Search

The development of highly efficient and stable visible-light-driven photocatalysts for the removal of herbicide 2,4-dichlorophenoxyacetic acid (2,4-D) from water is still a challenge. In this work, Bi 2 MoO 6 (BMO) materials with different morphology were successfully prepared via a simple hydrothermal method by altering the solvent. The morphology of the BMO material is mainly influenced by the solvent used in the synthesis (H 2 O, ethanol, and ethylene glycol or their mixtures) and to a lesser extent by subsequent thermal annealing. BMO with aggregated spheres and nanoplate-like structures hydrothermally synthesized in ethylene glycol (EG) and subsequently calcined at 400 °C (BMO-400 (EG)) showed the highest adsorption capacity and photocatalytic activity compared to other synthesized morphologies. Complete degradation of 2,4-D on BMO upon irradiation with a blue light-emitting diode (LED, λ max = 467 nm) was reached within 150 min, resulting in 2,4-dichlorophenol (2,4-DCP) as the main degradation product. Holes (h + ) and superoxide radicals (⋅O 2 - ) are assumed to be the reactive species observed for the rapid conversion of 2,4-D to 2,4-DCP. The addition of H 2 O 2 to the reaction mixture not only accelerates the degradation of 2,4-DCP but also significantly reduces the total organic carbon (TOC) content, indicating that hydroxyl radicals are crucial for the rapid mineralization of 2,4-D. Under optimal conditions, the TOC value was reduced by 84.5% within 180 min using BMO-400 (EG) and H 2 O 2 . The improved degradation performance of BMO-400 (EG) can be attributed to its particular morphology leading to lower charge transfer resistance, higher electron-hole separation, and larger specific surface area.

Reverse water-gas shift (RWGS) reaction has attracted much attention as a potential approach for CO 2 valorization via the production of synthesis gas, especially over Fe-modified supported Cu catalysts on CeO 2 . However, most studies have focused solely on investigating the RWGS reaction over catalysts with high Cu and Fe loadings, thus leading to an increase in the complexity of the catalytic system and, hence, preventing the gain of any reliable information about the nature of the active sites and reaction mechanism. In this work, a CeO 2 -supported single-atom Cu catalyst modified with iron was synthesized and evaluated for the RWGS reaction. The catalytic results reveal a significant synergistic effect between CuCeO 2 and Fe, demonstrating an activity up to three times higher than the combined catalytic activities of monometallic catalysts (Fe/CeO 2 + CuCeO 2 ) under identical conditions. Various ex situ and in situ/operando techniques are employed to unveil the concealed role of Fe in catalyst activity enhancement. The combined findings from hydrogen temperature-programmed reduction (H 2 -TPR) and operando electron paramagnetic resonance spectroscopy (EPR) reveal that the added Fe predominantly interacts with Cu-containing surface sites, resulting in the stabilization of higher proportions of Cu single sites. Near-ambient pressure X-ray photoelectron spectroscopy (NAP-XPS) and operando EPR results unveil a synergistic interplay of Fe with Cu-containing sites and CeO x domains, efficiently enhancing both the reoxidation of Cu + in Cu + -O v -Ce 3+ moieties and the reducibility of Ce 4+ in CeO x domains under RWGS conditions. Detailed mechanistic studies reveal that the RWGS reaction predominantly proceeds via the redox mechanism., Competing Interests: The authors declare no competing financial interest., (© 2024 The Authors. Published by American Chemical Society.)

Earth abundant metal-based heterogeneous catalysts with highly active and at the same time stable isolated metal sites constitute a key factor for the advancement of sustainable and cost-effective chemical synthesis. In particular, the development of more practical, and durable iron-based materials is of central interest for organic synthesis, especially for the preparation of chemical products related to life science applications. Here, we report the preparation of Fe-single atom catalysts (Fe-SACs) entrapped in N-doped mesoporous carbon support with unprecedented potential in the preparation of different kinds of amines, which represent privileged class of organic compounds and find increasing application in daily life. The optimal Fe-SACs allow for the reductive amination of a broad range of aldehydes and ketones with ammonia and amines to produce diverse primary, secondary, and tertiary amines including N-methylated products as well as drugs, agrochemicals, and other biomolecules (amino acid esters and amides) utilizing green hydrogen., (© 2024 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH.)

The nature of the support can fundamentally affect the function of a heterogeneous catalyst. For the novel type of isolated metal atom catalysts, sometimes referred to as single-atom catalysts, systematic correlations are still rare. Here, we report a general finding that Pd on nitride supports (non-metal and metal nitride) features a higher oxidation state compared to that on oxide supports (non-metal and metal oxide). Through thorough oxidation state investigations by X-ray absorption spectroscopy (XAS), X-ray photoelectron spectroscopy (XPS), CO-DRIFTS, and density functional theory (DFT) coupled with Bader charge analysis, it is found that Pd atoms prefer to interact with surface hydroxyl group to form a Pd(OH) x species on oxide supports, while on nitride supports, Pd atoms incorporate into the surface structure in the form of Pd-N bonds. Moreover, a correlation was built between the formal oxidation state and computational Bader charge, based on the periodic trend in electronegativity., (© 2024 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH.)

Improving the selectivity in the oxidative coupling of methane to ethane/ethylene poses a significant challenge for commercialization. The required improvements are hampered by the uncertainties associated with the reaction mechanism due to its complexity. Herein, we report about 90 % selectivity to the target products at 11 % methane conversion over Gd 2 O 3 -based catalysts at 700 °C using N 2 O as the oxidant. Sophisticated kinetic studies have suggested the nature of adsorbed oxygen species and their binding strength as key parameters for undesired methane oxidation to carbon oxides. These descriptors can be controlled by a metal oxide promoter for Gd 2 O 3 ., (© 2024 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH.)

Molecular copper catalysts have emerged as promising candidates for the electrochemical reduction of CO 2 . Notable features of such systems include the ability of Cu to generate C 2+  products and the well-defined active sites that allow for targeted structural tuning. However, the frequently observed in situ formation of Cu nanoclusters has undermined the advantages of the molecular frameworks. It is therefore desirable to develop Cu-based catalysts that retain their molecular structures during electrolysis. In this context, a heterogenized binuclear hydroxo-bridged phenanthroline Cu(II) compound with a short Cu···Cu distance is reported as a simple yet efficient catalyst for electrogeneration of ethylene and other C 2 products. In an aqueous electrolyte, the catalyst demonstrates remarkable performance, with excellent Faradaic efficiency for C 2 products (62%) and minimal H 2 evolution (8%). Furthermore, it exhibits high stability, manifested by no observable degradation during 15 h of continuous electrolysis. The preservation of the atomic distribution of the active sites throughout electrolysis is substantiated through comprehensive characterizations, including X-ray photoelectron and absorption spectroscopy, scanning and transmission electron microscopy, UV-vis spectroscopy, as well as control experiments. These findings establish a solid foundation for further investigations into targeted structural tuning, opening new avenues for enhancing the catalytic performance of Cu-based molecular electrocatalysts., (© 2023 The Authors. Advanced Materials published by Wiley-VCH GmbH.)

A protocol for efficient N -alkylation of benzamides with alcohols in the presence of cobalt-nanocatalysts is described. Key to the success of this general methodology is the use of highly dispersed cobalt nanoparticles supported on carbon, which are obtained from the pyrolysis of cobalt(ii) acetate and o -phenylenediamine as a ligand at suitable temperatures. The catalytic material shows a broad substrate scope and good tolerance to functional groups. Apart from the synthesis of a variety of secondary amides (>45 products), the catalyst allows for the conversion of more challenging aliphatic alcohols and amides, including biobased and macromolecular amides. The practical applicability of the catalyst is underlined by the successful recycling and reusability., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

Catalytic hydrogenations are important and widely applied processes for the reduction of organic compounds both in academic laboratories and in industry. To perform these reactions in sustainable and practical manner, the development and applicability of non-noble metal-based heterogeneous catalysts is crucial. Here, we report highly active and air-stable nickel nanoparticles supported on mesoporous silica (MCM-41) as a general and selective hydrogenation catalyst. This catalytic system allows for the hydrogenation of carbonyl compounds, nitroarenes, N-heterocycles, and unsaturated carbon─carbon bonds in good to excellent selectivity under very mild conditions (room temperature to 80°C, 2 to 10 bar H 2 ). Furthermore, the optimal nickel/meso-silicon dioxide catalyst is reusable (4 cycles) without loss of its catalytic activity.

A setup for dispersive X-ray absorption spectroscopy (XAS) with spatial, temporal and energy resolution is presented. Through investigation of a Mo/HZSM-5 catalyst during the dehydroaromatization of methane we observed a reduction gradient along the packed bed. Our new method represents an unprecedented addition to the analytical toolbox for in situ characterizations.

Low-dimensional materials have unique optical, electronic, mechanical, and chemical properties that make them desirable for a wide range of applications. Nano-scaling materials to confine transport in at least one direction is a common method of designing materials with low-dimensional electronic structures. However, bulk materials give rise to low-dimensional electronic structures when bonding is highly anisotropic. Layered Zintl phases are excellent candidates for investigation due to their directional bonding, structural variety, and tunability. However, the complexity of the structure and composition of many layered Zintl phases poses a challenge for producing phase-pure bulk samples to characterize. Eu 11 Zn 4 Sn 2 As 12 is a layered Zintl phase of significant complexity that is of interest for its magnetic, electronic, and thermoelectric properties. To prepare phase-pure Eu 11- x Na x Zn 4 Sn 2 As 12 , a binary EuAs phase was employed as a precursor, along with NaH. Experimental measurements reveal low thermal conductivity and a high Seebeck coefficient, while theoretical electronic structure calculations reveal a transition from a 3D to 2D electronic structure with increasing carrier concentration. Simulated thermoelectric properties also indicate anisotropic transport, and thermoelectric property measurements confirm the nonparabolicity of the relevant bands near the Fermi energy. Thermoelectric efficiency is known to improve as the dimensionality of the electronic structure is decreased, making this a promising material for further optimization and opening the door to further exploitation of layered Zintl phases with low-dimensional electronic structures for thermoelectric applications., Competing Interests: The authors declare no competing financial interest., (© 2023 The Authors. Published by American Chemical Society.)

Heterogeneously catalyzed N-formylation of amines to formamide with CO 2 /H 2 is highly attractive for the valorization of CO 2 . However, the relationship of the catalytic performance with the catalyst structure is still elusive. Herein, mixed valence catalysts containing Cu 2 O/Cu interface sites were constructed for this transformation. Both aliphatic primary and secondary amines with diverse structures were efficiently converted into the desired formamides with good to excellent yields. Combined ex and in situ catalyst characterization revealed that the presence of Cu 2 O/Cu interface sites was vital for the excellent catalytic activity. Density functional theory (DFT) calculations demonstrated that better catalytic activity of Cu 2 O/Cu(111) than Cu(111) is attributed to the assistance of oxygen at the Cu 2 O/Cu interface (O inter ) in formation of O inter -H moieties, which not only reduce the apparent barrier of HCOOH formation but also benefit the desorption of the desired N-formylated amine, leading to high activity and selectivity., (© 2023 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH.)

The selective hydrogenation of benzofurans in the presence of a heterogeneous non-noble metal catalyst is reported. The developed optimal catalytic material consists of cobalt-cobalt oxide core-shell nanoparticles supported on silica, which has been prepared by the immobilization and pyrolysis of cobalt-DABCO-citric acid complex on silica under argon at 800 °C. This novel catalyst allows for the selective hydrogenation of simple and functionalized benzofurans to 2,3-dihydrobenzofurans as well as related heterocycles. The versatility of the reported protocol is showcased by the reduction of selected drugs and deuteration of heterocycles. Further, the stability, recycling, and reusability of the Co-nanocatalyst are demonstrated., (© 2023 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH.)

The pronounced effects of the composition of four-atom monometallic Cu and Pd and bimetallic CuPd clusters and the support on the catalytic activity and selectivity in the oxidative dehydrogenation of cyclohexene are reported. The ultra-nanocrystalline diamond supported clusters are highly active and dominantly produce benzene; some of the mixed clusters also produce cyclohexadiene, which are all clusters with a much suppressed combustion channel. The also highly active TiO 2 -supported tetramers solely produce benzene, without any combustion to CO 2 . The selectivity of the zirconia-supported mixed CuPd clusters and the monometallic Cu cluster is entirely different; though they are less active in comparison to clusters with other supports, these clusters produce significant fractions of cyclohexadiene, with their selectivity towards cyclohexadiene gradually increasing with the increasing number of copper atoms in the cluster, reaching about 50% for Cu 3 Pd 1 . The zirconia-supported copper tetramer stands out from among all the other tetramers in this reaction, with a selectivity towards cyclohexadiene of 70%, which far exceeds those of all the other cluster-support combinations. The findings from this study indicate a positive effect of copper on the stability of the mixed tetramers and potential new ways of fine-tuning catalyst performance by controlling the composition of the active site and via cluster-support interactions in complex oxidative reactions under the suppression of the undesired combustion of the feed.

Hypothesis: Lateral adhesion forces are a fundamental property of liquid-solid interactions and a key aspect of dynamic droplet mobility. But, commonly applied conventional wetting analysis is limited to static and quasi-static methods and cannot resolve dynamic and spatial liquid-solid interactions. However, droplet mobility is assumed to be affected by chemical and topographic surface inhomogeneities introduced by femtosecond laser treatment., Experiments: In this study, we used a customized droplet adhesion force instrument to determine lateral adhesion forces on various femtosecond laser-structured surface designs to obtain a deeper understanding of the dynamic droplet motion with regard to chemical and topographic surface features., Findings: We show that the droplet motion was highly affected by the chemical and topographical surface design and local inhomogeneities. The droplet mobility on femtosecond laser-structured surfaces could be classified into a static, a transfer, and a kinetic regime, which is essential for designing surfaces with extreme wetting characteristics and a wide range of scientific and industrial processes. Furthermore, with proper tailoring of surface structures and chemical modification, we were able to provoke adhesion forces on self-organized laser microstructures similar to those found on the natural lotus leaves., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2022 The Author(s). Published by Elsevier Inc. All rights reserved.)

Silica supported ultrasmall Ni-nanoparticles allow for general and selective hydrogenation of all kinds of nitriles to primary amines under mild conditions. By calcination of a template material generated from Ni(ii)nitrate and colloidal silica under air and subsequent reduction in the presence of molecular hydrogen the optimal catalyst is prepared. The prepared supported nanoparticles are stable, can be conveniently used and easily recycled. The applicability of the optimal catalyst material is shown by hydrogenation of >110 diverse aliphatic and aromatic nitriles including functionalized and industrially relevant substrates. Challenging heterocyclic nitriles, specifically cyanopyridines, provided the corresponding primary amines in good to excellent yields. The resulting amines serve as important precursors and intermediates for the preparation of numerous life science products and polymers., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

We communicate the assembly of a solid, Ce-promoted Ni-based composite that was applied as catalyst for the hydrogenation of nitroarenes to afford the corresponding organic amines. The catalytically active material described herein was obtained through pyrolysis of a SiO 2 -pellet-supported bimetallic Ni-Ce complex that was readily synthesized prior to use from a MeO-functionalized salen congener, Ni(OAc) 2 ·4 H 2 O, and Ce(NO 3 ) 3 ·6 H 2 O. Rewardingly, the requisite ligand for the pertinent solution phase precursor was accessible upon straightforward and time-saving imine condensation of ortho -vanillin with 1,3-diamino-2,2'-dimethylpropane. The introduced catalytic protocol is operationally simple in that the whole reaction set-up is quickly put together on the bench without the need of cumbersome handling in a glovebox or related containment systems. Moreover, the advantageous geometry and compact-sized nature of the used pellets renders the catalyst separation and recycling exceptionally easy.

A convenient and practical diastereoselective cis -hydrogenation of multi-substituted pyridines and arenes is reported. Applying a novel heterogeneous ruthenium catalyst, the corresponding piperidines and cyclohexanes are obtained in high yields (typically >80%) with a good functional group tolerance under mild conditions. The robust ruthenium supported catalyst is smoothly prepared and can be reused multiple times without activity loss.

There is a constant need for deuterium-labelled products for multiple applications in life sciences and beyond. Here, a new class of heterogeneous catalysts is reported for practical deuterium incorporation in anilines, phenols, and heterocyclic substrates. The optimal material can be conveniently synthesised and allows for high deuterium incorporation using deuterium oxide as isotope source. This new catalyst has been fully characterised and successfully applied to the labelling of natural products as well as marketed drugs., (© 2022 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH.)

Isotope labelling, particularly deuteration, is an important tool for the development of new drugs, specifically for identification and quantification of metabolites. For this purpose, many efficient methodologies have been developed that allow for the small-scale synthesis of selectively deuterated compounds. Due to the development of deuterated compounds as active drug ingredients, there is a growing interest in scalable methods for deuteration. The development of methodologies for large-scale deuterium labelling in industrial settings requires technologies that are reliable, robust and scalable. Here we show that a nanostructured iron catalyst, prepared by combining cellulose with abundant iron salts, permits the selective deuteration of (hetero)arenes including anilines, phenols, indoles and other heterocycles, using inexpensive D 2 O under hydrogen pressure. This methodology represents an easily scalable deuteration (demonstrated by the synthesis of deuterium-containing products on the kilogram scale) and the air- and water-stable catalyst enables efficient labelling in a straightforward manner with high quality control., (© 2022. The Author(s).)

Hydrogenation of CO 2 is very attractive for transforming this greenhouse gas into valuable high energy density compounds. In this work, we developed a highly active and stable Ru/TiO 2 catalyst for CO 2 methanation prepared by a solgel method that revealed much higher activity in methanation of CO 2 (ca. 4-14 times higher turnover frequencies at 140-210°C) than state-of-the-art Ru/TiO 2 catalysts and a control sample prepared by wetness impregnation. This is attributed to a high concentration of O-vacancies, inherent to the solgel methodology, which play a dual role for 1) activation of CO 2 and 2) transfer of electrons to interfacial Ru sites as evident from operando DRIFTS and in situ EPR investigations. These results suggest that charge transfer from O-vacancies to interfacial Ru sites and subsequent electron donation from filled metal d-orbitals to antibonding orbitals of adsorbed CO are decisive factors in boosting the CO 2 methanation activity., Competing Interests: The authors declare no competing interests, (© 2022 The Author(s).)

The introduction of deuterium atoms into organic compounds is of importance for basic chemistry, material sciences, and the development of drugs in the pharmaceutical industry, specifically for identification and quantification of metabolites. Hence, methodologies for the synthesis of selectively labelled compounds continue to be a major area of interest for many scientists. Herein, we present a practical and stable heterogeneous copper catalyst, which permits for dehalogenative deuteration via water-gas shift reaction at comparably low temperature. This novel approach allows deuteration of diverse (hetero)aryl halides with good functional group tolerance, and no reduction of the aromatic rings or other easily reducible formyl and cyano groups. Multi-gram experiments show the potential of this method in organic synthesis and medicinal chemistry., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

Co-axial electrospinning was applied for the structuring of non-woven webs of TiO 2 nanofibers loaded with Ag, Au, and CuO nanoparticles. The composite layers were tested in an electrochromic half-cell assembly. A clear correlation between the nanoparticle composition and electrochromic effect in the nanofibrous composite is observed: TiO 2 loaded with Ag reveals a black-brown color, Au shows a dark-blue color, and CuO shows a dark-green color. For electrochromic applications, the Au/TiO 2 layer is the most promising choice, with a color modulation time of 6 s, transmittance modulation of 40%, coloration efficiency of 20 cm 2 /C, areal capacitance of 300 F/cm 2 , and cyclic stability of over 1000 cycles in an 18 h period. In this study, an unexplored path for the rational design of TiO 2 -based electrochromic device is offered with unique color-switching and optical efficiency gained by the fibrous layer. It is also foreseen that co-axial electrospinning can be an alternative nanofabrication technique for smart colored windows., Competing Interests: The authors declare no competing financial interest., (© 2021 The Authors. Published by American Chemical Society.)

In this study, different pretreatment strategies of sugarcane bagasse prior to citric acid modification were investigated in terms of Pb 2+ adsorption capacity. Pretreatment strategies included the use of NaOH, HCl, and C 2 H 5 OH in various concentrations. In order to fundamentally understand how these pretreatment methods affect the modification of sugarcane bagasse by citric acid as well as the Pb 2+ adsorption capacity of sugarcane bagasse, three main components of sugarcane bagasse namely cellulose, hemicellulose, and lignin were isolated and esterified by citric acid under the same conditions. ATR-FTIR, XPS, SEM, and an analysis of the number of carboxylic acid groups were used to investigate the physicochemical and chemical properties of the materials. These three components were proved to participate in adsorption and induce the esterification with citric acid. Hence, pretreatment with ethanol and 0.01 M NaOH which could retain cellulose, hemicellulose, and lignin in sugarcane bagasse achieved a high Pb 2+ adsorption capacity, i.e., 122.4 and 97 mg/g after the esterification with citric acid. In contrast, pretreatment with 0.5 M NaOH and 0.1 M HCl removed lignin and hemicellulose, leading to the lowest value of approximately 45 mg/g for citric acid esterified-pretreated sugarcane bagasse. XPS analysis and number of carboxylic group measurement confirmed the esterification between bagasse and citric acid. To understand the adsorption mechanism of adsorbent, two kinetic models including pseudo-first-order model and pseudo-second-order model were applied. The experimental data were well described by the pseudo-second-order model. The adsorption isotherm data were fitted Langmuir and Freundlich.

Investigating a catalyst under relevant application conditions is experimentally challenging and parameters like reaction conditions in terms of temperature, pressure, and reactant mixing ratios, as well as catalyst design, may significantly impact the obtained experimental results. For Pt catalysts widely used for the oxidation of carbon monoxide, there is keen debate on the oxidation state of the surface at high temperatures and at/above atmospheric pressure, as well as on the most active surface state under these conditions. Here, we employ a nanoreactor in combination with single-particle plasmonic nanospectroscopy to investigate individual Pt catalyst nanoparticles localized inside a nanofluidic model pore during carbon monoxide oxidation at 2 bar in the 450-550 K temperature range. As a main finding, we demonstrate that our single-particle measurements effectively resolve a kinetic phase transition during the reaction and that each individual particle has a unique response. Based on spatially resolved measurements, we furthermore observe how reactant concentration gradients formed due to conversion inside the model pore give rise to position-dependent kinetic phase transitions of the individual particles. Finally, employing extensive electrodynamics simulations, we unravel the surface chemistry of the individual Pt nanoparticles as a function of reactant composition and find strongly temperature-dependent Pt-oxide formation and oxygen spillover to the SiO 2 support as the main processes. These results therefore support the existence of a Pt surface oxide in the regime of high catalyst activity and demonstrate the possibility to use plasmonic nanospectroscopy in combination with nanofluidics as a tool for in situ studies of individual catalyst particles., Competing Interests: The authors declare no competing financial interest., (© 2021 American Chemical Society.)

The effect of chemical solvents on the wetting state of laser-structured surfaces over time is systematically examined in this paper. By using a 300-fs laser, nanostructures were generated on Ti6Al4V, subsequently cleaned in an ultrasonic bath with different solvents and stored in ambient air. The static contact angle showed significant differences for cleaning with various solvents, which, depending on the applied cleaning and time, amounted up to 100°. X-ray photoelectron spectroscopy analyses reveal that the cleaning of the laser-structured surfaces affects the surface chemistry and the aging behavior of the surfaces, even with highly volatile solvents. The effect of the chemical surface modification is particularly noticeable when using alcohols for cleaning, which, due to their OH groups, cause highly hydrophilic behavior of the surface after one day of storage. Over the course of 14 days, enrichment with organic groups from the atmosphere occurs on the surface, which leads to poorer wetting on almost every structured surface. In contrast, the cleaning in hexane leads to a fast saturation of the surface with long-chain carbon groups and thus to a time-independent hydrophobic behavior.

Nanoconfinement in porous catalysts may induce reactant concentration gradients inside the pores due to local conversion. This leads to inefficient active material use since parts of the catalyst may be trapped in an inactive state. Experimentally, these effects remain unstudied due to material complexity and required high spatial resolution. Here, we have nanofabricated quasi-two-dimensional mimics of porous catalysts, which combine the traits of nanofluidics with single particle plasmonics and online mass spectrometry readout. Enabled by single particle resolution at operando conditions during CO oxidation over a Cu model catalyst, we directly visualize reactant concentration gradient formation due to conversion on single Cu nanoparticles inside the "model pore" and how it dynamically controls oxidation state-and, thus, activity-of particles downstream. Our results provide a general framework for single particle catalysis in the gas phase and highlight the importance of single particle approaches for the understanding of complex catalyst materials., (Copyright © 2020 The Authors, some rights reserved; exclusive licensee American Association for the Advancement of Science. No claim to original U.S. Government Works. Distributed under a Creative Commons Attribution NonCommercial License 4.0 (CC BY-NC).)

The first examples of heterogeneous Fe-catalysed cyclopropanation reactions are presented. Pyrolysis of in situ -generated iron/phenanthroline complexes in the presence of a carbonaceous material leads to specific supported nanosized iron particles, which are effective catalysts for carbene transfer reactions. Using olefins as substrates, cyclopropanes are obtained in high yields and moderate diastereoselectivities. The developed protocol is scalable and the activity of the recycled catalyst after deactivation can be effectively restored using an oxidative reactivation protocol under mild conditions., (This journal is © The Royal Society of Chemistry 2020.)

For the first time, the oxidative dehydrogenation of (-)-menthol to (-)-menthone and (+)-isomenthone in a marketable quality was carried out in a continuous gas phase reactor as a sustainable process using molecular oxygen as green oxidant and solid catalysts which do not contaminate the product mixture and which are easily to remove. The diastereomeric purity remained largely unchanged. Three types of catalysts were found to be very active and selective in the formation of menthone and isomenthone: AgSr/SiO 2 , CuO distributed on a basic support and RuMnCe/CeO 2 , where Ru, Mn and Ce exist in an oxidized state. The best overall yield of menthon/isomenthone obtained with an Ag-based catalyst was 58 % at 64 % selectivity, with a Cu-based catalyst 41 % at 51 % selectivity and with a Ru-based catalyst 68 % at 73 % selectivity. Reaction conditions were widely optimized., Competing Interests: The authors declare no conflict of interest.

Hydroformylation of olefins has been studied in the presence of specific heterogeneous cobalt nanoparticles. The catalytic materials were prepared by pyrolysis of preformed cobalt complexes deposited onto different inorganic supports. Atomic absorption spectroscopy (AAS) measurements indicated a correlation of catalyst activity and cobalt leaching as well as a strong influence of the heterogeneous support on the productivity. These new, low-cost, easy-to-handle catalysts can substitute more toxic, unstable and volatile cobalt carbonyl complexes for hydroformylations on a laboratory scale., (© 2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

A combined experimental and theoretical investigation of Ag-Pt sub-nanometer clusters as heterogeneous catalysts in the CO→CO 2 reaction (COox) is presented. Ag 9 Pt 2 and Ag 9 Pt 3 clusters are size-selected in the gas phase, deposited on an ultrathin amorphous alumina support, and tested as catalysts experimentally under realistic conditions and by first-principles simulations at realistic coverage. In situ GISAXS/TPRx demonstrates that the clusters do not sinter or deactivate even after prolonged exposure to reactants at high temperature, and present comparable, extremely high COox catalytic efficiency. Such high activity and stability are ascribed to a synergic role of Ag and Pt in ultranano-aggregates, in which Pt anchors the clusters to the support and binds and activates two CO molecules, while Ag binds and activates O 2 , and Ag/Pt surface proximity disfavors poisoning by CO or oxidized species., (© 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Apart from large surface areas, low activation energies are essential for efficient reactions, particularly in heterogeneous catalysis. Here, we show that not only the size of nanoparticles but also their detailed morphology can crucially affect reaction kinetics, as demonstrated for mass-selected, soft-landed, and oxidized cobalt clusters in a 6 nm to 18 nm size range. The method of reflection high-energy electron diffraction is extended to the quantitative determination of particle activation energies which is applied for repeated oxidation and reduction cycles at the same particles. We find unexpectedly small activation barriers for the reduction reaction of the largest particles studied, despite generally increasing barriers for growing sizes. We attribute these observations to the interplay of reaction-specific material transport with a size-dependent inner particle morphology.

It is generally accepted that optimal particle sizes are key for efficient nanocatalysis. Much less attention is paid to the role of morphology and atomic arrangement during catalytic reactions. Here, we unravel the structural, stoichiometric, and morphological evolution of gas-phase produced and partially oxidized cobalt nanoparticles in a broad size range. Particles with diameters between 1.4 and 22 nm generated in cluster sources are size selected and deposited on amorphous alumina (Al2O3) and ultrananocrystalline diamond (UNCD) films. A combination of different techniques is employed to monitor particle properties at the stages of production, exposure to ambient conditions, and catalytic reaction, in this case, the oxidative dehydrogenation of cyclohexane at elevated temperatures. A pronounced size dependence is found, naturally classifying the particles into three size regimes. While small and intermediate clusters essentially retain their compact morphology, large particles transform into hollow spheres due to the nanoscale Kirkendall effect. Depending on the substrate, an isotropic (Al2O3) or anisotropic (UNCD) Kirkendall effect is observed. The latter results in dramatic lateral size changes. Our results shed light on the interplay between chemical reactions and the catalyst's structure and provide an approach to tailor the cobalt oxide phase composition required for specific catalytic schemes.

The diversity of nanoparticle shapes generated by condensation from gaseous matter reflects the fundamental competition between thermodynamic equilibration and the persistence of metastable configurations during growth. In the kinetically limited regime, intermediate geometries that are favoured only in early formation stages can be imprinted in the finally observed ensemble of differently structured specimens. Here we demonstrate that single-shot wide-angle scattering of femtosecond soft X-ray free-electron laser pulses allows three-dimensional characterization of the resulting metastable nanoparticle structures. For individual free silver particles, which can be considered frozen in space for the duration of photon exposure, both shape and orientation are uncovered from measured scattering images. We identify regular shapes, including species with fivefold symmetry and surprisingly large aspect ratio up to particle radii of the order of 100 nm. Our approach includes scattering effects beyond Born's approximation and is remarkably efficient-opening up new routes in ultrafast nanophysics and free-electron laser science.