with TiO2 as the host material. Under light irradiation, it results in production rates of ethylene glycol and propylene glycols of 146.8 mmol·gPd −1·h−1 and 28.6 mmol·gPd −1·h−1 with liquid-phase selectivities of 63.3 % and 80.0 %, respectively. Meanwhile, green hydrogen derived from water is produced as another valuable product. Combined spectroscopy investigation suggests that the reaction proceeds via π-bonded adsorption of olefins over Pd clusters with hydroxylation by hydroxyl radicals formed by photocatalytic dissociation of water.
Published: 2024
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2. Liquid metals for boosting stability of zeolite catalysts in the conversion of methanol to hydrocarbons

Author: Yong Zhou, Sara Santos, Mariya Shamzhy, Maya Marinova, Anne-Marie Blanchenet, Yury G. Kolyagin, Pardis Simon, Martine Trentesaux, Sharmin Sharna, Ovidiu Ersen, Vladimir L. Zholobenko, Mark Saeys, Andrei Y. Khodakov, and Vitaly V. Ordomsky
Subjects: Science
Abstract: Abstract Methanol-to-hydrocarbons (MTH) process has been considered one of the most practical approaches for producing value-added products from methanol. However, the commonly used zeolite catalysts suffer from rapid deactivation due to coke deposition and require regular regeneration treatments. We demonstrate that low-melting-point metals, such as Ga, can effectively promote more stable methanol conversion in the MTH process by slowing coke deposition and facilitating the desorption of carbonaceous species from the zeolite. The ZSM-5 zeolite physically mixed with liquid gallium exhibited an enhanced lifetime in the MTH reaction, which increased by a factor of up to ~14 as compared to the parent ZSM-5. These results suggest an alternative route to the design and preparation of deactivation-resistant zeolite catalysts.
Published: 2024
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3. Ion-exchanged zeolite P as a nanostructured catalyst for biodiesel production

Author: Aqeel Al-Ani, Natalie E. Mordvinova, Oleg I. Lebedev, Andrei Y. Khodakov, and Vladimir Zholobenko
Subjects: Electrical engineering. Electronics. Nuclear engineering, TK1-9971
Abstract: Nano-crystalline synthetic gismondine modified via cation exchange has been utilised as a highly active and selective catalyst for the production of biofuel. In comparison with low silica zeolites FAU and LTA, K-form of gismondine, based on the maximum aluminium P (MAP) zeolite, exhibited a significant improvement in catalytic performance in the methanolysis of bio-oil, which can be attributed to its nano-particle morphology and high basicity associated with the high Al content and high degree of ion exchange, as demonstrated by the TEM, XRD, TGA, NMR, XPS and CO2-TPD studies. To the best of our knowledge, this is the first report on a successful catalytic application of basic K-MAP zeolite. Keywords: Synthetic gismondine, Zeolites, Transesterification, Basic sites, Nanostructured catalysts
Published: 2019
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4. Selective photocatalytic conversion of methane into carbon monoxide over zinc-heteropolyacid-titania nanocomposites

Author: Xiang Yu, Vincent De Waele, Axel Löfberg, Vitaly Ordomsky, and Andrei Y. Khodakov
Subjects: Science
Abstract: While methane has become an increasingly important chemical feedstock, its selective conversion to other chemicals has proven challenging. Here, authors demonstrate a photocatalyst based on earth-abundant elements that selectively converts methane to carbon monoxide under mild conditions.
Published: 2019
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5. Structure–performance correlations in the hybrid oxide-supported copper–zinc SAPO-34 catalysts for direct synthesis of dimethyl ether from CO2

Author: Sara Navarro-Jaén, Mirella Virginie, Joëlle Thuriot-Roukos, Robert Wojcieszak, Andrei Y. Khodakov, Unité de Catalyse et Chimie du Solide - UMR 8181 (UCCS), Université d'Artois (UA)-Centrale Lille-Institut de Chimie du CNRS (INC)-Université de Lille-Centre National de la Recherche Scientifique (CNRS), Université de Lille, CNRS, Centrale Lille, ENSCL, Univ. Artois, Unité de Catalyse et Chimie du Solide - UMR 8181 [UCCS], and Unité de Catalyse et Chimie du Solide (UCCS) - UMR 8181
Subjects: Mechanics of Materials, Mechanical Engineering, [SDE]Environmental Sciences, [CHIM]Chemical Sciences, General Materials Science, hybrid catalysts, metal dispersion, acidity, CO2 mitigation, dimethyl ether
Abstract: Growing CO2 emissions lead to global warming, which is currently one of the most challenging environmental phenomena. Direct catalytic hydrogenation to dimethyl ether over hybrid catalysts enables CO2 utilization, hydrogen and energy storage and produces sustainable fuels and an important platform molecule. In this paper, we evaluated structure–performance correlations in the bifunctional hybrid copper–zinc SAPO-34 catalysts for direct synthesis of dimethyl ether via CO2 prepared using zirconia, alumina and ceria used as oxide carriers. Higher copper dispersion and higher CO2 conversion rate were uncovered over the alumina and zirconia supported catalysts followed by ceria supported counterpart. The CO2 hydrogenation seems to be principally favoured by higher copper dispersion and to a lesser extent depends on the concentration of Bronsted acid sites in the studied catalysts. Because of lower reverse water gas-shift activity, the alumina supported catalyst exhibited a higher dimethyl ether yield compared to the zirconia and ceria supported counterparts. 57;5
Published: 2022
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6. Direct Photocatalytic Synthesis of Acetic Acid from Methane and CO at Ambient Temperature Using Water as Oxidant

Author: Chunyang Dong, Maya Marinova, Karima Ben Tayeb, Olga V. Safonova, Yong Zhou, Di Hu, Sergei Chernyak, Massimo Corda, Jérémie Zaffran, Andrei Y. Khodakov, Vitaly V. Ordomsky, Unité de Catalyse et Chimie du Solide - UMR 8181 (UCCS), Université d'Artois (UA)-Centrale Lille-Institut de Chimie du CNRS (INC)-Université de Lille-Centre National de la Recherche Scientifique (CNRS), Unité Matériaux et Transformations - UMR 8207 (UMET), Institut National de la Recherche Agronomique (INRA)-Ecole Nationale Supérieure de Chimie de Lille (ENSCL)-Institut de Chimie du CNRS (INC)-Université de Lille-Centre National de la Recherche Scientifique (CNRS), Laboratoire Avancé de Spectroscopie pour les Intéractions la Réactivité et l'Environnement - UMR 8516 (LASIRE), Institut de Chimie du CNRS (INC)-Université de Lille-Centre National de la Recherche Scientifique (CNRS), and Paul Scherrer Institute (PSI)
Subjects: [CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry, Colloid and Surface Chemistry, Catalysts, Irradiation, Oxides, General Chemistry, [CHIM.CATA]Chemical Sciences/Catalysis, Biochemistry, Catalysis, Hydrocarbons, Platinum
Abstract: International audience; Direct functionalization of methane selectively to value-added chemicals is still one of the main challenges in modern science. Acetic acid is an important industrial chemical produced nowadays by expensive and environmentally unfriendly carbonylation of methanol using homogeneous catalysts. Here, we report a new photocatalytic reaction route to synthesize acetic acid from CH4 and CO at room temperature using water as the sole external oxygen source. The optimized photocatalyst consists of a TiO2 support and ammonium phosphotungstic polyoxometalate (NPW) clusters anchored with isolated Pt single atoms (Pt1). It enables a stable synthesis of 5.7 mmol·L–1 acetic acid solution in 60 h with the selectivity over 90% and 66% to acetic acid on liquid-phase and carbon basis, respectively, with the production of 99 mol of acetic acid per mol of Pt. Combined isotopic and in situ spectroscopy investigation suggests that synthesis of acetic acid proceeds via a photocatalytic oxidative carbonylation of methane over the Pt1 sites, with the methane activation facilitated by water-derived hydroxyl radicals.
Published: 2023
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7. Photocatalytic Partial Oxidation of Methane to Carbon Monoxide and Hydrogen over CIGS Solar Cell

Author: Chunyang Dong, Di Hu, Karima Ben Tayeb, Pardis Simon, Ahmed Addad, Martine Trentesaux, Danilo Oliveira de Souza, Sergei Chernyak, Deizi V. Peron, Amelle Rebai, Jean-Francois Guillemoles, Xavier Wallart, Bruno Grandidier, Andrei Y. Khodakov, Negar Naghavi, Vitaly V. Ordomsky, Unité de Catalyse et Chimie du Solide - UMR 8181 (UCCS), Université d'Artois (UA)-Centrale Lille-Institut de Chimie du CNRS (INC)-Université de Lille-Centre National de la Recherche Scientifique (CNRS), Institut Michel Eugène Chevreul - FR 2638 (IMEC), Université d'Artois (UA)-Centrale Lille-Institut de Chimie du CNRS (INC)-Université de Lille-Centre National de la Recherche Scientifique (CNRS)-Institut National de Recherche pour l’Agriculture, l’Alimentation et l’Environnement (INRAE), Elettra Sincrotrone Trieste, Institut Photovoltaïque d’Ile-de-France (UMR) (IPVF), École polytechnique (X)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-TOTAL FINA ELF-EDF (EDF)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut Photovoltaïque d’Ile-de-France (ITE) (IPVF)-Air Liquide [Siège Social], Institut Photovoltaïque d’Ile-de-France (ITE) (IPVF), Institut d’Électronique, de Microélectronique et de Nanotechnologie - UMR 8520 (IEMN), Centrale Lille-Université de Lille-Centre National de la Recherche Scientifique (CNRS)-Université Polytechnique Hauts-de-France (UPHF)-JUNIA (JUNIA), Université catholique de Lille (UCL)-Université catholique de Lille (UCL), EPItaxie et PHYsique des hétérostructures - IEMN (EPIPHY - IEMN), Université catholique de Lille (UCL)-Université catholique de Lille (UCL)-Centrale Lille-Université de Lille-Centre National de la Recherche Scientifique (CNRS)-Université Polytechnique Hauts-de-France (UPHF)-JUNIA (JUNIA), Physique - IEMN (PHYSIQUE - IEMN), Eco-Efficient Products & Processes Laboratory (E2P2L), RHODIA-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), The authors gratefully acknowledge the support of the French National Research Agency (SolarMethaCell project). We are grateful to the Elettra and Soleil synchrotrons for the use of beamtime., Renatech Network, and ANR-22-CE05-0019,SolarMethaCell,Conversion du méthane en molécules de plate-forme dans des conditions ambiantes à l'aide de cellules solaires(2022)
Subjects: [CHIM.ANAL]Chemical Sciences/Analytical chemistry, Process Chemistry and Technology, Photocatalysis, Oxidation, CIGS, [CHIM.CATA]Chemical Sciences/Catalysis, [CHIM.MATE]Chemical Sciences/Material chemistry, [CHIM.INOR]Chemical Sciences/Inorganic chemistry, Syngas, Methane, Catalysis, General Environmental Science
Abstract: International audience; Methane valorization is one of the main challenges in the modern chemical industry. However, existing processes require high reaction temperatures. The alternative photocatalytic routes for methane valorization at ambient conditions would be highly attractive. Today, photovoltaic (PV) generation of electricity is one of the main sources of renewable energy. PV absorbers could be excellent candidates for photochemical applications. Herein, we report selective methane photocatalytic oxidation at ambient conditions into CO and H2 by conventional Cu(In,Ga)Se2 (CIGS) absorbers used in solar cells. A thin film of CIGS coated over Mo exhibits exceptional performance in methane partial oxidation to CO and H2 with a stable CO productivity of 2.4 mmol per g of CIGS and a selectivity to CO of over 80 %. The reaction proceeds via the facile dissociation of methane into disordered carbon and hydrogen over CIGS surface with subsequent regeneration of the surface by partial oxidation of carbon into CO.
Published: 2023
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8. Light olefin synthesis from a diversity of renewable and fossil feedstocks: state-of the-art and outlook

Author: Sergei A. Chernyak, Massimo Corda, Jean-Pierre Dath, Vitaly V. Ordomsky, Andrei Y. Khodakov, Université de Lille, CNRS, Centrale Lille, ENSCL, Univ. Artois, Unité de Catalyse et Chimie du Solide - UMR 8181 [UCCS], Total Energies, Unité de Catalyse et Chimie du Solide (UCCS) - UMR 8181, Total Research and Technology Feluy ( [TRTF]), Unité de Catalyse et Chimie du Solide - UMR 8181 (UCCS), and Université d'Artois (UA)-Centrale Lille-Institut de Chimie du CNRS (INC)-Université de Lille-Centre National de la Recherche Scientifique (CNRS)
Subjects: Fossils, Methanol, Alkanes, [CHIM]Chemical Sciences, General Chemistry, Alkenes, Carbon Dioxide
Abstract: Light olefins are important feedstocks and platform molecules for the chemical industry. Their synthesis has been a research priority in both academia and industry. There are many different approaches to the synthesis of these compounds, which differ by the choice of raw materials, catalysts and reaction conditions. The goals of this review are to highlight the most recent trends in light olefin synthesis and to perform a comparative analysis of different synthetic routes using several quantitative characteristics: selectivity, productivity, severity of operating conditions, stability, technological maturity and sustainability. Traditionally, on an industrial scale, the cracking of oil fractions has been used to produce light olefins. Methanol-to-olefins, alkane direct or oxidative dehydrogenation technologies have great potential in the short term and have already reached scientific and technological maturities. Major progress should be made in the field of methanol-mediated CO and CO2 direct hydrogenation to light olefins. The electrocatalytic reduction of CO2 to light olefins is a very attractive process in the long run due to the low reaction temperature and possible use of sustainable electricity. The application of modern concepts such as electricity-driven process intensification, looping, CO2 management and nanoscale catalyst design should lead in the near future to more environmentally friendly, energy efficient and selective large-scale technologies for light olefin synthesis. 51
Published: 2022
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9. Highly Efficient and Selective N-Alkylation of Amines with Alcohols Catalyzed by in Situ Rehydrated Titanium Hydroxide

Author: Feng Niu, Zhen Yan, Bright T. Kusema, Qiyan Wang, Andrei Y. Khodakov, Vitaly V. Ordomsky, Eco-Efficient Products &Processes Laboratory (E2PL2), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-RHODIA, Unité de Catalyse et Chimie du Solide - UMR 8181 (UCCS), Centrale Lille Institut (CLIL)-Université d'Artois (UA)-Centrale Lille-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Lille, Université d'Artois (UA)-Centrale Lille-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Lille, Eco-Efficient Products & Processes Laboratory (E2P2L), RHODIA-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), and Université d'Artois (UA)-Centrale Lille-Institut de Chimie du CNRS (INC)-Université de Lille-Centre National de la Recherche Scientifique (CNRS)
Subjects: In situ, [CHIM.ORGA]Chemical Sciences/Organic chemistry, 010405 organic chemistry, Chemistry, [CHIM.CATA]Chemical Sciences/Catalysis, General Chemistry, Alkylation, 010402 general chemistry, 01 natural sciences, Catalysis, 0104 chemical sciences, Homogeneous, [CHIM]Chemical Sciences, Organic chemistry, Titanium hydroxide, ComputingMilieux_MISCELLANEOUS
Abstract: International audience; Catalytic N-alkylation of amines by alcohols to produce desired amines is an important catalytic reaction in industry. Various noble-metal-based homogeneous and heterogeneous catalysts have been reported for this process. The development of cheap non-noble-metal heterogeneous catalysts for the N-alkylation reaction would be highly desirable. Hereby, we propose the N-alkylation of amines by alcohols over a cheap and efficient heterogeneous catalyst—titanium hydroxide. This catalyst provides a selectivity higher than 90% to secondary amines for functionalized aromatic and aliphatic alcohols and amines with high catalytic activity and stability. Mild Brönsted acidity formed by the continuous rehydration of Lewis acidity excludes the side reactions and deactivation by adsorbed species. The mechanism of the reaction involves dehydration of alcohols to ethers with subsequent C–O bond cleavage by amine with the formation of secondary amine and recovery of alcohol.
Published: 2020
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10. Efficient Promoters and Reaction Paths in the CO 2 Hydrogenation to Light Olefins over Zirconia-Supported Iron Catalysts

Author: Alan J. Barrios, Deizi V. Peron, Anoop Chakkingal, Achim Iulian Dugulan, Simona Moldovan, Kalthoum Nakouri, Joëlle Thuriot-Roukos, Robert Wojcieszak, Joris W. Thybaut, Mirella Virginie, Andrei Y. Khodakov, Unité de Catalyse et Chimie du Solide - UMR 8181 (UCCS), Université d'Artois (UA)-Centrale Lille-Institut de Chimie du CNRS (INC)-Université de Lille-Centre National de la Recherche Scientifique (CNRS), Laboratory for Chemical Technology, Universiteit Gent = Ghent University (UGENT), Delft University of Technology (TU Delft), Groupe de physique des matériaux (GPM), Université de Rouen Normandie (UNIROUEN), Normandie Université (NU)-Normandie Université (NU)-Institut national des sciences appliquées Rouen Normandie (INSA Rouen Normandie), Institut National des Sciences Appliquées (INSA)-Normandie Université (NU)-Institut National des Sciences Appliquées (INSA)-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche sur les Matériaux Avancés (IRMA), Université de Caen Normandie (UNICAEN), Normandie Université (NU)-Normandie Université (NU)-École Nationale Supérieure d'Ingénieurs de Caen (ENSICAEN), Normandie Université (NU)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université de Rouen Normandie (UNIROUEN), Normandie Université (NU)-Institut national des sciences appliquées Rouen Normandie (INSA Rouen Normandie), Institut National des Sciences Appliquées (INSA)-Normandie Université (NU)-Institut National des Sciences Appliquées (INSA)-Centre National de la Recherche Scientifique (CNRS)-Université de Caen Normandie (UNICAEN), Normandie Université (NU)-École Nationale Supérieure d'Ingénieurs de Caen (ENSICAEN), Normandie Université (NU)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Centre National de la Recherche Scientifique (CNRS), Université de Lille, CNRS, Centrale Lille, ENSCL, Univ. Artois, Unité de Catalyse et Chimie du Solide - UMR 8181 [UCCS], and Unité de Catalyse et Chimie du Solide (UCCS) - UMR 8181
Subjects: iron catalysts, COmitigation, [SDE]Environmental Sciences, [CHIM]Chemical Sciences, CO2 mitigation, hydrogenation, light olefins, high throughput, General Chemistry, Catalysis
Abstract: Hydrogenation into light olefins is an attractive strategy for CO2fixation into chemicals. In this article, high throughput experimentation and extended characterization were employed to identify the most efficient promoters and to elucidate structure-performance correlations and reaction paths in the CO2hydrogenation to light olefins over zirconia-supported iron catalysts. K, Cs, Ba, Ce, Nb, Mo, Mn, Cu, Zn, Ga, In, Sn, Sb, Bi, and V were added in the same molar concentrations to zirconia-supported iron catalyst and evaluated as promoters. The CO2hydrogenation proceeds via intermediate formation of CO followed by surface polymerization. Over the iron catalysts containing alkaline promoters, initially higher selectivity to light olefins shows a significant decrease with the CO2conversion, because of further surface polymerization and the formation of longer chain hydrocarbons. A relatively low selectivity to light olefins over the promoted catalysts, without potassium, is not much affected by the CO2conversion. Essential characteristics of iron catalysts to obtain a higher yield of light olefins seem to be a higher iron dispersion, a higher extent of carbidization, and optimized basicity. The strongest promoting effect is reported for the alkaline metals. A further increase in the light olefin selectivity is observed after simultaneous addition of potassium with copper, molybdenum, gallium, or cerium.
Published: 2022
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11. Hybrid monometallic and bimetallic copper–palladium zeolite catalysts for direct synthesis of dimethyl ether from CO 2

Author: Sara Navarro-Jaén, Mirella Virginie, Jean-Charles Morin, Joëlle Thuriot-Roukos, Robert Wojcieszak, Andrei Y. Khodakov, Unité de Catalyse et Chimie du Solide - UMR 8181 (UCCS), and Université d'Artois (UA)-Centrale Lille-Institut de Chimie du CNRS (INC)-Université de Lille-Centre National de la Recherche Scientifique (CNRS)
Subjects: [SDE]Environmental Sciences, Materials Chemistry, [CHIM]Chemical Sciences, General Chemistry, Catalysis
Abstract: International audience; Currently, carbon dioxide in the atmosphere is the major contributor toward global climate change. Direct CO2 hydrogenation to dimethyl ether produces an important platform molecule for the synthesis of fuels and chemicals and at the same time, utilizes large amounts of this greenhouse gas. In this paper, we prepared a series of hybrid catalysts, which are composed of alumina supported copper–palladium nanoparticles and HZSM-5 zeolite for the direct synthesis of dimethyl ether from CO2. Copper active sites showed a higher intrinsic activity for CO2 hydrogenation compared to palladium. The low palladium content in the copper–palladium bimetallic catalysts was particularly beneficial for the dimethyl ether production. Undesirable methane and ethane production was completely suppressed, while the dimethyl ether selectivity was considerably increased. Extensive catalyst characterization combined with catalytic measurements was indicative of the presence of copper and palladium monometallic and bimetallic particles with different sizes and reducibility in the hybrid catalysts. The presence of even small amounts of palladium significantly improved copper reducibility and copper dispersion. Some decrease in the Brønsted acidity in the copper containing catalysts was due to the migration of unreduced copper ions in the zeolite channels during the reduction. The methanol dehydration to dimethyl ether was only slightly affected by the amounts of Brønsted acid sites in the hybrid catalysts.
Published: 2022
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12. Thermocatalysis enables photocatalytic oxidation of methane to formic acid at room temperature beyond the selectivity limits

Author: Di Hu, Ahmed Addad, Karima Ben Tayeb, Vitaly V. Ordomsky, Andrei Y. Khodakov, Unité de Catalyse et Chimie du Solide - UMR 8181 (UCCS), Université d'Artois (UA)-Centrale Lille-Institut de Chimie du CNRS (INC)-Université de Lille-Centre National de la Recherche Scientifique (CNRS), Unité Matériaux et Transformations - UMR 8207 (UMET), Institut National de la Recherche Agronomique (INRA)-Ecole Nationale Supérieure de Chimie de Lille (ENSCL)-Institut de Chimie du CNRS (INC)-Université de Lille-Centre National de la Recherche Scientifique (CNRS), Laboratoire Avancé de Spectroscopie pour les Intéractions la Réactivité et l'Environnement - UMR 8516 (LASIRE), and Institut de Chimie du CNRS (INC)-Université de Lille-Centre National de la Recherche Scientifique (CNRS)
Subjects: General Energy, General Engineering, General Physics and Astronomy, General Materials Science, [CHIM.CATA]Chemical Sciences/Catalysis, General Chemistry
Abstract: International audience; Direct conversion of methane into fuels and chemicals remains a major challenge in modern science. Formic acid is one of the most promising platform molecules. Photocatalysis proposes an attractive route for methane partial oxidation under mild conditions. The radical mechanism of methane photocatalytic oxidation restricts the selectivity to target products. In this article, we propose a strategy to break conventional limitations of methane photocatalytic oxidation by adding a thermocatalyst and conducting the process in a one-pot reactor. In this strategy, the methane selective conversion into formic acid proceeds first over cesium salt of phosphotungstic acid on titania, which photocatalytically oxidizes methane into a mixture of C1 oxygenates. These oxygenates are then selectively converted into formic acid over a heterogeneous alumina-supported ruthenium catalyst. All reactions occur at room temperature in the same reactor. A selectivity to formic acid of 85% and a productivity of 5 mmol g−1photocatalyst are achieved.
Published: 2023
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13. Synthesis of stack plate covalent organic framework nanotubes using a self-assembled acid as a soft template

Author: Dan Wu, Dandan Han, Yong Zhou, Zhen Zhang, Hang Qian, Qian Zhou, Yongsheng Zhang, Andrei Y. Khodakov, Vitaly V. Ordomsky, Unité de Catalyse et Chimie du Solide - UMR 8181 (UCCS), Université d'Artois (UA)-Centrale Lille-Institut de Chimie du CNRS (INC)-Université de Lille-Centre National de la Recherche Scientifique (CNRS), Zhengzhou University, Henan Agricultural University, Université de Lille, CNRS, Centrale Lille, ENSCL, Univ. Artois, Unité de Catalyse et Chimie du Solide - UMR 8181 [UCCS], Unité de Catalyse et Chimie du Solide (UCCS) - UMR 8181, Anhui University [Hefei], Huawei Technologies France, and Huawei Technologies France [Boulogne-Billancourt]
Subjects: [CHIM.ORGA]Chemical Sciences/Organic chemistry, Materials Chemistry, Metals and Alloys, Ceramics and Composites, [CHIM]Chemical Sciences, General Chemistry, [CHIM.MATE]Chemical Sciences/Material chemistry, Catalysis, Surfaces, Coatings and Films, Electronic, Optical and Magnetic Materials
Abstract: International audience; COF-LZU1 with nanotube-like morphology has been synthesized with high crystallinity and pore volume in the presence of trimesic acid as a template. The as-synthesized COF nanotubes consist of a stack of plates with a diameter of about 100 nm with a hollow channel inside of about 20 nm.
Published: 2022
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14. Machine learning based interpretation of microkinetic data: a Fischer–Tropsch synthesis case study

Author: Andrei Y. Khodakov, Anoop Chakkingal, Joris Thybaut, Alan J. Barrios, Jeroen Poissonnier, Mirella Virginie, Pieter Janssens, Laboratory for Chemical Technology, Universiteit Gent = Ghent University (UGENT), UCCS Équipe Catalyse Supramoléculaire, Unité de Catalyse et Chimie du Solide - UMR 8181 (UCCS), Université d'Artois (UA)-Centrale Lille-Institut de Chimie du CNRS (INC)-Université de Lille-Centre National de la Recherche Scientifique (CNRS)-Université d'Artois (UA)-Centrale Lille-Institut de Chimie du CNRS (INC)-Université de Lille-Centre National de la Recherche Scientifique (CNRS), and Université d'Artois (UA)-Centrale Lille-Institut de Chimie du CNRS (INC)-Université de Lille-Centre National de la Recherche Scientifique (CNRS)
Subjects: Technology and Engineering, Computer science, Machine learning, computer.software_genre, Catalysis, Interpretation (model theory), Permutation, DESIGN, Range (statistics), Chemical Engineering (miscellaneous), [CHIM]Chemical Sciences, [INFO]Computer Science [cs], OPTIMIZATION, Fluid Flow and Transfer Processes, Artificial neural network, Basis (linear algebra), business.industry, Process Chemistry and Technology, ARTIFICIAL-INTELLIGENCE, Process (computing), Fischer–Tropsch process, MODEL, Ranking, Chemistry (miscellaneous), Artificial intelligence, business, computer
Abstract: Machine-learning (ML) methods, such as artificial neural networks (ANNs), bring the data-driven design of chemical reactions within reach. Simultaneously with the verification of the absence of any bias in the machine learning model as compared to the microkinetic data, interpretation techniques such as permutation importance, SHAP values and partial dependence plots allow for a more systematic (model agnostic) analysis of these data. In the present work, this methodology is demonstrated for Fischer–Tropsch synthesis (FTS) on a cobalt catalyst, with methane yield as the single dominant output, as a case study. For the purpose of this case study, the dataset required for training the ANN model is synthetically generated using a single-event microkinetic (SEMK) model. With a number of 3 hidden layers with 20 nodes, the ANN model is able to adequately reproduce the SEMK results. The relative ranking of the process variables, as learnt by the ANN model, is identified using interpretation techniques, with the methane yield being most dependent on the temperature, followed by the space-time and syngas molar inlet ratio, in the investigated range of operating conditions. This is in line with the physicochemical understanding from SEMK. A systematic approach for analysing microkinetic data, generally analysed on a case-specific basis, is thus developed by combining more widely used interpretation techniques in data science with the ANN.
Published: 2021
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15. Design of ruthenium-zeolite nanocomposites for enhanced hydrocarbon synthesis from syngas

Author: Debora R. Strossi Pedrolo, Vitaly V. Ordomsky, Marcio Schwaab, Andrei Y. Khodakov, Nilson Romeu Marcilio, Unité de Catalyse et Chimie du Solide - UMR 8181 (UCCS), Université d'Artois (UA)-Centrale Lille-Institut de Chimie du CNRS (INC)-Université de Lille-Centre National de la Recherche Scientifique (CNRS), Instituto Federal do Rio Grande do Sul (IFRS), ANR-16-CE06-0013,NANO4FuT,Synthèse des carburants alternatifs et des molécules plateforme sur nanoréacteurs(2016), and Centrale Lille Institut (CLIL)-Université d'Artois (UA)-Centrale Lille-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Lille
Subjects: Nanocomposite, Materials science, 010405 organic chemistry, Mechanical Engineering, Nanoparticle, chemistry.chemical_element, Carbon nanotube, 010402 general chemistry, 01 natural sciences, 0104 chemical sciences, law.invention, Catalysis, Ruthenium, Metal, chemistry, Chemical engineering, Mechanics of Materials, law, visual_art, visual_art.visual_art_medium, [CHIM]Chemical Sciences, General Materials Science, Zeolite, ComputingMilieux_MISCELLANEOUS, Syngas
Abstract: The purpose of this work is the design of metal-zeolite nanocomposite catalysts for Fischer–Tropsch synthesis, containing ruthenium nanoparticles, uniformly distributed in the hierarchical BEA zeolites. The use of ruthenium avoids the formation of inert hardly reducible inert metal silicates and metal aluminates. Carbon nanotubes with supported metal oxide nanoparticles play the role of sacrificial template, which allows creating mesoporosity and bringing metallic functionality inside the zeolite matrix. Both mesoporosity and larger micropores of the BEA zeolite facilitate the localization of metal nanoparticles within the zeolite structure and diffusion of the reacting molecules. Compared to the conventional zeolite supported metal catalysts, the synthesized hierarchical ruthenium-zeolites exhibited much higher activity and lower methane selectivity in Fischer–Tropsch synthesis.
Published: 2021
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16. Iron and Copper Nanoparticles Inside and Outside Carbon Nanotubes: Nanoconfinement, Migration, Interaction and Catalytic Performance in Fischer-Tropsch Synthesis

Author: Ahmed Addad, Jingping Hong, Yuliia Kosto, Břetislav Šmíd, Gang Ji, Ana Katiuce Fellenberg, Andrei Y. Khodakov, Pardis Simon, Unité de Catalyse et Chimie du Solide - UMR 8181 (UCCS), Centrale Lille Institut (CLIL)-Université d'Artois (UA)-Centrale Lille-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Lille, Unité Matériaux et Transformations - UMR 8207 (UMET), Institut de Chimie du CNRS (INC)-Université de Lille-Centre National de la Recherche Scientifique (CNRS)-Institut National de Recherche pour l’Agriculture, l’Alimentation et l’Environnement (INRAE)-Centrale Lille Institut (CLIL), Kyung Hee University (KHU), Charles University [Prague] (CU), Université de Lille, CNRS, INRA, ENSCL, Unité Matériaux et Transformations - UMR 8207 [UMET], Unité de Catalyse et Chimie du Solide (UCCS) - UMR 8181, Unité Matériaux et Transformations (UMET) - UMR 8207, Central South University [Changsha], Charles University [Prague] [CU], Université d'Artois (UA)-Centrale Lille-Institut de Chimie du CNRS (INC)-Université de Lille-Centre National de la Recherche Scientifique (CNRS), and Centrale Lille-Institut de Chimie du CNRS (INC)-Université de Lille-Centre National de la Recherche Scientifique (CNRS)-Institut National de Recherche pour l’Agriculture, l’Alimentation et l’Environnement (INRAE)
Subjects: NAP-XPS, chemistry.chemical_element, 02 engineering and technology, Carbon nanotube, 010402 general chemistry, 7. Clean energy, 01 natural sciences, Catalysis, Fischer-Tropsch, law.invention, chemistry.chemical_compound, law, [CHIM]Chemical Sciences, Physical and Theoretical Chemistry, Bimetallic strip, nanoconfinement, iron carbide, Fischer–Tropsch process, promotion, syngas, 021001 nanoscience & nanotechnology, Copper, mobility, 0104 chemical sciences, chemistry, Chemical engineering, copper, 0210 nano-technology, Carbon, Syngas, Carbon monoxide
Abstract: International audience; Carbon materials have attracted increasing attention as supports for metal catalysts. Ironcontaining carbon nanotubes often promoted with copper have found application in Fischer-Tropsch synthesis, which provides an alternative way for conversion of renewable feedstocks to chemicals and fuels. In carbon nanotubes, the active phase can be nanoconfined inside the channels or localized on the outer surface. In most of previous work, the distribution of metal nanoparticles inside or outside carbon nanotubes is considered to be immobile during the catalyst activation or catalytic reaction. In this paper, we uncovered remarkable mobility of both iron and copper species in the bimetallic catalysts between inner carbon nanotube channels and outer surface, which occurs in carbon monoxide and syngas, while almost no migration of iron species proceeds in the monometallic catalysts. This mobility is enhanced by noticeable fragility and defects in carbon nanotubes, which appear on their impregnation with the acid solutions of metal precursors and precursor decomposition. Remarkable mobility of iron and copper species in bimetallic catalysts affects the genesis of iron active sites, and enhances interaction of iron with the promoter. In the bimetallic iron-copper catalysts, the major increase in the activity was attributed to higher reaction turnover frequency over iron surface sites located in a close proximity with copper.
Published: 2021
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17. Bismuth mobile promoter and cobalt-bismuth nanoparticles in carbon nanotube supported Fischer-Tropsch catalysts with enhanced stability

Author: Alan J. Barrios, Vitaly V. Ordomsky, Camille La Fontaine, Andrei Y. Khodakov, Bang Gu, Thobani G. Gambu, Siddardha Koneti, Mark Saeys, Deizi V. Peron, Simona Moldovan, Mykhailo Vorokhta, Břetislav Šmíd, Mirella Virginie, Valérie Briois, Unité de Catalyse et Chimie du Solide - UMR 8181 (UCCS), Centrale Lille Institut (CLIL)-Université d'Artois (UA)-Centrale Lille-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Lille, Synchrotron SOLEIL (SSOLEIL), Centre National de la Recherche Scientifique (CNRS), Charles University [Prague] (CU), Institut de Physique et Chimie des Matériaux de Strasbourg (IPCMS), Université de Strasbourg (UNISTRA)-Matériaux et nanosciences d'Alsace (FMNGE), Institut de Chimie du CNRS (INC)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS)-Réseau nanophotonique et optique, Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA), Groupe de physique des matériaux (GPM), Centre National de la Recherche Scientifique (CNRS)-Institut national des sciences appliquées Rouen Normandie (INSA Rouen Normandie), Institut National des Sciences Appliquées (INSA)-Normandie Université (NU)-Institut National des Sciences Appliquées (INSA)-Normandie Université (NU)-Université de Rouen Normandie (UNIROUEN), Normandie Université (NU), Université d'Artois (UA)-Centrale Lille-Institut de Chimie du CNRS (INC)-Université de Lille-Centre National de la Recherche Scientifique (CNRS), Université de Rouen Normandie (UNIROUEN), Normandie Université (NU)-Normandie Université (NU)-Institut national des sciences appliquées Rouen Normandie (INSA Rouen Normandie), Institut National des Sciences Appliquées (INSA)-Normandie Université (NU)-Institut National des Sciences Appliquées (INSA)-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche sur les Matériaux Avancés (IRMA), Université de Caen Normandie (UNICAEN), Normandie Université (NU)-Normandie Université (NU)-École Nationale Supérieure d'Ingénieurs de Caen (ENSICAEN), Normandie Université (NU)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université de Rouen Normandie (UNIROUEN), Normandie Université (NU)-Institut national des sciences appliquées Rouen Normandie (INSA Rouen Normandie), Institut National des Sciences Appliquées (INSA)-Normandie Université (NU)-Institut National des Sciences Appliquées (INSA)-Centre National de la Recherche Scientifique (CNRS)-Université de Caen Normandie (UNICAEN), Normandie Université (NU)-École Nationale Supérieure d'Ingénieurs de Caen (ENSICAEN), Normandie Université (NU)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Centre National de la Recherche Scientifique (CNRS), Laboratory for Chemical Technology, Universiteit Gent = Ghent University (UGENT), UCCS Équipe Catalyse Supramoléculaire, Université d'Artois (UA)-Centrale Lille-Institut de Chimie du CNRS (INC)-Université de Lille-Centre National de la Recherche Scientifique (CNRS)-Université d'Artois (UA)-Centrale Lille-Institut de Chimie du CNRS (INC)-Université de Lille-Centre National de la Recherche Scientifique (CNRS), Université de Strasbourg (UNISTRA)-Centre National de la Recherche Scientifique (CNRS)-Matériaux et nanosciences d'Alsace (FMNGE), and Institut de Chimie du CNRS (INC)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Réseau nanophotonique et optique
Subjects: Technology and Engineering, INITIO MOLECULAR-DYNAMICS, XAS, chemistry.chemical_element, Sintering, Nanoparticle, 02 engineering and technology, Carbon nanotube, REDUCIBILITY, 010402 general chemistry, RAY-ABSORPTION-SPECTROSCOPY, 7. Clean energy, 01 natural sciences, Catalysis, Fischer-Tropsch, law.invention, Bismuth, law, XPS, LIGHT OLEFINS, [CHIM]Chemical Sciences, Operando, Physical and Theoretical Chemistry, Bimetallic strip, ComputingMilieux_MISCELLANEOUS, Fischer–Tropsch process, Cobalt, 021001 nanoscience & nanotechnology, MULTIVARIATE CURVE RESOLUTION, 0104 chemical sciences, IRON CATALYSTS, MCR-ALS, chemistry, Chemical engineering, CO CATALYSTS, 0210 nano-technology, Stability, Liquid metals
Abstract: Metal nanoparticles on the surface of porous supports have found numerous applications in different areas of science. Fischer-Tropsch synthesis, which proceeds on the surface of cobalt metal nanoparticles, is an efficient way to convert renewables and fossil feedstocks into alternative fuels. The stability of cobalt catalysts is an essential and even crucial parameter and can be significantly improved by promotion. In this paper, a combination of operando Quick-XAS, NAP-XPS, high resolution electron microscopy imaging, DFT modeling alongside with Fischer-Tropsch catalytic experiments has provided deep insights into the evolution of bismuth promoter and structure of cobalt-bismuth nanoparticles in the catalysts supported by carbon nanotubes. We uncovered noticeable migration of metallic bismuth occurring during the reduction step, which leads to bismuth redispersion over the surface of cobalt nanoparticles. Cobalt reduction is facilitated in the presence of bismuth. The working Fischer-Tropsch catalyst contains cobalt-bismuth bimetallic nanoparticles, with bismuth located in the nanoparticle shell. The promotion with bismuth has resulted in a noticeable increase in catalyst stability. Characterization and DFT modeling suggest preferential localization of bismuth mobile promoter at the steps and edges of cobalt nanoparticles, which hinders cobalt sintering and carbon deposition and improves the catalyst stability.
Published: 2021
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18. Active phases for high temperature Fischer-Tropsch synthesis in the silica supported iron catalysts promoted with antimony and tin

Author: Joris W. Thybaut, Alan J. Barrios, Alan Taschin, Simona Moldovan, Andrei Y. Khodakov, Iulian Dugulan, Robert Wojcieszak, Mirella Virginie, Deizi V. Peron, Siddardha Koneti, Giulio Gorni, Carlo Marini, CNRS, Centrale Lille, ENSCL, Univ. Artois, Université de Lille, Unité de Catalyse et de Chimie du Solide (UCCS) - UMR 8181, Unité de Catalyse et Chimie du Solide (UCCS) - UMR 8181, Unité de Catalyse et Chimie du Solide - UMR 8181 (UCCS), Université d'Artois (UA)-Centrale Lille-Institut de Chimie du CNRS (INC)-Université de Lille-Centre National de la Recherche Scientifique (CNRS), and Centrale Lille Institut (CLIL)-Université d'Artois (UA)-Centrale Lille-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Lille
Subjects: inorganic chemicals, chemistry.chemical_element, Nanoparticle, 02 engineering and technology, 010402 general chemistry, 7. Clean energy, 01 natural sciences, Catalysis, Reaction rate, Antimony, [CHIM]Chemical Sciences, Bimetallic strip, ComputingMilieux_MISCELLANEOUS, General Environmental Science, organic chemicals, Process Chemistry and Technology, Fischer–Tropsch process, 021001 nanoscience & nanotechnology, 0104 chemical sciences, chemistry, Chemical engineering, 0210 nano-technology, Tin, biomass, syngas, Fischer-Tropsch, iron, promotion, Syngas
Abstract: Fischer-Tropsch synthesis provides an important opportunity for utilization of biomass and plastic waste. Iron catalysts are the catalysts of choice for light olefin synthesis using Fischer-Tropsch reaction. In this paper, we investigate strong promoting effects of antimony and tin on the catalytic performance of silica supported iron Fischer-Tropsch catalysts using a combination of advanced and in-situ techniques. The catalyst doping with these elements added via impregnation results in a major increase in the reaction rate and much better catalyst stability. No enhancement of iron dispersion was observed after the promotion, while somewhat higher extent of iron carbidization was observed in the antimony promoted catalysts. Iron-bismuth bimetallic nanoparticles are detected by several techniques. In the working catalysts, the promoters are located in close proximity to the iron nanoparticles. The promotion leads to the 7–10 times increase in the intrinsic activity of iron surface sites due to their interaction with the promoters. 292
Published: 2021
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19. Selective Deposition of Cobalt and Copper Oxides on BiVO 4 Facets for Enhancement of CO 2 Photocatalytic Reduction to Hydrocarbons

Author: Andrei Y. Khodakov, Vitaly V. Ordomsky, Xiang Yu, Unité de Catalyse et Chimie du Solide - UMR 8181 (UCCS), Centrale Lille Institut (CLIL)-Université d'Artois (UA)-Centrale Lille-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Lille, Eco-Efficient Products &Processes Laboratory (E2PL2), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-RHODIA, Université d'Artois (UA)-Centrale Lille-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Lille, Université d'Artois (UA)-Centrale Lille-Institut de Chimie du CNRS (INC)-Université de Lille-Centre National de la Recherche Scientifique (CNRS), Eco-Efficient Products & Processes Laboratory (E2P2L), and RHODIA-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)
Subjects: Materials science, Inorganic chemistry, chemistry.chemical_element, 02 engineering and technology, 010402 general chemistry, 01 natural sciences, 7. Clean energy, Catalysis, Inorganic Chemistry, Reduction (complexity), chemistry.chemical_compound, [CHIM]Chemical Sciences, Physical and Theoretical Chemistry, ComputingMilieux_MISCELLANEOUS, Organic Chemistry, [CHIM.MATE]Chemical Sciences/Material chemistry, [CHIM.CATA]Chemical Sciences/Catalysis, 021001 nanoscience & nanotechnology, Selective deposition, Copper, 0104 chemical sciences, chemistry, Bismuth vanadate, Photocatalysis, 0210 nano-technology, Cobalt
Abstract: International audience; The nanostructure of a semiconductor is a crucial parameter for efficient photocatalytic performance. Hereby, we have synthesized monoclinic bismuth vanadate (BiVO4) crystals with controlled ratio of {010} and {110} facets. The selective deposition of CuOx and CoOx over {010} and {110} facets has been performed using photo-reduction and photo-oxidation methods, respectively. It resulted in a highly efficient charge separation of photogenerated electrons and holes and enhancement of the photocatalytic reduction of CO2 by H2O into hydrocarbons, including CH4, C2H6 and C3H8. The controlled co-catalyst deposition over different semiconductor facets provides a strategy for the synthesis of hydrocarbons from CO2 and H2O by efficient charge separation.
Published: 2020
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20. The Fischer–Tropsch reaction in the aqueous phase over rhodium catalysts: a promising route to selective synthesis and separation of oxygenates and hydrocarbons

Author: Alan J. Barrios, Vitaly V. Ordomsky, Andrei Y. Khodakov, Nataliya E. Borisova, Aleksandra S. Peregudova, Unité de Catalyse et Chimie du Solide - UMR 8181 (UCCS), Centrale Lille Institut (CLIL)-Université d'Artois (UA)-Centrale Lille-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Lille, Université d'Artois (UA)-Centrale Lille-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Lille, Université d'Artois (UA)-Centrale Lille-Institut de Chimie du CNRS (INC)-Université de Lille-Centre National de la Recherche Scientifique (CNRS), and ANR-16-CE06-0013,NANO4FuT,Synthèse des carburants alternatifs et des molécules plateforme sur nanoréacteurs(2016)
Subjects: chemistry.chemical_element, Alcohol, 02 engineering and technology, 010402 general chemistry, 01 natural sciences, Catalysis, Rhodium, Metal, chemistry.chemical_compound, Materials Chemistry, [CHIM]Chemical Sciences, ComputingMilieux_MISCELLANEOUS, Oxygenate, Metals and Alloys, Aqueous two-phase system, Fischer–Tropsch process, [CHIM.CATA]Chemical Sciences/Catalysis, General Chemistry, 021001 nanoscience & nanotechnology, Combinatorial chemistry, 0104 chemical sciences, Surfaces, Coatings and Films, Electronic, Optical and Magnetic Materials, chemistry, visual_art, Ceramics and Composites, visual_art.visual_art_medium, 0210 nano-technology, Selectivity
Abstract: In the present communication, we uncovered the aqueous phase Fischer-Tropsch reaction over rhodium catalysts. The reaction results in the synthesis and consecutive separation of hydrocarbons and oxygenates into two phases. Use of a rhodium Schiff base complex as a precursor for catalyst preparation allows efficient control of the Rh metal nanoparticle size distribution and leads to higher alcohol selectivity.
Published: 2020
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21. Alcohol amination over titania-supported ruthenium nanoparticles

Author: Zhen Yan, Vitaly V. Ordomsky, Feng Niu, Andrei Y. Khodakov, Bright T. Kusema, and Shaohua Xie
Subjects: chemistry.chemical_compound, Ammonia, Chemical engineering, chemistry, Nanoparticle, chemistry.chemical_element, Alcohol, Amine gas treating, Selectivity, Catalysis, Amination, Ruthenium
Abstract: Metal nanoparticles for heterogeneous catalytic reactions are often supported on porous materials. The catalytic performance of supported catalysts usually depends on the size of the metal nanoparticles and catalytic supports. Selective synthesis of valuable primary amines is an important target in the modern industry. In this work, the catalytic performance of TiO2 supported Ru nanoparticles with sizes from 1.4 to 9.9 nm was investigated in both direct gas-phase amination of 1-butanol and liquid-phase amination of 1-octanol into primary amines in the presence of ammonia. Our results suggest that ruthenium nanoparticle size is one of the most important parameters, which affects the catalytic performance of titania supported catalysts in the amination reactions. The selectivity to primary amines is much higher over smaller supported Ru nanoparticles than over larger ones, especially in the liquid-phase amination of 1-octanol. The 95% selectivity to octylamine is obtained over small supported Ru nanoparticles with a diameter of 1.4 nm even at 95% conversion, whereas for larger Ru nanoparticles, the octylamine selectivity drops as the 1-octanol conversion approached 80–90%. The drop of the selectivity to octylamine at higher conversion is due to the increase in the intrinsic rate of octylamine coupling over larger ruthenium nanoparticles. The support can also contribute to some extent to the rate of primary amine self-coupling, while its effect on the overall catalytic performance is not significant for the titania-supported catalysts.
Published: 2020
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22. Mobility and versatility of the liquid bismuth promoter in the working iron catalysts for light olefin synthesis from syngas

Author: Mykhailo Vorokhta, Alan J. Barrios, Mounib Bahri, Bang Gu, Andrei Y. Khodakov, Ovidiu Ersen, Eric Marceau, Robert Wojcieszak, Vitaly V. Ordomsky, Deizi V. Peron, Dipanjan Banerjee, Břetislav Šmíd, Mirella Virginie, Unité de Catalyse et Chimie du Solide - UMR 8181 (UCCS), Centrale Lille Institut (CLIL)-Université d'Artois (UA)-Centrale Lille-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Lille, Institut de Physique et Chimie des Matériaux de Strasbourg (IPCMS), Université Louis Pasteur - Strasbourg I-Centre National de la Recherche Scientifique (CNRS), Laboratoire de photonique et de nanostructures (LPN), Centre National de la Recherche Scientifique (CNRS), Université de Strasbourg (UNISTRA)-Matériaux et nanosciences d'Alsace (FMNGE), Institut de Chimie du CNRS (INC)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS)-Réseau nanophotonique et optique, Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA), Institute of Resource Ecology [Dresden], Helmholtz-Zentrum Dresden-Rossendorf (HZDR), Laboratoire de Réactivité de Surface (LRS), Université Pierre et Marie Curie - Paris 6 (UPMC)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Université d'Artois (UA)-Centrale Lille-Institut de Chimie du CNRS (INC)-Université de Lille-Centre National de la Recherche Scientifique (CNRS), Université de Strasbourg (UNISTRA)-Centre National de la Recherche Scientifique (CNRS)-Matériaux et Nanosciences Grand-Est (MNGE), Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Réseau nanophotonique et optique, Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Centre National de la Recherche Scientifique (CNRS), Charles University [Prague] (CU), European Synchroton Radiation Facility [Grenoble] (ESRF), ANR-16-CE06-0013,NANO4FuT,Synthèse des carburants alternatifs et des molécules plateforme sur nanoréacteurs(2016), Université de Lille, CNRS, Centrale Lille, ENSCL, Univ. Artois, Unité de Catalyse et Chimie du Solide - UMR 8181 [UCCS], Institut de Physique et Chimie des Matériaux de Strasbourg [IPCMS], and Université d'Artois (UA)-Centrale Lille-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Lille
Subjects: MECHANISM, inorganic chemicals, Materials science, FISCHER-TROPSCH SYNTHESIS, Chemistry, Multidisciplinary, chemistry.chemical_element, 02 engineering and technology, Carbon nanotube, 010402 general chemistry, CARBON NANOTUBES, 01 natural sciences, Catalysis, Bismuth, law.invention, ACTIVATION, Reaction rate, chemistry.chemical_compound, Adsorption, law, NANOPARTICLES, HYDROGENATION, KINETICS, ComputingMilieux_MISCELLANEOUS, Olefin fiber, Science & Technology, SPECTROSCOPY, HETEROGENEOUS CATALYSTS, [CHIM.MATE]Chemical Sciences/Material chemistry, [CHIM.CATA]Chemical Sciences/Catalysis, General Chemistry, 021001 nanoscience & nanotechnology, 0104 chemical sciences, CO, Chemistry, chemistry, Chemical engineering, Physical Sciences, 0210 nano-technology, Syngas, Carbon monoxide
Abstract: Localization and migration of highly mobile and extremely efficient bismuth promoter in iron Fischer–Tropsch catalysts were elucidated using in situ methods., Liquid metals are a new emerging and rapidly growing class of materials and can be considered as efficient promoters and active phases for heterogeneous catalysts for sustainable processes. Because of low cost, high selectivity and flexibility, iron-based catalysts are the catalysts of choice for light olefin synthesis via Fischer–Tropsch reaction. Promotion of iron catalysts supported by carbon nanotubes with bismuth, which is liquid under the reaction conditions, results in a several fold increase in the reaction rate and in a much higher light olefin selectivity. In order to elucidate the spectacular enhancement of the catalytic performance, we conducted extensive in-depth characterization of the bismuth-promoted iron catalysts under the reacting gas and reaction temperatures by a combination of cutting-edge in situ techniques: in situ scanning transmission electron microscopy, near-atmospheric pressure X-ray photoelectron spectroscopy and in situ X-ray adsorption near edge structure. In situ scanning transmission electron microscopy conducted under atmospheric pressure of carbon monoxide at the temperature of catalyst activation showed iron sintering proceeding via the particle migration and coalescence mechanism. Catalyst activation in carbon monoxide and in syngas leads to liquid bismuth metallic species, which readily migrate over the catalyst surface with the formation of larger spherical bismuth droplets and iron–bismuth core–shell structures. In the working catalysts, during Fischer–Tropsch synthesis, metallic bismuth located at the interface of iron species undergoes continuous oxidation and reduction cycles, which facilitate carbon monoxide dissociation and result in the substantial increase in the reaction rate.
Published: 2020
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23. External surface phenomena in dealumination and desilication of large single crystals of ZSM-5 zeolite synthesized from a sustainable source

Author: Vladimir L. Zholobenko, Michèle Oberson de Souza, Nilson Romeu Marcilio, Deizi V. Peron, Liliana Amaral Féris, Nicolas Nuns, James Henrique dos Santos de Melo, Andrei Y. Khodakov, Vitaly V. Ordomsky, Mickaël Capron, Unité de Catalyse et Chimie du Solide - UMR 8181 (UCCS), Centrale Lille Institut (CLIL)-Université d'Artois (UA)-Centrale Lille-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Lille, Keele University [Keele], Université d'Artois (UA)-Centrale Lille-Institut de Chimie du CNRS (INC)-Université de Lille-Centre National de la Recherche Scientifique (CNRS), ANR-16-CE06-0013,NANO4FuT,Synthèse des carburants alternatifs et des molécules plateforme sur nanoréacteurs(2016), and Université d'Artois (UA)-Centrale Lille-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Lille
Subjects: Materials science, Oxalic acid, 02 engineering and technology, 010402 general chemistry, 01 natural sciences, chemistry.chemical_compound, [CHIM.GENI]Chemical Sciences/Chemical engineering, Adsorption, [CHIM]Chemical Sciences, QD, General Materials Science, Zeolite, ComputingMilieux_MISCELLANEOUS, [CHIM.CATA]Chemical Sciences/Catalysis, [CHIM.MATE]Chemical Sciences/Material chemistry, General Chemistry, 021001 nanoscience & nanotechnology, Condensed Matter Physics, Alkali metal, Anisole, 0104 chemical sciences, chemistry, Chemical engineering, Mechanics of Materials, Sodium hydroxide, Crystallite, 0210 nano-technology, Mesoporous material
Abstract: Zeolite dealumination and desilication are common methods, which improve accessibility of the active sites located inside the zeolite crystallites and tune the zeolite acidity. The exact mechanism of these post-synthesis zeolite treatments remains under discussion. In this paper, a series of dealuminated and desilicated ZSM-5 zeolites are prepared using single or combined post-synthesis dealumination and desilication of large zeolite single crystals with oxalic acid and sodium hydroxide. The ZSM-5 zeolite has been synthesized using silica extracted from fly ash. Zeolite desilication results in the potholes, leaf-type structures and other clearly visible defects on the surface of zeolite crystallites, while the effect of dealumination is less pronounced. The low temperature nitrogen adsorption suggests the formation of mesopores in the zeolites formed by the voids between and in the irregular zeolite crystallites produced during post-synthesis treatments. 27Al and 29Si MAS NMR in combination with XRD data are indicative of only minor modifications of the bulk zeolite structure during dealumination and desilication. The total Bronsted acidity only slightly decreases and is not affected by the type of zeolite post-synthesis treatment. After desilication of large single crystals of ZSM-5, noticeable enhancement of the Bronsted acidity on the zeolite external surface has been detected by FTIR of adsorbed collidine. The zeolites with higher acidity on the external surface have shown higher activity in the anisole acylation with hexanoic acid. A combination of characterization techniques suggests that the dealumination and desilication of the large crystals of ZSM-5 zeolite using post-synthesis treatments respectively with acid and alkali selectively starts at the zeolite external surface.
Published: 2019
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24. Multi-output machine learning models for kinetic data evaluation : A Fischer–Tropsch synthesis case study

Author: Anoop Chakkingal, Pieter Janssens, Jeroen Poissonnier, Mirella Virginie, Andrei Y. Khodakov, Joris W. Thybaut, Centrale Lille, Laboratory for Chemical Technology, Universiteit Gent = Ghent University (UGENT), Unité de Catalyse et Chimie du Solide - UMR 8181 (UCCS), and Université d'Artois (UA)-Centrale Lille-Institut de Chimie du CNRS (INC)-Université de Lille-Centre National de la Recherche Scientifique (CNRS)
Subjects: General Chemical Engineering, [CHIM]Chemical Sciences, Environmental Chemistry, [INFO]Computer Science [cs], General Chemistry, Industrial and Manufacturing Engineering
Abstract: International audience
Published: 2022
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25. Highlights and challenges in the selective reduction of carbon dioxide to methanol

Author: Sara Navarro-Jaén, Julien Bonin, Marc Robert, Mirella Virginie, Andrei Y. Khodakov, Robert Wojcieszak, Unité de Catalyse et Chimie du Solide - UMR 8181 (UCCS), Université d'Artois (UA)-Centrale Lille-Institut de Chimie du CNRS (INC)-Université de Lille-Centre National de la Recherche Scientifique (CNRS), Laboratoire d'Electrochimie Moléculaire (LEM (UMR_7591)), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Paris Cité (UPCité), Centrale Lille Institut (CLIL)-Université d'Artois (UA)-Centrale Lille-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Lille, and Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université de Paris (UP)
Subjects: General Chemical Engineering, Homogeneous catalysis, 02 engineering and technology, 010402 general chemistry, Heterogeneous catalysis, Electrocatalyst, 01 natural sciences, 7. Clean energy, 12. Responsible consumption, Catalysis, chemistry.chemical_compound, electrocatalysis, [CHIM]Chemical Sciences, Selective reduction, methanol, catalysis, Chemistry, General Chemistry, 021001 nanoscience & nanotechnology, 0104 chemical sciences, 13. Climate action, CO2 reduction, Greenhouse gas, Photocatalysis, Methanol, Biochemical engineering, 0210 nano-technology, photocatalysis
Abstract: Carbon dioxide (CO2) is the iconic greenhouse gas and the major factor driving present global climate change, incentivizing its capture and recycling into valuable products and fuels. The 6H+/6e− reduction of CO2 affords CH3OH, a key compound that is a fuel and a platform molecule. In this Review, we compare different routes for CO2 reduction to CH3OH, namely, heterogeneous and homogeneous catalytic hydrogenation, as well as enzymatic catalysis, photocatalysis and electrocatalysis. We describe the leading catalysts and the conditions under which they operate, and then consider their advantages and drawbacks in terms of selectivity, productivity, stability, operating conditions, cost and technical readiness. At present, heterogeneous hydrogenation catalysis and electrocatalysis have the greatest promise for large-scale CO2 reduction to CH3OH. The availability and price of sustainable electricity appear to be essential prerequisites for efficient CH3OH synthesis. This Review identifies competitive advantages and drawbacks of heterogeneous and homogeneous catalytic hydrogenation, as well as enzymatic catalysis, photocatalysis and electrocatalysis, for CO2 reduction to methanol.
Published: 2021
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26. Surface molecular imprinting over supported metal catalysts for size-dependent selective hydrogenation reactions

Author: Vitaly V. Ordomsky, Olga V. Safonova, Willinton Y. Hernández, Dan Wu, Ahmed Addad, Andrei Y. Khodakov, Evgeny I. Vovk, Walid Baaziz, Bang Gu, Maya Marinova, Ovidiu Ersen, Nicolas Nuns, Wen-Juan Zhou, Unité de Catalyse et Chimie du Solide - UMR 8181 (UCCS), Université d'Artois (UA)-Centrale Lille-Institut de Chimie du CNRS (INC)-Université de Lille-Centre National de la Recherche Scientifique (CNRS), Institut de chimie et procédés pour l'énergie, l'environnement et la santé (ICPEES), Université de Strasbourg (UNISTRA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Matériaux et Nanosciences Grand-Est (MNGE), Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS), Institut Michel Eugène Chevreul - FR 2638 (IMEC), Université d'Artois (UA)-Centrale Lille-Institut de Chimie du CNRS (INC)-Université de Lille-Centre National de la Recherche Scientifique (CNRS)-Institut National de Recherche pour l’Agriculture, l’Alimentation et l’Environnement (INRAE), Eco-Efficient Products & Processes Laboratory (E2P2L), RHODIA-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Laboratoire de Chimie - UMR5182 (LC), École normale supérieure de Lyon (ENS de Lyon)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Institut de Physique et Chimie des Matériaux de Strasbourg (IPCMS), Université de Strasbourg (UNISTRA)-Centre National de la Recherche Scientifique (CNRS)-Matériaux et Nanosciences Grand-Est (MNGE), Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Réseau nanophotonique et optique, Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Centre National de la Recherche Scientifique (CNRS), Paul Scherrer Institute (PSI), Unité Matériaux et Transformations - UMR 8207 (UMET), Centrale Lille-Institut de Chimie du CNRS (INC)-Université de Lille-Centre National de la Recherche Scientifique (CNRS)-Institut National de Recherche pour l’Agriculture, l’Alimentation et l’Environnement (INRAE), Centrale Lille Institut (CLIL)-Université d'Artois (UA)-Centrale Lille-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Lille, Université de Strasbourg (UNISTRA)-Matériaux et nanosciences d'Alsace (FMNGE), Institut de Chimie du CNRS (INC)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS), Université d'Artois (UA)-Institut de Chimie du CNRS (INC)-Université de Lille-Centre National de la Recherche Scientifique (CNRS)-Institut National de Recherche pour l’Agriculture, l’Alimentation et l’Environnement (INRAE)-Centrale Lille Institut (CLIL), Eco-Efficient Products &Processes Laboratory (E2PL2), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-RHODIA, Centre National de la Recherche Scientifique (CNRS)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-École normale supérieure - Lyon (ENS Lyon)-Institut de Chimie du CNRS (INC), Institut de Chimie du CNRS (INC)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS)-Réseau nanophotonique et optique, Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA), and Institut de Chimie du CNRS (INC)-Institut National de la Recherche Agronomique (INRA)-Centre National de la Recherche Scientifique (CNRS)-Université de Lille-Ecole Nationale Supérieure de Chimie de Lille (ENSCL)
Subjects: Steric effects, chemistry.chemical_classification, Chemistry, Process Chemistry and Technology, Bioengineering, 02 engineering and technology, Polymer, 010402 general chemistry, 021001 nanoscience & nanotechnology, Heterogeneous catalysis, 01 natural sciences, Biochemistry, Combinatorial chemistry, Catalysis, 0104 chemical sciences, Adsorption, Molecule, [CHIM]Chemical Sciences, 0210 nano-technology, Selectivity, Molecular imprinting, ComputingMilieux_MISCELLANEOUS
Abstract: Molecular imprinting of polymer matrices enables the creation of template-shaped cavities with high affinity for molecules of given shape and size. Here we introduce a surface molecular imprinting strategy to control the hydrogenation selectivity of various aromatic molecules over a supported palladium catalyst. This strategy involves the sequential adsorption over the metal surface of an aromatic template molecule followed by poisoners, resulting in the formation of non-poisoned active islands of predetermined shape and size. Because of steric constraints, these active islands exhibit high selectivity in the chemical conversion of aromatic molecules that correspond in size and shape to the templates. The elaborated strategy enables a practical application relevant to selective hydrogenation and removal of carcinogenic benzene from mixtures of aromatics. Molecular imprinting can facilitate size- and shape-selective reactions beyond traditional approaches based on porous materials, but is still not fully established for heterogeneous catalysts. Here a molecular imprinting approach is introduced to generate a supported palladium catalyst for the selective hydrogenation of benzene from mixtures of aromatic molecules.
Published: 2021
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27. Lignin Compounds to Monoaromatics: Selective Cleavage of C−O Bonds over a Brominated Ruthenium Catalyst

Author: Deizi V. Peron, Vitaly V. Ordomsky, Wen-Juan Zhou, Andrei Y. Khodakov, Maya Marinova, Zhen Yan, Dan Wu, Olga V. Safonova, Qiyan Wang, Unité de Catalyse et Chimie du Solide - UMR 8181 (UCCS), Université d'Artois (UA)-Centrale Lille-Institut de Chimie du CNRS (INC)-Université de Lille-Centre National de la Recherche Scientifique (CNRS), Eco-Efficient Products & Processes Laboratory (E2P2L), RHODIA-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Paul Scherrer Institute (PSI), Laboratoire de Chimie - UMR5182 (LC), École normale supérieure de Lyon (ENS de Lyon)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Institut Michel Eugène Chevreul - FR 2638 (IMEC), Université d'Artois (UA)-Centrale Lille-Institut de Chimie du CNRS (INC)-Université de Lille-Centre National de la Recherche Scientifique (CNRS)-Institut National de Recherche pour l’Agriculture, l’Alimentation et l’Environnement (INRAE), Centrale Lille Institut (CLIL)-Université d'Artois (UA)-Centrale Lille-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Lille, Eco-Efficient Products &Processes Laboratory (E2PL2), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-RHODIA, Centre National de la Recherche Scientifique (CNRS)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-École normale supérieure - Lyon (ENS Lyon)-Institut de Chimie du CNRS (INC), Université d'Artois (UA)-Institut de Chimie du CNRS (INC)-Université de Lille-Centre National de la Recherche Scientifique (CNRS)-Institut National de Recherche pour l’Agriculture, l’Alimentation et l’Environnement (INRAE)-Centrale Lille Institut (CLIL), The Swiss Light Source (SLS) (SLS-PSI), Unité Matériaux et Transformations - UMR 8207 (UMET), and Centrale Lille-Institut de Chimie du CNRS (INC)-Université de Lille-Centre National de la Recherche Scientifique (CNRS)-Institut National de Recherche pour l’Agriculture, l’Alimentation et l’Environnement (INRAE)
Subjects: Depolymerization, 010405 organic chemistry, Aryl, Diphenyl ether, Aromaticity, General Chemistry, General Medicine, Heterogeneous catalysis, 010402 general chemistry, 01 natural sciences, Catalysis, 3. Good health, 0104 chemical sciences, chemistry.chemical_compound, chemistry, Polymer chemistry, [CHIM]Chemical Sciences, Benzene, Bond cleavage, ComputingMilieux_MISCELLANEOUS
Abstract: The cleavage of C-O linkages in aryl ethers in biomass-derived lignin compounds without hydrogenation of the aromatic rings is a major challenge for the production of sustainable mono-aromatics. Conventional strategies over the heterogeneous metal catalysts require the addition of homogeneous base additives causing environmental problems. Herein, we propose a heterogeneous Ru/C catalyst modified by Br atoms for the selective direct cleavage of C-O bonds in diphenyl ether without hydrogenation of aromatic rings reaching the yield of benzene and phenol as high as 90.3 % and increased selectivity to mono-aromatics (97.3 vs. 46.2 % for initial Ru) during depolymerization of lignin. Characterization of the catalyst indicates selective poisoning by Br of terrace sites over Ru nanoparticles, which are active in the hydrogenation of aromatic rings, while the defect sites on the edges and corners remain available and provide higher intrinsic activity in the C-O bond cleavage.
Published: 2021
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28. Embryonic zeolites for highly efficient synthesis of dimethyl ether from syngas

Author: Andrei Y. Khodakov, Vitaly V. Ordomsky, Sara Navarro Jaén, Dan Wu, Ana Palčić, Valentin Valtchev, Evgeny A. Pidko, Chong Liu, Mengdie Cai, Unité de Catalyse et Chimie du Solide - UMR 8181 (UCCS), Université d'Artois (UA)-Centrale Lille-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Lille, Ruđer Bošković Institute (IRB), Delft University of Technology (TU Delft), Laboratoire catalyse et spectrochimie (LCS), Centre National de la Recherche Scientifique (CNRS)-École Nationale Supérieure d'Ingénieurs de Caen (ENSICAEN), Normandie Université (NU)-Normandie Université (NU)-Institut de Chimie du CNRS (INC)-Université de Caen Normandie (UNICAEN), Normandie Université (NU), Université d'Artois (UA)-Centrale Lille-Institut de Chimie du CNRS (INC)-Université de Lille-Centre National de la Recherche Scientifique (CNRS), Université de Caen Normandie (UNICAEN), Normandie Université (NU)-Normandie Université (NU)-École Nationale Supérieure d'Ingénieurs de Caen (ENSICAEN), Normandie Université (NU)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), ANR-16-CE06-0013,NANO4FuT,Synthèse des carburants alternatifs et des molécules plateforme sur nanoréacteurs(2016), and Centrale Lille Institut (CLIL)-Université d'Artois (UA)-Centrale Lille-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Lille
Subjects: Embryonic zeolite, acid sites, DME synthesis, syngas, MFI-type zeolite, 02 engineering and technology, 010402 general chemistry, 01 natural sciences, Catalysis, chemistry.chemical_compound, Acid sites, Pyridine, [CHIM]Chemical Sciences, General Materials Science, Dimethyl ether, Zeolite, ComputingMilieux_MISCELLANEOUS, General Chemistry, [CHIM.MATE]Chemical Sciences/Material chemistry, 021001 nanoscience & nanotechnology, Condensed Matter Physics, Syngas, 0104 chemical sciences, chemistry, Chemical engineering, Mechanics of Materials, Methanol, 0210 nano-technology, Selectivity, Brønsted–Lowry acid–base theory
Abstract: International audience; Embryonic X-ray amorphous semi-formed MFI-type zeolite units mixed with the Cu–Zn–Al catalyst have been used for the direct synthesis of dimethyl ether (DME) from syngas. The hybrid catalyst with embryonic zeolite (EZ) with the particle size of 5 nm has demonstrated superior performance in terms of activity, selectivity, and stability compared to the crystalline ZSM-5 zeolite counterpart and the amorphous aluminosilicate material. The FTIR pyridine adsorption uncovered several types of active sites in EZ, including Brønsted acid sites of medium strength. The DFT modeling pointed out the key role of defect sites leading to lower strength of the acid sites in the embryonic MFI zeolite in comparison with the fully crystalline material. The effect of embryonic zeolite on the DME synthesis has been assigned to enhanced transport of methanol from Cu to ultra-small zeolite precursor units with moderate acidity, hence promoting the efficient dehydration to DME with high selectivity and stability.
Published: 2021
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29. Preparation of alumina based tubular asymmetric membranes incorporated with coal fly ash by centrifugal casting

Author: Melissa Rodrigues de la Rocha, Nilson Romeu Marcilio, Isabel Cristina Tessaro, Mirella Virginie, Liliane Damaris Pollo, Andrei Y. Khodakov, Unité de Catalyse et Chimie du Solide - UMR 8181 (UCCS), Université d'Artois (UA)-Centrale Lille-Institut de Chimie du CNRS (INC)-Université de Lille-Centre National de la Recherche Scientifique (CNRS), and Centrale Lille Institut (CLIL)-Université d'Artois (UA)-Centrale Lille-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Lille
Subjects: Materials science, Scanning electron microscope, Sintering, 02 engineering and technology, 01 natural sciences, 12. Responsible consumption, Centrifugal casting (industrial), 0103 physical sciences, Materials Chemistry, [CHIM]Chemical Sciences, Ceramic, Porosity, ComputingMilieux_MISCELLANEOUS, 010302 applied physics, Process Chemistry and Technology, Green body, 021001 nanoscience & nanotechnology, 6. Clean water, Surfaces, Coatings and Films, Electronic, Optical and Magnetic Materials, Membrane, Chemical engineering, Fly ash, visual_art, Ceramics and Composites, visual_art.visual_art_medium, 0210 nano-technology
Abstract: Design of new efficient membranes from sustainable sources such as coal fly ash (CFA) has been receiving rapidly growing attention. In the present work, alumina-based tubular asymmetric membranes were incorporated with different amounts of CFA using the centrifugal casting technique. The amount of CFA added to the matrix of the alumina tubes was varied from 10 to 40 wt% on a dry weight basis. The development of the ceramic membranes containing CFA comprised the following steps: raw materials dispersion, membrane preparation by centrifugal casting using high-speed mold rotation, drying of the green body followed by sintering at 1200 °C. The techniques used for membrane characterization included measuring mechanical strength, apparent porosity, morphology by scanning electron microscopy, linear shrinkage, hydraulic performance, and cornstarch retention. High CFA fraction in the alumina-based membranes resulted in higher porosity and higher water permeability, accompanied by a decrease in mechanical strength and linear shrinkage. The observed permeate flux was between 116 and 370 L m−2 h−1 bar−1, and the observed retention was above 99% for all the membranes tested. The addition of CFA for the preparation of asymmetric tubular membranes based on alumina allows utilization of industrial waste, reduces the cost and is interesting from both an economic and environmental points of view. These membranes have the potential for applications such as wastewater treatment and as a support for selective layer coatings.
Published: 2020
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30. Identification of efficient promoters and selectivity trends in high temperature Fischer-Tropsch synthesis over supported iron catalysts

Author: Andrei Y. Khodakov, Petr A. Chernavskii, Robert Wojcieszak, Joris W. Thybaut, Alan J. Barrios, Vitaly V. Ordomsky, Yuan Luo, Mirella Virginie, Bang Gu, Deizi-Vanessa Peron, Université de Lille, CNRS, Centrale Lille, ENSCL, Univ. Artois, Unité de Catalyse et Chimie du Solide - UMR 8181 [UCCS], Lomonosov Moscow State University [MSU], ND Zelinsky Institute of Organic Chemistry [Moscow, Russia], Universiteit Gent = Ghent University [UGENT], Unité de Catalyse et Chimie du Solide - UMR 8181 (UCCS), Centrale Lille Institut (CLIL)-Université d'Artois (UA)-Centrale Lille-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Lille, Universiteit Gent = Ghent University [Belgium] (UGENT), Université d'Artois (UA)-Centrale Lille-Institut de Chimie du CNRS (INC)-Université de Lille-Centre National de la Recherche Scientifique (CNRS), and Universiteit Gent = Ghent University (UGENT)
Subjects: Olefin fiber, Process Chemistry and Technology, Inorganic chemistry, chemistry.chemical_element, Fischer–Tropsch process, 02 engineering and technology, [CHIM.CATA]Chemical Sciences/Catalysis, [CHIM.MATE]Chemical Sciences/Material chemistry, 010402 general chemistry, 021001 nanoscience & nanotechnology, 01 natural sciences, Catalysis, 0104 chemical sciences, Bismuth, Renewable fuels, Fischer-Tropsch, Iron catalysts, Promotion, High throughput, Light olefins, chemistry, Transition metal, Antimony, [CHIM]Chemical Sciences, 0210 nano-technology, Selectivity, Tin, ComputingMilieux_MISCELLANEOUS, General Environmental Science
Abstract: In this work, 29 elements were evaluated as promoters for silica supported iron catalysts for high temperature Fischer-Tropsch synthesis using a high-throughput experimentation unit. The selected promoters include alkali/alkaline metals, transition metals, precious metals and lanthanides. Several general selectivity trends were observed and discussed. The selectivity enhancement to light olefins requires maintaining low selectivity to methane and light paraffins and at the same time, slowing the chain growth to the C5+ hydrocarbons. A major increase in Fischer-Tropsch rate principally due to higher intrinsic site activity, was observed over the catalysts promoted with metals with low melting points such as tin, antimony, bismuth and lead. These promoted catalysts also exhibited better stability. The effect of the promotion with tin and antimony on the olefin selectivity was not noticeable, while the presence of bismuth and lead results in the major enhancement of the selectivity to light olefins, lower methane and C2-C4 paraffin selectivities.
Published: 2020
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31. Disassembly of Supported Co and Ni Nanoparticles by Carbon Deposition for the Synthesis of Highly Dispersed and Active Catalysts

Author: Vitaly V. Ordomsky, Feng Niu, Bright T. Kusema, Ovidiu Ersen, Mounib Bahri, Andrei Y. Khodakov, Zhen Yan, Eco-Efficient Products & Processes Laboratory (E2P2L), RHODIA-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Institut de Physique et Chimie des Matériaux de Strasbourg (IPCMS), Université de Strasbourg (UNISTRA)-Centre National de la Recherche Scientifique (CNRS)-Matériaux et Nanosciences Grand-Est (MNGE), Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Réseau nanophotonique et optique, Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Centre National de la Recherche Scientifique (CNRS), Unité de Catalyse et Chimie du Solide - UMR 8181 (UCCS), Université d'Artois (UA)-Centrale Lille-Institut de Chimie du CNRS (INC)-Université de Lille-Centre National de la Recherche Scientifique (CNRS), Eco-Efficient Products &Processes Laboratory (E2PL2), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-RHODIA, Université de Strasbourg (UNISTRA)-Matériaux et nanosciences d'Alsace (FMNGE), Institut de Chimie du CNRS (INC)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS)-Réseau nanophotonique et optique, Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA), Centrale Lille Institut (CLIL)-Université d'Artois (UA)-Centrale Lille-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Lille, and Université d'Artois (UA)-Centrale Lille-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Lille
Subjects: inorganic chemicals, Materials science, 010405 organic chemistry, business.industry, Precipitation (chemistry), organic chemicals, chemistry.chemical_element, Nanoparticle, General Chemistry, Chemical industry, 010402 general chemistry, 01 natural sciences, Catalysis, 0104 chemical sciences, Carbon deposition, Nickel, chemistry, Chemical engineering, [CHIM]Chemical Sciences, heterocyclic compounds, business, Cobalt, ComputingMilieux_MISCELLANEOUS
Abstract: Supported cobalt and nickel nanoparticles are commonly used as catalysts in the modern chemical industry. Traditional methods of catalyst preparation such as impregnation or precipitation lead to f...
Published: 2020
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32. Tuning the Metal–Support Interaction and Enhancing the Stability of Titania-Supported Cobalt Fischer–Tropsch Catalysts via Carbon Nitride Coating

Author: Andrei Y. Khodakov, Jinlin Li, Jingping Hong, Ning Wang, Guiqin Xiao, Bo Wang, Yuhua Zhang, Unité de Catalyse et Chimie du Solide - UMR 8181 (UCCS), Université d'Artois (UA)-Centrale Lille-Institut de Chimie du CNRS (INC)-Université de Lille-Centre National de la Recherche Scientifique (CNRS), and Centrale Lille Institut (CLIL)-Université d'Artois (UA)-Centrale Lille-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Lille
Subjects: Materials science, chemistry.chemical_element, engineering.material, 010402 general chemistry, 01 natural sciences, 7. Clean energy, Catalysis, Metal, chemistry.chemical_compound, Coating, [CHIM]Chemical Sciences, Metal catalyst, Carbon nitride, ComputingMilieux_MISCELLANEOUS, 010405 organic chemistry, Fischer–Tropsch process, General Chemistry, 0104 chemical sciences, chemistry, Chemical engineering, visual_art, engineering, visual_art.visual_art_medium, Dispersion (chemistry), Cobalt
Abstract: Supported metal catalysts have found numerous applications in many catalytic reactions, including Fischer–Tropsch (FT) synthesis. Metal dispersion, metal reducibility, catalytic performance, and ca...
Published: 2020
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33. Number and intrinsic activity of cobalt surface sites in platinum promoted zeolite catalysts for carbon monoxide hydrogenation

Author: Nilson Romeu Marcilio, Andrei Y. Khodakov, Vitaly V. Ordomsky, Alexandre Carvalho, Unité de Catalyse et Chimie du Solide - UMR 8181 (UCCS), Centrale Lille Institut (CLIL)-Université d'Artois (UA)-Centrale Lille-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Lille, Universidade Federal do Rio Grande do Sul [Porto Alegre] (UFRGS), Université d'Artois (UA)-Centrale Lille-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Lille, Université d'Artois (UA)-Centrale Lille-Institut de Chimie du CNRS (INC)-Université de Lille-Centre National de la Recherche Scientifique (CNRS), and ANR-16-CE06-0013,NANO4FuT,Synthèse des carburants alternatifs et des molécules plateforme sur nanoréacteurs(2016)
Subjects: inorganic chemicals, Hydrogen, 010405 organic chemistry, Inorganic chemistry, chemistry.chemical_element, [CHIM.CATA]Chemical Sciences/Catalysis, 010402 general chemistry, 01 natural sciences, Catalysis, 0104 chemical sciences, Reaction rate, chemistry.chemical_compound, chemistry, [CHIM]Chemical Sciences, Reactivity (chemistry), Zeolite, Platinum, Cobalt, ComputingMilieux_MISCELLANEOUS, Carbon monoxide
Abstract: International audience; Supported cobalt catalysts are the catalysts of choice for synthesis of paraffinic hydrocarbons from carbon monoxide and hydrogen. In this paper, the number and intrinsic activity of cobalt nanoparticles promoted with Pt localized in zeolites with different structures and pore diameters (ZSM-5, MOR and BEA) have been investigated by steady state isotopic kinetic analysis (SSITKA) under conditions favouring higher methane selectivity. Promotion with Pt resulted in a higher number and higher reactivity of surface intermediates leading to methane. The cobalt catalyst supported by MOR zeolite displayed the highest SSITKA reaction rate in carbon monoxide hydrogenation, followed by Co supported on BEA and then Co supported on the zeolite ZSM-5. Good dispersion of cobalt nanoparticles inside and outside the surface of the MOR and BEA zeolites led to a higher number of active sites. On the other hand, poor dispersion of cobalt nanoparticles on the external surface of ZSM-5 resulted in the lowest intrinsic catalytic activity and lowest number of active sites. The intrinsic activity of cobalt sites was, however, almost unaffected by the inclusion of cobalt nanoparticles in the zeolite pores.
Published: 2020
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34. Influence of Impregnation and Ion Exchange Sequence on Metal Localization, Acidity and Catalytic Performance of Cobalt BEA Zeolite Catalysts in Fischer‐Tropsch Synthesis

Author: Vitaly V. Ordomsky, Camila Gomes Flores, Nilson Romeu Marcilio, Andrei Y. Khodakov, Nuno Batalha, Unité de Catalyse et Chimie du Solide - UMR 8181 (UCCS), Université d'Artois (UA)-Centrale Lille-Institut de Chimie du CNRS (INC)-Université de Lille-Centre National de la Recherche Scientifique (CNRS), ANR-16-CE06-0013,NANO4FuT,Synthèse des carburants alternatifs et des molécules plateforme sur nanoréacteurs(2016), Centrale Lille Institut (CLIL)-Université d'Artois (UA)-Centrale Lille-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Lille, and Université d'Artois (UA)-Centrale Lille-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Lille
Subjects: inorganic chemicals, Inorganic chemistry, chemistry.chemical_element, 010402 general chemistry, 01 natural sciences, Catalysis, law.invention, Inorganic Chemistry, Metal, law, [CHIM]Chemical Sciences, Calcination, Physical and Theoretical Chemistry, Zeolite, ComputingMilieux_MISCELLANEOUS, Ion exchange, 010405 organic chemistry, Chemistry, Organic Chemistry, Fischer–Tropsch process, [CHIM.CATA]Chemical Sciences/Catalysis, [CHIM.MATE]Chemical Sciences/Material chemistry, 0104 chemical sciences, visual_art, visual_art.visual_art_medium, Selectivity, Cobalt
Abstract: Cobalt distribution between the external surface and micropores and acidity of the large pore BEA zeolite were controlled by choosing the sequence of impregnation and ion exchange procedures. Higher concentration of ion exchangeable cobalt was observed in the catalyst prepared by ion-exchange of the zeolite proton form. The presence of Na+ instead of H+ ions in the exchange positions of zeolite favored deposition of cobalt on the external surface. The acid sites in the zeolite micropores can be then restored by subsequent ion exchange of sodium with ammonium nitrate and calcination. The catalytic performance of the cobalt zeolite catalysts prepared using different impregnation and ion exchange procedures was tested in the Fischer-Tropsch synthesis. Higher reaction rates were observed over the catalysts, which did not contain cobalt ions in the cation sites of the zeolite. Lower methane selectivity, higher selectivity to long chain hydrocarbons and high fraction of isomerized products are observed when cobalt species are located on the zeolite outer surface and acid sites inside the BEA zeolite micropores.
Published: 2018
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35. Unravelling the influence of catalyst properties on light olefin production via Fischer–Tropsch synthesis: A descriptor space investigation using Single-Event MicroKinetics

Author: Laura Pirro, A.R. Costa da Cruz, Andrei Y. Khodakov, Joris Thybaut, Alan J. Barrios, Anoop Chakkingal, Mirella Virginie, Laboratory for Chemical Technology, Universiteit Gent = Ghent University (UGENT), Unité de Catalyse et Chimie du Solide - UMR 8181 (UCCS), and Université d'Artois (UA)-Centrale Lille-Institut de Chimie du CNRS (INC)-Université de Lille-Centre National de la Recherche Scientifique (CNRS)
Subjects: Technology and Engineering, Materials science, Circular economy, Hydrogen, FUELS, General Chemical Engineering, chemistry.chemical_element, 02 engineering and technology, 010402 general chemistry, 01 natural sciences, Industrial and Manufacturing Engineering, Catalysis, COAL, Methanation, KINETIC-MODEL, [CHIM]Chemical Sciences, Environmental Chemistry, UBI-QEP METHOD, [INFO]Computer Science [cs], chemistry.chemical_classification, Single-Event MicroKinetic modelling, Olefin fiber, Fischer–Tropsch process, General Chemistry, Fischer-Tropsch synthesis, 021001 nanoscience & nanotechnology, 0104 chemical sciences, Virtual catalyst, Hydrocarbon, chemistry, Chemisorption, Yield (chemistry), Physical chemistry, Light olefins, 0210 nano-technology
Abstract: Kinetic models constitute a useful tool to provide fundamental insights for catalyst development. Single-Event MicroKinetic modelling (SEMK) is a versatile strategy to assess complex reactions with a limited number of parameters. Particularly for Fischer-Tropsch synthesis SEMK modelling has focused on explaining the performances of individual catalysts within a wide range of operating conditions. In this work, we extend the capabilities of the SEMK modelling approach to investigate the influence of variation in catalyst properties i.e. catalyst descriptors, on the yield of desired component, light olefins (C-2 -C-4 =). We explore the catalyst descriptor space around three literature-reported iron-based catalysts. The three catalyst descriptors, i.e. atomic chemisorption enthalpies of hydrogen (Q(H)), carbon (Q(C)), and oxygen (Q(O)) in the SEMK modelling approach have a combined effect on the conversion, whereas the selectivity to light olefins is found to be less sensitive to Q(O). These effects can be rationalized in terms of relative surface coverages of different species, leading to different dominant reaction pathways, and thus resulting in product yield variations. Using this approach, a "promising catalyst" with catalyst descriptors, Q(H) approximate to 234 kJ/mol, Q(C) approximate to 622 kJ/mol and Q(O) approximate to 575 kJ/mol resulting in 55% light olefins yield with lower methanation and long-chain hydrocarbon formation, is identified.
Published: 2021
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36. Solid micellar Ru single-atom catalysts for the water-free hydrogenation of CO2 to formic acid

Author: Willinton Y. Hernández, Olga V. Safonova, Vitaly V. Ordomsky, Evgeny I. Vovk, César A. Urbina-Blanco, Mark Saeys, Maya Marinova, Marianne Impéror-Clerc, Walid Baaziz, Qiyan Wang, Sara Santos, Andrei Y. Khodakov, Ovidiu Ersen, Unité de Catalyse et Chimie du Solide - UMR 8181 (UCCS), Centrale Lille Institut (CLIL)-Université d'Artois (UA)-Centrale Lille-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Lille, Eco-Efficient Products &Processes Laboratory (E2PL2), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-RHODIA, Laboratoire de Physique des Solides (LPS), Université Paris-Saclay-Centre National de la Recherche Scientifique (CNRS), Institut Michel Eugène Chevreul - FR 2638 (IMEC), Université d'Artois (UA)-Institut de Chimie du CNRS (INC)-Université de Lille-Centre National de la Recherche Scientifique (CNRS)-Institut National de Recherche pour l’Agriculture, l’Alimentation et l’Environnement (INRAE)-Centrale Lille Institut (CLIL), Institut de Physique et Chimie des Matériaux de Strasbourg (IPCMS), Université de Strasbourg (UNISTRA)-Matériaux et nanosciences d'Alsace (FMNGE), Institut de Chimie du CNRS (INC)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS)-Réseau nanophotonique et optique, Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA), Institut de chimie et procédés pour l'énergie, l'environnement et la santé (ICPEES), Institut de Chimie du CNRS (INC)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS), Paul Scherrer Institute (PSI), Eco-Efficient Products & Processes Laboratory (E2P2L), RHODIA-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Universiteit Gent = Ghent University (UGENT), University of Shanghai for Science and Technology, Université d'Artois (UA)-Centrale Lille-Institut de Chimie du CNRS (INC)-Université de Lille-Centre National de la Recherche Scientifique (CNRS)-Institut National de Recherche pour l’Agriculture, l’Alimentation et l’Environnement (INRAE), Université de Strasbourg (UNISTRA)-Centre National de la Recherche Scientifique (CNRS)-Matériaux et Nanosciences Grand-Est (MNGE), Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Réseau nanophotonique et optique, Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Centre National de la Recherche Scientifique (CNRS), Université de Strasbourg (UNISTRA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Matériaux et Nanosciences Grand-Est (MNGE), Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS), Université d'Artois (UA)-Centrale Lille-Institut de Chimie du CNRS (INC)-Université de Lille-Centre National de la Recherche Scientifique (CNRS), and ANR-16-CE06-0013,NANO4FuT,Synthèse des carburants alternatifs et des molécules plateforme sur nanoréacteurs(2016)
Subjects: Tertiary amine, Hydrogen, Formic acid, CO2 hydrogenation, chemistry.chemical_element, 02 engineering and technology, 010402 general chemistry, Photochemistry, 01 natural sciences, 7. Clean energy, Micelle, Heterolysis, Catalysis, chemistry.chemical_compound, [CHIM]Chemical Sciences, Formate, ComputingMilieux_MISCELLANEOUS, General Environmental Science, Hydride, Process Chemistry and Technology, Ru, 021001 nanoscience & nanotechnology, Solid micelles, 0104 chemical sciences, chemistry, 0210 nano-technology, Single-atom catalysts
Abstract: International audience; The catalytic hydrogenation of CO2 to formic acid is one of the most promising pathways towards a renewable hydrogen-storage system. The reaction is usually performed in aqueous phase in the presence of basic molecules over homogeneous or heterogeneous catalysts, generating relatively dilute formate solutions (
Published: 2021
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37. Soldering of Iron Catalysts for Direct Synthesis of Light Olefins from Syngas under Mild Reaction Conditions

Author: Vitaly V. Ordomsky, Andrei Y. Khodakov, Bang Gu, Alexandre Monteiro de Carvalho, Yuan Luo, Petr A. Chernavskii, and Kang Cheng
Subjects: Olefin fiber, 010405 organic chemistry, Chemistry, Inorganic chemistry, Nanoparticle, Fischer–Tropsch process, General Chemistry, 010402 general chemistry, 01 natural sciences, Catalysis, Dissociation (chemistry), 0104 chemical sciences, Carbide, Soldering, Syngas
Abstract: High-temperature Fischer–Tropsch synthesis represents a sustainable alternative for direct light olefin synthesis from syngas derived from fossil and renewable feedstocks. It is found that the promotion of iron catalysts with metals used for soldering (Bi and Pb) results in a remarkable increase in the light olefin production rate with a possibility to conduct Fischer–Tropsch synthesis at low reaction pressure. A combination of characterization techniques uncovered notable migration of the promoting elements during the reaction and decoration of iron carbide nanoparticles with the promoters. The promoters seem to facilitate CO dissociation by removing O atoms from iron carbide.
Published: 2017
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38. Effect of potassium promotion on the structure and performance of alumina supported carburized molybdenum catalysts for Fischer-Tropsch synthesis

Author: Mirella Virginie, Andrei Y. Khodakov, Tong Li, Unité de Catalyse et Chimie du Solide - UMR 8181 (UCCS), Centrale Lille Institut (CLIL)-Université d'Artois (UA)-Centrale Lille-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Lille, and Université d'Artois (UA)-Centrale Lille-Institut de Chimie du CNRS (INC)-Université de Lille-Centre National de la Recherche Scientifique (CNRS)
Subjects: Olefin fiber, Chemistry, Process Chemistry and Technology, Potassium, Inorganic chemistry, chemistry.chemical_element, Fischer–Tropsch process, [CHIM.CATA]Chemical Sciences/Catalysis, 02 engineering and technology, 010402 general chemistry, 021001 nanoscience & nanotechnology, 01 natural sciences, Catalysis, 0104 chemical sciences, chemistry.chemical_compound, Molybdenum, Hydrogenolysis, 0210 nano-technology, ComputingMilieux_MISCELLANEOUS, Carbon monoxide, Syngas
Abstract: Fischer-Tropsch synthesis produces light olefins and long chain hydrocarbons from syngas generated from fossil and renewable feedstocks. Molybdenum carbide exhibits catalytic properties approaching those of metal catalysts in a number of hydrogenation reactions. The present paper focuses on the effect of promotion with potassium on the structure and performance of alumina supported carburized molybdenum catalysts in Fischer-Tropsch synthesis. Molybdenum carbide catalysts were synthesized by temperature programmed carburization in methane and hydrogen. Molybdenum was highly dispersed in both calcined and carburized alumina supported catalysts. Mixed oxides of potassium, molybdenum and aluminium were uncovered in the calcined promoted catalysts. These oxides are converted in molybdenum carbide species on their carburization. Potassium promotion strengthens interaction between molybdenum and aluminium. The potassium promoted catalysts exhibited higher selectivity to light olefins and long chain hydrocarbons but lower Fischer-Tropsch reaction rate compared to the unpromoted counterpart. The observed lower Fischer-Tropsch reaction rate on the promoted catalysts was attributed to more difficult carburization of the molybdenum species and electronic effects due to the presence of potassium. The light olefin and C 5+ selectivities decrease at higher carbon monoxide conversion probably because of secondary olefin hydrogenation and hydrocarbon hydrogenolysis.
Published: 2017
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39. New molybdenum-based catalysts for dry reforming of methane in presence of sulfur: A promising way for biogas valorization

Author: Andrei Y. Khodakov, Mirella Virginie, Marine Gaillard, Unité de Catalyse et Chimie du Solide - UMR 8181 (UCCS), Université d'Artois (UA)-Centrale Lille-Institut de Chimie du CNRS (INC)-Université de Lille-Centre National de la Recherche Scientifique (CNRS), and Centrale Lille Institut (CLIL)-Université d'Artois (UA)-Centrale Lille-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Lille
Subjects: inorganic chemicals, Thermogravimetric analysis, Carbon dioxide reforming, Inorganic chemistry, chemistry.chemical_element, [CHIM.CATA]Chemical Sciences/Catalysis, 02 engineering and technology, General Chemistry, 010402 general chemistry, 021001 nanoscience & nanotechnology, 7. Clean energy, 01 natural sciences, Sulfur, Catalysis, Methane, 0104 chemical sciences, chemistry.chemical_compound, chemistry, 13. Climate action, Molybdenum, Temperature-programmed reduction, 0210 nano-technology, ComputingMilieux_MISCELLANEOUS, Incipient wetness impregnation
Abstract: Mo-based catalysts supported on γ-Al 2 O 3 were synthesized by an incipient wetness impregnation method. They have been tested in the methane dry reforming reaction in a fixed-bed reactor at temperatures from 650 to 800 °C. Additional tests have been carried out in presence of 50 ppm of H 2 S to verify their stability towards sulfur poisoning. The influence of Mo loading and Ni promotion on the catalyst activity, stability, and coke deposition were investigated. The fresh and spent catalysts were characterized using N 2 physisorption, X-ray Diffraction, Temperature Programmed Reduction and Thermogravimetric Analysis. Carbon deposition was the major reason of deactivation of the molybdenum catalysts, while nickel catalysts rapidly lost their activity in the presence of sulfur. The optimized nickel-promoted molybdenum catalysts exhibit a synergetic effect conferring to them better reducibility, smaller carbon deposition and better stability in presence of sulfur.
Published: 2017
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40. Syngas to Chemicals: The Incorporation of Aldehydes into Fischer-Tropsch Synthesis

Author: Vitaly V. Ordomsky and Andrei Y. Khodakov
Subjects: chemistry.chemical_classification, 010405 organic chemistry, Organic Chemistry, Fischer–Tropsch process, 010402 general chemistry, 01 natural sciences, 7. Clean energy, Aldehyde, Catalysis, 0104 chemical sciences, Inorganic Chemistry, Hydrocarbon, chemistry, Polymerization, Yield (chemistry), Organic chemistry, Physical and Theoretical Chemistry, Oxygenate, Syngas
Abstract: Syngas is an important intermediate for synthesis of chemicals and fuels; it can be produced from renewable and fossil feedstocks. Syngas conversion on iron catalysts results mostly in linear paraffins, olefins and oxygenates. In the produced olefins or oxygenates, the functional groups or double bonds are always located in the hydrocarbon α-positon. The yield of non-linear functionalized hydrocarbons or chemical compounds with secondary and tertiary functional groups is low. The present paper explores a possibility of direct synthesis of divers functionalized and branched hydrocarbons in Fischer-Tropsch reaction by co-feeding syngas with aldehydes. Aldehydes added to syngas initiate surface polymerization. Quantitative stoichiometric incorporation of aldehydes in the growing hydrocarbon chain was observed. The hydrocarbons containing incorporated aldehyde fragment exhibit Anderson-Schulz-Flory distribution similar to the conventional Fischer-Tropsch synthesis.
Published: 2017
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41. Core–Shell Metal Zeolite Composite Catalysts for In Situ Processing of Fischer–Tropsch Hydrocarbons to Gasoline Type Fuels

Author: Michal Mazur, Aleksandra S. Peregudova, Valentin Valtchev, Debora R. Strossi Pedrolo, Bang Gu, Vitaly V. Ordomsky, Andrei Y. Khodakov, Jan Přech, Nilson Romeu Marcilio, Laboratoire catalyse et spectrochimie (LCS), Université de Caen Normandie (UNICAEN), Normandie Université (NU)-Normandie Université (NU)-École Nationale Supérieure d'Ingénieurs de Caen (ENSICAEN), Normandie Université (NU)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Unité de Catalyse et Chimie du Solide - UMR 8181 (UCCS), Université d'Artois (UA)-Centrale Lille-Institut de Chimie du CNRS (INC)-Université de Lille-Centre National de la Recherche Scientifique (CNRS), Instituto Federal do Rio Grande do Sul (IFRS), University of St Andrews [Scotland], ANR-16-CE06-0013,NANO4FuT,Synthèse des carburants alternatifs et des molécules plateforme sur nanoréacteurs(2016), Centre National de la Recherche Scientifique (CNRS)-École Nationale Supérieure d'Ingénieurs de Caen (ENSICAEN), Normandie Université (NU)-Normandie Université (NU)-Institut de Chimie du CNRS (INC)-Université de Caen Normandie (UNICAEN), Normandie Université (NU), Centrale Lille Institut (CLIL)-Université d'Artois (UA)-Centrale Lille-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Lille, Normandie Université (NU)-Centre National de la Recherche Scientifique (CNRS), Université de Lille-Centre National de la Recherche Scientifique (CNRS)-Ecole Nationale Supérieure de Chimie de Lille (ENSCL)-Ecole Centrale de Lille-Université d'Artois (UA), Universidade Federal do Rio Grande do Sul [Porto Alegre] (UFRGS), and Charles University [Prague]
Subjects: core−shell structure, Materials science, Composite number, Fischer−Tropsch synthesis, 010402 general chemistry, 01 natural sciences, Catalysis, isomerization, core-shell structure, [CHIM]Chemical Sciences, Gasoline, Zeolite, ruthenium, Nanocomposite, nanocomposite, 010405 organic chemistry, Fischer–Tropsch process, General Chemistry, Fischer-Tropsch synthesis, 0104 chemical sciences, Bifunctional catalyst, Chemical engineering, hierarchical zeolite, bifunctional catalyst, Isomerization
Abstract: International audience; Fischer–Tropsch synthesis has two main challenges related to direct production of gasoline fuels. First, the chain length distribution of the products follows a broad and unselective Anderson–Schulz–Flory distribution. Second, mostly linear hydrocarbons are formed in the Fischer–Tropsch reaction, thus requiring isomerization while manufacturing gasoline fuels. The present paper addresses a synthetic strategy for the preparation of hierarchical metal and zeolite nanocomposite catalysts for direct synthesis of iso-paraffins from syngas. The nanocomposites are synthesized in three steps. In the first step, the parent (core) zeolite is etched with an ammonium fluoride solution. The etching creates small mesopores inside the zeolite crystals. In the second step, the Ru nanoparticles prepared using water-in-oil microemulsion are deposited in the mesopores of the zeolite. In the third step, a zeolite shell of MFI-type zeolites (silicalite-1 or ZSM-5) is grown on the parent zeolite crystals coating both the etched surface and metallic nanoparticles. Thus, the metal nanoparticles become entirely encapsulated inside the zeolite matrix. Most important parameters such as ruthenium content, zeolite mesoporosity, and more particularly, the acidity of the catalyst shell, which affect the catalytic performance of the synthesized nanocomposite materials in low-temperature Fischer–Tropsch synthesis were identified in this work. The higher relative amount of iso-paraffins was observed on the catalysts containing a shell of ZSM-5. The proximity between metal and acid sites in the zeolite shell of the nanocomposite catalysts is a crucial parameter for the design of efficient metal zeolite bifunctional catalysts for selective synthesis of gasoline-type fuels via Fischer–Tropsch synthesis, while the acidity of the catalyst core has only a limited impact on the catalytic performance.
Published: 2020
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42. A multifaceted role of a mobile bismuth promoter in alcohol amination over cobalt catalysts

Author: Bright T. Kusema, Ovidiu Ersen, Feng Niu, Mounib Bahri, Andrei Y. Khodakov, Zhen Yan, Vitaly V. Ordomsky, Ordomsky, Vitaly, Unité de Catalyse et Chimie du Solide - UMR 8181 (UCCS), Université d'Artois (UA)-Centrale Lille-Institut de Chimie du CNRS (INC)-Université de Lille-Centre National de la Recherche Scientifique (CNRS), Eco-Efficient Products & Processes Laboratory (E2P2L), RHODIA-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Institut de Physique et Chimie des Matériaux de Strasbourg (IPCMS), Université de Strasbourg (UNISTRA)-Centre National de la Recherche Scientifique (CNRS)-Matériaux et Nanosciences Grand-Est (MNGE), Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Réseau nanophotonique et optique, Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Centre National de la Recherche Scientifique (CNRS), Centrale Lille Institut (CLIL)-Université d'Artois (UA)-Centrale Lille-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Lille, Eco-Efficient Products &Processes Laboratory (E2PL2), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-RHODIA, Université de Strasbourg (UNISTRA)-Matériaux et nanosciences d'Alsace (FMNGE), Institut de Chimie du CNRS (INC)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS)-Réseau nanophotonique et optique, and Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)
Subjects: inorganic chemicals, 010405 organic chemistry, [CHIM.ORGA]Chemical Sciences/Organic chemistry, chemistry.chemical_element, [CHIM.CATA] Chemical Sciences/Catalysis, Alcohol, [CHIM.CATA]Chemical Sciences/Catalysis, 010402 general chemistry, [CHIM.ORGA] Chemical Sciences/Organic chemistry, 01 natural sciences, Pollution, Combinatorial chemistry, Coupling reaction, 0104 chemical sciences, Catalysis, Bismuth, chemistry.chemical_compound, chemistry, Environmental Chemistry, Temperature-programmed reduction, Selectivity, Cobalt, Amination
Abstract: International audience; Promotion with small amounts of different elements is an efficient strategy for the enhancement of the performance of many heterogeneous catalysts. Supported cobalt catalysts exhibit significant activity in the synthesis of primary amines via alcohol amination with ammonia, which is an economically efficient and environmentally friendly process. Insufficient selectivity to primary amines, low activity and fast cobalt catalyst deactivation remain serious issues restricting the application of alcohol amination in the industry. In this work, we have discovered the multifaceted role of the bismuth promoter, which is highly mobile under reaction conditions, in 1-octanol amination over supported cobalt catalysts. First, the overall reaction rate was enhanced more than twice on promotion with bismuth. Second, the selectivity to primary amines increased 6 times in the presence of Bi at high alcohol conversion. Finally, the bismuth promotion resulted in extremely high stability of the cobalt catalyst. Characterization by XRD, temperature programmed reduction, STEM, CO chemisorption, BET, TGA and FTIR has showed that the enhancement of the catalytic performance on promotion with bismuth is due to better cobalt reducibility, easy removal of strongly adsorbed intermediates and products by the mobile promoter and suppression of amine coupling reactions resulting in secondary and tertiary amines.
Published: 2020
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43. Dual Metal-Acid Pd-Br Catalyst for Selective Hydrodeoxygenation of 5-Hydroxymethylfurfural (HMF) to 2, 5-Dimethylfuran at Ambient Temperature

Author: Dan Wu, Maya Marinova, Andrei Y. Khodakov, Songwei Zhang, Willinton Y. Hernández, Vitaly V. Ordomsky, Ovidiu Ersen, Walid Baaziz, Eco-Efficient Products & Processes Laboratory (E2P2L), RHODIA-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Institut de chimie et procédés pour l'énergie, l'environnement et la santé (ICPEES), Université de Strasbourg (UNISTRA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Matériaux et Nanosciences Grand-Est (MNGE), Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS), Institut de Physique et Chimie des Matériaux de Strasbourg (IPCMS), Université de Strasbourg (UNISTRA)-Centre National de la Recherche Scientifique (CNRS)-Matériaux et Nanosciences Grand-Est (MNGE), Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Réseau nanophotonique et optique, Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Centre National de la Recherche Scientifique (CNRS), Institut Michel Eugène Chevreul - FR 2638 (IMEC), Université d'Artois (UA)-Centrale Lille-Institut de Chimie du CNRS (INC)-Université de Lille-Centre National de la Recherche Scientifique (CNRS)-Institut National de Recherche pour l’Agriculture, l’Alimentation et l’Environnement (INRAE), Unité de Catalyse et Chimie du Solide - UMR 8181 (UCCS), Université d'Artois (UA)-Centrale Lille-Institut de Chimie du CNRS (INC)-Université de Lille-Centre National de la Recherche Scientifique (CNRS), ShanghaiTech University [Shanghai], Ecole Nationale Supérieure de Chimie de Lille (ENSCL), Eco-Efficient Products &Processes Laboratory (E2PL2), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-RHODIA, Université de Strasbourg (UNISTRA)-Matériaux et nanosciences d'Alsace (FMNGE), Institut de Chimie du CNRS (INC)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS), Institut de Chimie du CNRS (INC)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS)-Réseau nanophotonique et optique, Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA), Université d'Artois (UA)-Institut de Chimie du CNRS (INC)-Université de Lille-Centre National de la Recherche Scientifique (CNRS)-Institut National de Recherche pour l’Agriculture, l’Alimentation et l’Environnement (INRAE)-Centrale Lille Institut (CLIL), Centrale Lille Institut (CLIL)-Université d'Artois (UA)-Centrale Lille-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Lille, and univOAK, Archive ouverte
Subjects: 2,5-Dimethylfuran, chemistry.chemical_element, hydrodeoxygenation, 010402 general chemistry, Heterogeneous catalysis, 01 natural sciences, Catalysis, Metal, chemistry.chemical_compound, [CHIM]Chemical Sciences, ComputingMilieux_MISCELLANEOUS, biomass, 010405 organic chemistry, Chemistry, [CHIM.CATA] Chemical Sciences/Catalysis, General Chemistry, bifunctional catalysis, [CHIM.CATA]Chemical Sciences/Catalysis, Combinatorial chemistry, 0104 chemical sciences, Bifunctional catalyst, heterogeneous catalysis, dimethylfuran, visual_art, visual_art.visual_art_medium, Brønsted–Lowry acid–base theory, Hydrodeoxygenation, Palladium
Abstract: Supported metal catalysts have found broad applications in heterogeneous catalysis. In the conventional bifunctional catalyst, the active metal sites are associated with the metal nanoparticles, while the acid sites are usually localized over the oxide support. Herein, we report a novel type of supported metal bifunctional catalyst, which combined the advantages of the promotion and bifunctionality. The catalyst was designed by the pretreatment of supported palladium catalysts with bromobenzene. The promotion with bromine creates Bronsted acid sites, which are localized directly on the surface of metal nanoparticles. An intimacy between metal and acid functions in this bifunctional catalyst generates unique catalytic properties in hydrodeoxygenation of 5-hydroxymethylfurfural to dimethylfuran, occurring with the yield up to 96% at ambient temperature under 5 bar of H-2. The catalyst exhibits stable catalytic performance.
Published: 2020
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44. Assessment of metal sintering in the copper- zeolite hybrid catalyst for direct dimethyl ether synthesis using synchrotron-based X-ray absorption and diffraction

Author: Vijayanand Subramanian, Valentin Valtchev, Yuan Luo, Simona Moldovan, Vitaly V. Ordomsky, Andrei Y. Khodakov, Ana Palčić, Ovidiu Ersen, Mengdie Cai, Unité de Catalyse et Chimie du Solide - UMR 8181 (UCCS), Université de Lille-Centre National de la Recherche Scientifique (CNRS)-Ecole Nationale Supérieure de Chimie de Lille (ENSCL)-Ecole Centrale de Lille-Université d'Artois (UA), Rudjer Boskovic Institute [Zagreb], Laboratoire catalyse et spectrochimie (LCS), Université de Caen Normandie (UNICAEN), Normandie Université (NU)-Normandie Université (NU)-École Nationale Supérieure d'Ingénieurs de Caen (ENSICAEN), Normandie Université (NU)-Centre National de la Recherche Scientifique (CNRS), Institut de Physique et Chimie des Matériaux de Strasbourg (IPCMS), Université de Strasbourg (UNISTRA)-Centre National de la Recherche Scientifique (CNRS)-Matériaux et nanosciences d'Alsace, Centre National de la Recherche Scientifique (CNRS)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Université de Strasbourg (UNISTRA)-Centre National de la Recherche Scientifique (CNRS)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Université de Strasbourg (UNISTRA)-Réseau nanophotonique et optique, Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Université de Strasbourg (UNISTRA), Centrale Lille Institut (CLIL)-Université d'Artois (UA)-Centrale Lille-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Lille, Centre National de la Recherche Scientifique (CNRS)-École Nationale Supérieure d'Ingénieurs de Caen (ENSICAEN), Normandie Université (NU)-Normandie Université (NU)-Institut de Chimie du CNRS (INC)-Université de Caen Normandie (UNICAEN), Normandie Université (NU), Université de Strasbourg (UNISTRA)-Matériaux et nanosciences d'Alsace (FMNGE), Institut de Chimie du CNRS (INC)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS)-Réseau nanophotonique et optique, Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA), Université d'Artois (UA)-Centrale Lille-Institut de Chimie du CNRS (INC)-Université de Lille-Centre National de la Recherche Scientifique (CNRS), Normandie Université (NU)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Université de Strasbourg (UNISTRA)-Centre National de la Recherche Scientifique (CNRS)-Matériaux et Nanosciences Grand-Est (MNGE), Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Réseau nanophotonique et optique, and Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Centre National de la Recherche Scientifique (CNRS)
Subjects: Materials science, Absorption spectroscopy, dimethyl ether, chemistry.chemical_element, Sintering, 02 engineering and technology, 010402 general chemistry, 7. Clean energy, 01 natural sciences, Catalysis, chemistry.chemical_compound, [CHIM]Chemical Sciences, Dimethyl ether, zeolite, Zeolite, Bifunctional, ComputingMilieux_MISCELLANEOUS, Syngas Dimethyl-ether, Hybrid catalyst, Deactivation, Hydrogenation, General Chemistry, [CHIM.CATA]Chemical Sciences/Catalysis, syngas, 021001 nanoscience & nanotechnology, Copper, 0104 chemical sciences, Chemical engineering, chemistry, hybrid catalyst, hydrogenation, 0210 nano-technology, deactivation, Syngas
Abstract: International audience; Dimethyl ether is one of the most promising environmentally optimized alternatives to the conventional fossil fuels and an important platform molecule for chemical industry. Catalyst deactivation is one of the most important challenges of the single-step dimethyl ether synthesis from syngas. Because of the lack of direct characterization techniques working under harsh reaction conditions, the information about deactivation mechanisms of bifunctional Cu/ZSM-5 catalysts is rather contradictory. In this paper, a combination of synchrotron-based in-situ time-resolved X-ray diffraction and X-ray absorption spectroscopy operating under high pressure and temperature alongside with the conventional ex-situ characterization uncovered very rapid copper sintering occurring under realistic conditions of direct dimethyl ether synthesis. Copper sintering was strongly affected by the presence of water either produced by the reaction or co-fed to the reactor. No copper oxidation was observed under a wide range of experimental conditions.
Published: 2020
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45. Stoichiometric methane conversion to ethane using photochemical looping at ambient temperature

Author: Vitaly V. Ordomsky, Dan Wu, Simona Moldovan, Vladimir L. Zholobenko, Xiang Yu, Di Hu, Andrei Y. Khodakov, Unité de Catalyse et Chimie du Solide - UMR 8181 (UCCS), Université d'Artois (UA)-Centrale Lille-Institut de Chimie du CNRS (INC)-Université de Lille-Centre National de la Recherche Scientifique (CNRS), Keele University [Keele], Groupe de physique des matériaux (GPM), Université de Rouen Normandie (UNIROUEN), Normandie Université (NU)-Normandie Université (NU)-Institut national des sciences appliquées Rouen Normandie (INSA Rouen Normandie), Institut National des Sciences Appliquées (INSA)-Normandie Université (NU)-Institut National des Sciences Appliquées (INSA)-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche sur les Matériaux Avancés (IRMA), Université de Caen Normandie (UNICAEN), Normandie Université (NU)-Normandie Université (NU)-École Nationale Supérieure d'Ingénieurs de Caen (ENSICAEN), Normandie Université (NU)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université de Rouen Normandie (UNIROUEN), Normandie Université (NU)-Institut national des sciences appliquées Rouen Normandie (INSA Rouen Normandie), Institut National des Sciences Appliquées (INSA)-Normandie Université (NU)-Institut National des Sciences Appliquées (INSA)-Centre National de la Recherche Scientifique (CNRS)-Université de Caen Normandie (UNICAEN), Normandie Université (NU)-École Nationale Supérieure d'Ingénieurs de Caen (ENSICAEN), Normandie Université (NU)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Centre National de la Recherche Scientifique (CNRS), ANR-11-EQPX-0020,GENESIS,Groupe d'Etudes et de Nanoanalyses des Effets d'IrradiationS(2011), Université d'Artois (UA)-Centrale Lille-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Lille, Centrale Lille Institut (CLIL)-Université d'Artois (UA)-Centrale Lille-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Lille, Centre National de la Recherche Scientifique (CNRS)-Institut national des sciences appliquées Rouen Normandie (INSA Rouen Normandie), Institut National des Sciences Appliquées (INSA)-Normandie Université (NU)-Institut National des Sciences Appliquées (INSA)-Normandie Université (NU)-Université de Rouen Normandie (UNIROUEN), and Normandie Université (NU)
Subjects: Materials science, Radical, Energy Engineering and Power Technology, 02 engineering and technology, Raw material, 010402 general chemistry, Photochemistry, Q1, 7. Clean energy, 01 natural sciences, Methane, 12. Responsible consumption, Metal, chemistry.chemical_compound, [CHIM]Chemical Sciences, QD, ComputingMilieux_MISCELLANEOUS, Renewable Energy, Sustainability and the Environment, [CHIM.ORGA]Chemical Sciences/Organic chemistry, Cationic polymerization, [CHIM.CATA]Chemical Sciences/Catalysis, 021001 nanoscience & nanotechnology, 0104 chemical sciences, Electronic, Optical and Magnetic Materials, Fuel Technology, chemistry, 13. Climate action, Yield (chemistry), visual_art, visual_art.visual_art_medium, 0210 nano-technology, Selectivity, Stoichiometry, QD415
Abstract: International audience; Methane is the main component of natural and shale gas, methane clathrates and biogas, and is a potent greenhouse gas. About 90% of methane is currently burnt in various combustion processes, releasing carbon dioxide into the atmosphere 1-7. Finding ways to efficiently convert methane into fuels and chemicals is important for the rational utilization of fossil and renewable energy feedstocks, as well as for reducing the emission of greenhouse gases. Methane is a highly stable molecule; it has no functional groups and a very high C-H bond enthalpy (439 kJ mol −1). Methane is also inert relative to acid attack and has a very low proton affinity (544 kJ mol −1) and acidity (pK a = 40). Therefore, direct chemical conversion of methane to value-added chemicals and fuels remains a formidable challenge for modern science 8-10. Commercial technologies of methane utilization, other than combustion, are rather limited. They involve methane steam reforming, partial oxidation, autothermal reforming or the Andrussow reaction 11-13. The non-commercial routes for methane conversion can be divided into oxidative and non-oxidative routes 8-21. The non-oxidative routes, such as methane aromatization, result in substantial carbon deposition, while the oxidative routes, such as methane thermocatalytic coupling and methane partial oxidation, usually suffer from insufficient selectivity and abundant production of CO 2. Most of the known methane conversion reactions require very high temperatures (>800 °C). Generally, these thermochemical processes are accompanied by CO 2 emissions arising from the combustion of fossil fuels utilized to maintain the reactor at high temperatures 18-23. Photocatalytic non-oxidative coupling of methane with very low quantum efficiencies and yields was observed over silica, highly dispersed Ga or Ce species 24-26. Activation of methane over Zn 2+ / ZSM-5 and Ga 3+ /EST-10 photocatalysts has been reported, with the photocatalytic activity attributed to the presence of extra-framework zinc cations and Ti-OH groups on titanate wires 27,28. Photocatalytic non-oxidative coupling of methane has been observed when
Published: 2020
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46. Design of core–shell titania–heteropolyacid–metal nanocomposites for photocatalytic reduction of CO 2 to CO at ambient temperature

Author: Andrei Y. Khodakov, Xiang Yu, Simona Moldovan, Vitaly V. Ordomsky, Unité de Catalyse et Chimie du Solide - UMR 8181 (UCCS), Université d'Artois (UA)-Centrale Lille-Institut de Chimie du CNRS (INC)-Université de Lille-Centre National de la Recherche Scientifique (CNRS), Groupe de physique des matériaux (GPM), Université de Rouen Normandie (UNIROUEN), Normandie Université (NU)-Normandie Université (NU)-Institut national des sciences appliquées Rouen Normandie (INSA Rouen Normandie), Institut National des Sciences Appliquées (INSA)-Normandie Université (NU)-Institut National des Sciences Appliquées (INSA)-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche sur les Matériaux Avancés (IRMA), Université de Caen Normandie (UNICAEN), Normandie Université (NU)-Normandie Université (NU)-École Nationale Supérieure d'Ingénieurs de Caen (ENSICAEN), Normandie Université (NU)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université de Rouen Normandie (UNIROUEN), Normandie Université (NU)-Institut national des sciences appliquées Rouen Normandie (INSA Rouen Normandie), Institut National des Sciences Appliquées (INSA)-Normandie Université (NU)-Institut National des Sciences Appliquées (INSA)-Centre National de la Recherche Scientifique (CNRS)-Université de Caen Normandie (UNICAEN), Normandie Université (NU)-École Nationale Supérieure d'Ingénieurs de Caen (ENSICAEN), Normandie Université (NU)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Centre National de la Recherche Scientifique (CNRS), Eco-Efficient Products & Processes Laboratory (E2P2L), RHODIA-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), ANR-11-EQPX-0020,GENESIS,Groupe d'Etudes et de Nanoanalyses des Effets d'IrradiationS(2011), Centrale Lille Institut (CLIL)-Université d'Artois (UA)-Centrale Lille-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Lille, Centre National de la Recherche Scientifique (CNRS)-Institut national des sciences appliquées Rouen Normandie (INSA Rouen Normandie), Institut National des Sciences Appliquées (INSA)-Normandie Université (NU)-Institut National des Sciences Appliquées (INSA)-Normandie Université (NU)-Université de Rouen Normandie (UNIROUEN), Normandie Université (NU), Eco-Efficient Products &Processes Laboratory (E2PL2), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-RHODIA, and Université d'Artois (UA)-Centrale Lille-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Lille
Subjects: Reaction mechanism, Materials science, chemistry.chemical_element, Bioengineering, 02 engineering and technology, Reaction intermediate, Zinc, 010402 general chemistry, 01 natural sciences, 7. Clean energy, Catalysis, Transition metal, [CHIM]Chemical Sciences, General Materials Science, ComputingMilieux_MISCELLANEOUS, Nanocomposite, General Engineering, General Chemistry, [CHIM.CATA]Chemical Sciences/Catalysis, 021001 nanoscience & nanotechnology, Atomic and Molecular Physics, and Optics, 0104 chemical sciences, chemistry, Chemical engineering, 13. Climate action, Photocatalysis, Water splitting, 0210 nano-technology
Abstract: The photocatalytic conversion of CO2 not only reduces the greenhouse effect, but also provides value-added solar fuels and chemicals. Herein, we report the design of new efficient core–shell nanocomposites for selective photocatalytic CO2 to CO conversion, which occurs at ambient temperature. A combination of characterization techniques (TEM, STEM-EDX, XPS, XRD, FTIR photoluminescence) indicates that the CO2 reduction occurs over zinc species highly dispersed on the heteropolyacid/titania core–shell nanocomposites. These core–shell structures create a semiconductor heterojunction, which increases charge separation and the lifetime of charge carriers' and leads to higher electron flux. In situ FTIR investigation of the reaction mechanism revealed that the reaction involved surface zinc bicarbonates as key reaction intermediates. In a series of catalysts containing noble and transition metals, zinc phosphotungstic acid–titania nanocomposites exhibit high activity reaching 50 μmol CO g−1 h−1 and selectivity (73%) in the CO2 photocatalytic reduction to CO at ambient temperature. The competitive water splitting reaction has been significantly suppressed over the Zn sites in the presence of CO2.
Published: 2019
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47. Ion-exchanged Zeolite P as a Nanostructured Catalyst for Biodiesel Production

Author: Oleg I. Lebedev, Andrei Y. Khodakov, Natalie E. Mordvinova, Aqeel Al-Ani, Vladimir L. Zholobenko, Keele University [Keele], Laboratoire de cristallographie et sciences des matériaux (CRISMAT), École Nationale Supérieure d'Ingénieurs de Caen (ENSICAEN), Normandie Université (NU)-Normandie Université (NU)-Centre National de la Recherche Scientifique (CNRS)-Université de Caen Normandie (UNICAEN), Normandie Université (NU)-Institut de Chimie du CNRS (INC), Unité de Catalyse et Chimie du Solide - UMR 8181 (UCCS), Centrale Lille Institut (CLIL)-Université d'Artois (UA)-Centrale Lille-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Lille, SL-144-03Keele University, Centre National de la Recherche Scientifique (CNRS)-École Nationale Supérieure d'Ingénieurs de Caen (ENSICAEN), Normandie Université (NU)-Normandie Université (NU)-Université de Caen Normandie (UNICAEN), Normandie Université (NU), Unité de Catalyse et de Chimie du Solide - UMR 8181 (UCCS), Université d'Artois (UA)-Ecole Centrale de Lille-Ecole Nationale Supérieure de Chimie de Lille (ENSCL)-Université de Lille-Centre National de la Recherche Scientifique (CNRS), Université de Caen Normandie (UNICAEN), Normandie Université (NU)-Normandie Université (NU)-École Nationale Supérieure d'Ingénieurs de Caen (ENSICAEN), Normandie Université (NU)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche sur les Matériaux Avancés (IRMA), Normandie Université (NU)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université de Rouen Normandie (UNIROUEN), Normandie Université (NU)-Institut national des sciences appliquées Rouen Normandie (INSA Rouen Normandie), Institut National des Sciences Appliquées (INSA)-Normandie Université (NU)-Institut National des Sciences Appliquées (INSA)-Centre National de la Recherche Scientifique (CNRS)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université de Rouen Normandie (UNIROUEN), Institut National des Sciences Appliquées (INSA)-Normandie Université (NU)-Institut National des Sciences Appliquées (INSA)-Centre National de la Recherche Scientifique (CNRS), Université d'Artois (UA)-Centrale Lille-Institut de Chimie du CNRS (INC)-Université de Lille-Centre National de la Recherche Scientifique (CNRS), and Université d'Artois (UA)-Centrale Lille-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Lille
Subjects: Materials science, 020209 energy, chemistry.chemical_element, 02 engineering and technology, [CHIM.INOR]Chemical Sciences/Inorganic chemistry, 7. Clean energy, Catalysis, Basic sites, 020401 chemical engineering, X-ray photoelectron spectroscopy, Aluminium, ddc:330, 0202 electrical engineering, electronic engineering, information engineering, [CHIM.CRIS]Chemical Sciences/Cristallography, [CHIM]Chemical Sciences, QD, 0204 chemical engineering, Gismondine, Zeolite, ComputingMilieux_MISCELLANEOUS, Ion exchange, Transesterification, [CHIM.CATA]Chemical Sciences/Catalysis, Synthetic gismondine, [CHIM.MATE]Chemical Sciences/Material chemistry, Nanostructured catalysts, [CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry, General Energy, Chemical engineering, chemistry, Biodiesel production, Zeolites, lcsh:Electrical engineering. Electronics. Nuclear engineering, lcsh:TK1-9971
Abstract: Nano-crystalline synthetic gismondine modified via cation exchange has been utilised as a highly active and selective catalyst for the production of biofuel. In comparison with low silica zeolites FAU and LTA, K-form of gismondine, based on the maximum aluminium P (MAP) zeolite, exhibited a significant improvement in catalytic performance in the methanolysis of bio-oil, which can be attributed to its nano-particle morphology and high basicity associated with the high Al content and high degree of ion exchange, as demonstrated by the TEM, XRD, TGA, NMR, XPS and CO2-TPD studies. To the best of our knowledge, this is the first report on a successful catalytic application of basic K-MAP zeolite. Keywords: Synthetic gismondine, Zeolites, Transesterification, Basic sites, Nanostructured catalysts
Published: 2019
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48. Synergy of nanoconfinement and promotion in the design of efficient supported iron catalysts for direct olefin synthesis from syngas

Author: Debora R. Strossi Pedrolo, Simona Moldovan, Vitaly V. Ordomsky, Bang Gu, Shun He, Andrei Y. Khodakov, Bruno Lobato, Deizi V. Peron, Petr A. Chernavskii, Mauro C. Ribeiro, Unité de Catalyse et Chimie du Solide - UMR 8181 (UCCS), Université d'Artois (UA)-Centrale Lille-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Lille, Centrale Lille Institut (CLIL)-Université d'Artois (UA)-Centrale Lille-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Lille, Xiamen University, Groupe de physique des matériaux (GPM), Centre National de la Recherche Scientifique (CNRS)-Institut national des sciences appliquées Rouen Normandie (INSA Rouen Normandie), Institut National des Sciences Appliquées (INSA)-Normandie Université (NU)-Institut National des Sciences Appliquées (INSA)-Normandie Université (NU)-Université de Rouen Normandie (UNIROUEN), Normandie Université (NU), Universidade Federal Fluminense [Rio de Janeiro] (UFF), Universidade Federal Rural do Rio de Janeiro (UFRRJ), Lomonosov Moscow State University (MSU), Université d'Artois (UA)-Centrale Lille-Institut de Chimie du CNRS (INC)-Université de Lille-Centre National de la Recherche Scientifique (CNRS), Université de Rouen Normandie (UNIROUEN), Normandie Université (NU)-Normandie Université (NU)-Institut national des sciences appliquées Rouen Normandie (INSA Rouen Normandie), Institut National des Sciences Appliquées (INSA)-Normandie Université (NU)-Institut National des Sciences Appliquées (INSA)-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche sur les Matériaux Avancés (IRMA), Université de Caen Normandie (UNICAEN), Normandie Université (NU)-Normandie Université (NU)-École Nationale Supérieure d'Ingénieurs de Caen (ENSICAEN), Normandie Université (NU)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université de Rouen Normandie (UNIROUEN), Normandie Université (NU)-Institut national des sciences appliquées Rouen Normandie (INSA Rouen Normandie), Institut National des Sciences Appliquées (INSA)-Normandie Université (NU)-Institut National des Sciences Appliquées (INSA)-Centre National de la Recherche Scientifique (CNRS)-Université de Caen Normandie (UNICAEN), Normandie Université (NU)-École Nationale Supérieure d'Ingénieurs de Caen (ENSICAEN), Normandie Université (NU)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Centre National de la Recherche Scientifique (CNRS), and ANR-11-EQPX-0020,GENESIS,Groupe d'Etudes et de Nanoanalyses des Effets d'IrradiationS(2011)
Subjects: 010405 organic chemistry, business.industry, chemistry.chemical_element, Carbon nanotube, [CHIM.CATA]Chemical Sciences/Catalysis, 010402 general chemistry, 01 natural sciences, 7. Clean energy, Catalysis, XANES, 0104 chemical sciences, Bismuth, law.invention, X-ray photoelectron spectroscopy, chemistry, Chemical engineering, law, [CHIM]Chemical Sciences, Coal, Physical and Theoretical Chemistry, business, Dispersion (chemistry), ComputingMilieux_MISCELLANEOUS, Syngas
Abstract: Light olefins are important building blocks in chemical industry. High temperature Fischer-Tropsch synthesis provides a remarkable opportunity for direct synthesis of light olefins from syngas derived from a wide range of alternative feedstocks (biomass, organic or plastic wastes, natural gas, shale gas or coal). The present work focuses on the combined effects of the iron nanoconfinement, on the one hand, and promotion with bismuth and lead, on the other hand, on the structure and catalytic performance of iron catalysts supported by carbon nanotubes in high temperature Fischer-Tropsch synthesis. A wide range of techniques (TEM, XRD, TPR, synchrotron-based XPS, in-situ XANES and in-situ magnetic measurements) was used to characterize the catalysts. Iron carbidization proceeds much easier for iron species confined inside carbon nanotubes and promoted with Bi and Pb. Iron nanoconfinement inside carbon nanotubes combined with the promotion with Bi or Pb result in a 10-fold higher yield of light olefins. Nanoconfinement in carbon nanotubes mostly leads to better iron dispersion and stability, while the intrinsic activity is only slightly affected. Promotion with Bi and Pb results in a major increase in the site intrinsic activity in both confined and non-confined catalysts. Moreover, over the optimised promoted and confined catalysts, Fischer-Tropsch synthesis occurs even under atmospheric pressure with high conversion and enhanced selectivity to light olefins.
Published: 2019
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49. Versatile Roles of Metal Species in Carbon Nanotube Templates for the Synthesis of Metal–Zeolite Nanocomposite Catalysts

Author: Ovidiu Ersen, Vladimir L. Zholobenko, Valentin Valtchev, Walid Baaziz, Vitaly V. Ordomsky, Bang Gu, Andrei Y. Khodakov, Nuno Batalha, Nilson Romeu Marcilio, Camila Gomes Flores, Laboratoire catalyse et spectrochimie (LCS), Centre National de la Recherche Scientifique (CNRS)-École Nationale Supérieure d'Ingénieurs de Caen (ENSICAEN), Normandie Université (NU)-Normandie Université (NU)-Institut de Chimie du CNRS (INC)-Université de Caen Normandie (UNICAEN), Normandie Université (NU), Unité de Catalyse et Chimie du Solide - UMR 8181 (UCCS), Université d'Artois (UA)-Centrale Lille-Institut de Chimie du CNRS (INC)-Université de Lille-Centre National de la Recherche Scientifique (CNRS), Keele University [Keele], Université de Caen Normandie (UNICAEN), Normandie Université (NU)-Normandie Université (NU)-École Nationale Supérieure d'Ingénieurs de Caen (ENSICAEN), Normandie Université (NU)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Institut de Physique et Chimie des Matériaux de Strasbourg (IPCMS), Université de Strasbourg (UNISTRA)-Centre National de la Recherche Scientifique (CNRS)-Matériaux et Nanosciences Grand-Est (MNGE), Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Réseau nanophotonique et optique, Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Centre National de la Recherche Scientifique (CNRS), Université d'Artois (UA)-Centrale Lille-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Lille, Centrale Lille Institut (CLIL)-Université d'Artois (UA)-Centrale Lille-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Lille, Université de Strasbourg (UNISTRA)-Matériaux et nanosciences d'Alsace (FMNGE), Institut de Chimie du CNRS (INC)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS)-Réseau nanophotonique et optique, and Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)
Subjects: Materials science, chemistry.chemical_element, 02 engineering and technology, Carbon nanotube, replicas, 010402 general chemistry, Heterogeneous catalysis, 01 natural sciences, Catalysis, law.invention, Metal, law, [CHIM]Chemical Sciences, QD, General Materials Science, metal nanoparticles, Zeolite, acidity, ComputingMilieux_MISCELLANEOUS, Nanocomposite, nanocomposite, [CHIM.CATA]Chemical Sciences/Catalysis, [CHIM.MATE]Chemical Sciences/Material chemistry, 021001 nanoscience & nanotechnology, 0104 chemical sciences, promotors, chemistry, Chemical engineering, visual_art, visual_art.visual_art_medium, 0210 nano-technology, Mesoporous material, Cobalt, hard template, catalyst
Abstract: International audience; Metal-zeolite nanocomposites are extensively used in heterogeneous catalysis. The small size of zeolite micropores and non-uniform distribution of the metal component within the zeolite structure can severely reduce the efficiency of these catalysts. In this work, we propose a new single-pot synthesis strategy for the design of metal-zeolite nanocomposites with specific shape, enhanced mesoporosity and uniform distribution of highly dispersed metals such as cobalt, nickel, and magnesium within the zeolite crystals. The strategy involves using metal carbon nanotubes as a secondary hard template. The presence of metal species in carbon nanotube templates is crucial and indispensable for the synthesis of metal zeolite nanocomposites. The multiple roles of the metal carbon nanotubes in the zeolite synthesis are revealed. First, they serve as a replica to create zeolites with specific fibrous morphology. Second, they fulfill the role of a mesoporogen and markedly increase the zeolite secondary porosity. Finally, they act as a vehicle to uniformly introduce the metal functions inside the mesoporous zeolites. Nanocomposites prepared using metal carbon nanotubes have shown enhanced catalytic performance in Fischer-Tropsch synthesis, hydrogenation of aromatics and anisole acylation.
Published: 2019
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50. Design of core-shell titania-heteropolyacid-metal nanocomposites for photocatalytic reduction of CO

Author: Xiang, Yu, Simona, Moldovan, Vitaly V, Ordomsky, and Andrei Y, Khodakov
Abstract: The photocatalytic conversion of CO
Published: 2019

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