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Catalytic converting the lignin-derived bio-oil to liquid fuel is one promising methodology to reduce the dependence on petroleum-based fuel while easing the atmospheric carbon dioxide burden. Hydrodeoxygenation (HDO) is one commonly used method to convert and upgrade bio-oil from biomass. In the present work, a Ru-promoted MoFeP/Al 2 O 3 catalyst was prepared and evaluated the HDO performance by converting two model compounds, guaiacol and anisole with a batch reactor at 250 °C. This catalyst shows a quite good HDO performance over the two model compounds, in which, oxygen was removed from the phenolic and hydrocarbons were produced as the product. Kinetic studies were also performed to build the reaction network and elucidate the reaction pathway of guaiacol and anisole HDO reactions. The primary, secondary, and tertiary products can be identified for the HDO reactions. A better understanding of HDO chemistry from the fundamental study can lead to more efficient catalysts for the target products. [Display omitted] • A highly active Ru-MoFeP/Al 2 O 3 was proposed in HDO reaction. • Reaction network of guaiacol and anisole HDO reaction were proposed. • Primary product, secondary or tertiary products can be identified. [ABSTRACT FROM AUTHOR]

Bioproducts are chemicals derived from renewable biological resources and have the potential to replace petrochemicals in the future to tackle the arising environmental problems. Among them, lactic acid (LaA) is attracting significant focus from both academia and industry due to its wide application in our daily life. In this study, lactic acid is produced from the chemo-catalytic converting the glucose over the homogeneous ErCl 3 catalyst in an aqueous solution. The highest LaA yield of 97% was obtained at a full glucose conversion on this homogeneous catalyst at 260 °C through process optimization. Furthermore, the techno-economic analysis (TEA) was leveraged for the concept design of LaA biorefineries. Three parameters, namely the selling price of LaA, the price of glucose, and the catalyst recyclability were identified for the overall profit. Therefore, this work highlights the notable ability of TEA for the concept design or simulation to screen the promising biorefinery industrial process, and intuitively provide us with the internal rate of return of a certain chemical process. Thus, this work is supposed to provide the feasibility of LaA acid production from a chemo-catalytic process from both the technical and scientific points of view. [Display omitted] • A high lactic acid yield was obtained on the ErCl 3 homogeneous catalyst. • The potential of using converting glucose to lactic acid was analyzed. • Concept design and tech-economic analysis were performed. [ABSTRACT FROM AUTHOR]

[Display omitted] • Using UV–vis-NIR to analyze the kinetics of ethylene oxychlorination. • Co-promoter effect of alkali and alkali earth metals on ethylene oxychlorination. • Methods to design and predict the reaction rate and Cu2+ concentration for the steady-state. The comprehensive kinetic study for CuCl 2 /γ-Al 2 O 3 -based catalysts was performed to elucidate the co-promoter effect in the ethylene oxychlorination, one of the most significant industrial processes to produce vinyl chloride monomer. Kinetic analysis was performed separately by transient kinetic studies, taking account of the reduction and oxidation steps in the catalytic cycle. The promoter effects on ethylene oxychlorination were ascribed to their influence on the Cu2+ reduction or Cu+ oxidation in the catalytic cycle. The reaction rate-diagram was gained and used to predict the steady-state reaction rate and Cu oxidation state by an operando setup combing MS and UV–vis-NIR spectroscopy. The results indicated that the K-doped catalyst could greatly increase the reaction rate of the oxidation step, which gave rise to higher Cu2+ concentration on the catalyst. Mg-doped catalyst had a great effect on enhancing the reaction rate for the reduction step. K and Mg co-doped catalyst had the dual effect, both the reaction rate and Cu oxidation state were located between K and Mg mono-doped catalyst. The results of steady-state reactions indicated that the reaction rates were quite close with that predicated by the rate-diagram. Byproduct analysis during the steady-state was also performed, the results demonstrated that the co-promoted catalysts can also reduce the byproduct formation. The current study is expected to provide one way for exploring the potential benefits of co-promotion on CuCl 2 /γ-Al 2 O 3 -based industrial oxychlorination catalysts to improve the catalytic performance and understand the reaction further. [ABSTRACT FROM AUTHOR]

[Display omitted] • Initiation and progress of carbon formation on alloy 601 surfaces captured. • Less carbon under infinite (I- a c) than under finite low carbon (FL- a c) activity. • Raman spectroscopy: different degree of ordering of the carbon formed. • CO only (I- a c): Thin Cr 2 O 3 surface scale stabilized; grain boundaries beneficial. • In synthesis gas (FL- a c): (Ni, Fe, Cr) 3 O 4 spinel redox process promotes carbon. Ni and Fe are excellent catalysts for carbon formation, and industrial alloys are therefore susceptible to metal dusting corrosion; a costly issue in e.g. synthesis gas manufacture. The objective of this work is to better understand the initial reaction phenomena leading to metal dusting, and thereby minimize the corrosion through optimum alloy selection and pretreatment. Pre-oxidized alloy 601 samples were subjected to carburizing gaseous environments at 750 °C, and carbon formation and surface oxide layer development were investigated by SEM, optical microscopy, AES and Raman spectroscopy. Thin (S)TEM/EDS cross-section lamellae were prepared by Focussed Ion Beam milling. Beyond the initial incubation period, less carbon is formed under 10% CO/Ar than under synthesis gas with finite low carbon activity. Cr 2 O 3 evolves as a thin surface oxide layer with only CO reacting and more ordered carbon develops with increasing exposure time. In contrast, oxidation yields (Ni, Fe, Cr) 3 O 4 spinel formation while the materializing carbon remains its disorder during prolonged exposure to synthesis gas. The metal dusting corrosion rate is hence lowered due to Cr 2 O 3 stabilization, while the spinel represents an unstable redox state that continuously yields new carbon. A fine-grained alloy surface structure is also found beneficial to the Cr 2 O 3 formation. [ABSTRACT FROM AUTHOR]

[Display omitted] • Polyethylenimine over mesoporous carbon spheres solid sorbent for CO 2 capture. • CO 2 capture capacity (3.22 mmol/g) was achieved on 62.5PEI/MCS-1.1. • PEI /MCS will be one of the ideal candidates for CO 2 capture in the future. A novel low-concentration CO 2 capture material (PEI/MCS) was developed by loading polyethylenimine (PEI) over mesoporous carbon spheres (MCS) with high porosity. The effects of pore structure, PEI loading, capture temperature, and promoters on CO 2 capture of PEI/MCS were studied. The MCS with perfect spherical morphology was successfully synthesized by a hard-template assisted reverse emulsion method. The pore structure of MCS was adjusted by tuning the ratio of silica to carbon (Si/C) in the precursors. With increasing the Si/C from 0.8 to 1.1, the pore volume of MCS increased from 1.25 to 2.68 cm3/g. The optimal PEI loadings depending on the pore volume of MCS were 45, 62.5, and 65 wt.% for MCS-0.8, MCS-1.1, and MCS-1.5, respectively. The highest CO 2 capture capacity (3.22 mmol/g) was achieved on 62.5PEI/MCS-1.1 at CO 2 partial pressure of 0.05 bar (5 vol.%, a typical concentration of the tail gas from natural gas power plant and natural gas processing plant) and temperature of 75 °C, outperforming most of the solid amine sorbents reported at similar condition. However, the cycling stability of PEI/MCS is poor at the capture-regeneration temperature of 75 °C. The promoters Span 80 and 1,2-epoxybutane did not show remarkable effect on the cycling stability of PEI/MCS at 75 °C. Decreasing the capture-regeneration temperature can significantly improve the stability of PEI/MCS and there is almost no CO 2 capacity loss (regeneration >99.5 %) when the temperature decreased to 50 °C. As a result of high CO 2 capacity and excellent regenerability and stability, PEI /MCS will be one of the ideal candidates for CO 2 capture in the future. [ABSTRACT FROM AUTHOR]

[Display omitted] • The electronic structure of V 2 O 3 upon single-atom doping is examined. • A weak Lewis acid-base interaction is found to occur on the pristine surface. • The first dehydrogenation step is identified as the rate-limiting step for PDH. • Mn 1 -V 2 O 3 is suggested to be a good catalyst candidate for PDH. Vanadium-oxide-based catalysts have recently been found very promising for the catalytic dehydrogenation of propane. In this work, self-consistent density functional theory calculations have been performed to examine how the electronic structure of the V 2 O 3 (0001) surface is modified by single-atom doping and how the catalytic properties can be tailored to propane dehydrogenation. The structural stability of single-atom-doped V 2 O 3 (0001) surfaces is assessed by comparing the adsorption energies of single atoms with the cohesive energies of bulk metals. A weak Lewis acid-base interaction is found to occur on the pristine surface, which can be strengthened and weakened by substitution of single atoms for V and O, respectively. On these two types of oxide surfaces, single atoms act as promoters and active sites. The first dehydrogenation step is identified as the rate-limiting step by microkinetic analysis. On all the single-atom-doped surfaces, the activation energy for water formation is higher than that for hydrogen recombination, implying that reduction of the oxide surfaces is difficult to take place during the course of the reaction. If a compromise between the catalytic activity and catalyst selectivity is made, Mn 1 -V 2 O 3 is suggested to be a good candidate as the catalyst for propane dehydrogenation. [ABSTRACT FROM AUTHOR]

[Display omitted] • Support effects exist on Cs/Al 2 O 3 catalyzed aldol condensation of MeOAc with HCHO. • The strong interaction promotes the dispersion of Cs on Al 2 O 3. • The composition of Cs species varies with the identity of Al 2 O 3. • A balance between acidic and basic sites contributes to the production of MA. In this work, the support effects on vapor-phase aldol condensation of methyl acetate (MeOAc) with formaldehyde (HCHO) over cesium catalysts are understood by the employment of Al 2 O 3 with different morphologies and crystal phases. The structural and electronic properties of these supported Cs catalysts are characterized by multiple techniques, such as XRD, HAADF-STEM, EDS-mapping, XPS, NH 3 -TPD and CO 2 -TPD. The Cs species are found to be highly dispersed on the Al 2 O 3 surfaces, and their compositions vary with the identity of Al 2 O 3. A combined catalyst characterization and testing results indicates a balance between acidic and basic sites, i.e., an acid-base synergy, for the production of MA: the excess acidic sites lead to the lower MA selectivity due to the promoted further condensation, while the excess basic sites with the lower MeOAc conversion due to the insufficient activated HCHO species. These insights could be valuable for the design and optimization of catalysts for this reaction. [ABSTRACT FROM AUTHOR]

Nanocrystalline ZnO/CNT with enhanced electrochemical reduction of CO 2 to syngas [Display omitted] • Faradaic efficiency of synthesis gas of more than 75% was achieved on small ZnO particles. • The H 2 /CO ratio can be tailored by the ZnO particle size. • DFT study revealed the ZnO surface stabilizes CO 2 * and COOH* intermediates, therefore more active for CO 2 activation. • ZnO is promising for electrochemical syngas production. Electrochemical reduction of CO 2 and H 2 O can provide a promising pathway to synthesis gas generation for renewable electric energy storage and fuel production with the closed anthropogenic carbon cycle. However, the lack of affordable highly active catalysts to activate the stable CO 2 and H 2 O molecules presents a substantial challenge. Here we report ZnO supported on nanocarbon as a cost-effective and active catalyst for selective conversion of CO 2 and H 2 O to predominately synthesis gas, with higher selectivity and activity compared to polycrystalline metal catalysts such as Ag and Cu. The H 2 /CO ratio can be tailored for different industrial processes by tuning the applied potential and the particle size of ZnO. Density functional theory calculations showed that the higher activity of ZnO is related to more significantly stabilized intermediates, CO 2 *, COOH, and CO* compared to Cu and Ag. Our results highlight a promising class of low-cost, abundant oxide as active electrocatalysts for synthetic fuel production from CO 2. [ABSTRACT FROM AUTHOR]

Enhanced electrochemical reduction of CO 2 to syngas on CuZnOCNT catalyst. • Copper doping on ZnO shifts the ECR activity towards CO formation closer to the top of the volcano. • The optimal amount of copper is around 20 at% for CO formation from electrochemical reduction of CO 2. • Higher amount of Cu doping leads to metallic Cu segregation, resulting in higher H 2 evolution activity. • The 14Cu86ZnO/CNT catalyst shows best performance in terms of syngas (1:1 ratio) production at -0.9 V, better than Ag foil. Electrochemical CO 2 reduction is a promising method for the production of CO 2 neutral fuels and chemicals from renewable electricity. ZnO supported on CNT is a low-cost electro catalyst that can produce syngas from CO 2 and H 2 O. A rational catalyst design strategy for further improvement of the ZnO/CNT catalyst is to dope with copper to strengthen the binding energy of the CO intermediate, which could improve the activity. In this work, a series of CuZnO/CNT catalysts with intimate Cu and Zn contact and various Cu loadings are prepared. By varying the copper content we show that the synergy of copper and zinc improves the activity for CO formation, and the optimal copper content is 20 at%. On hydrogen evolution, the addition of copper has a two-fold effect. This reaction is enhanced by the reduced ZnO particle size obtained when copper is added, but at similar particle sizes of ZnO, a suppression is observed with increasing copper content as CO evolution is enhanced. Stability tests showed that pure ZnO phase is more stable than metallic copper on ZnO. Compared with polycrystalline silver, the CuZnO/CNT catalysts are more active for syngas formation at a useful CO: H 2 composition. This work demonstrates that the viability of DFT based rational design of electrochemical CO 2 reduction catalyst. By varying CuZnO composition as well as crystallite size, one is able to tune the electrochemical reduction activity towards CO and H 2 , and therefore achieve desired syngas ratio. [ABSTRACT FROM AUTHOR]

• Small Ni particles exhibit higher steam methane reforming activity than large ones. • The size-dependent activity of Ni catalysts is related to the surface-dependent activity. • Ni(2 1 1) is the most active surface for steam methane reforming. • Decreased Ni(2 1 1) surface fraction results in reduced Ni activity as size increases. Fundamental understanding of the size-dependent activity is essential to harness powers of the nanocatalysts. Here we report an experimental and theoretical study of the Ni particle size effect on activity of steam methane reforming (SMR) to achieve a better understanding of the size dependence of kinetic behavior at an atomic level. A kinetic study illustrated the higher forward methane turnover frequency on the smaller sized Ni particles. The size-dependent activity was well reproduced by microkinetic modeling on a truncated octahedron model with the kinetic parameters estimated by the improved unity bond index-quadratic exponential potential (UBI-QEP) and the Brønsted–Evans–Polanyi (BEP) relationship. Microkinetic modeling suggested that the size-dependent activity of Ni catalysts is associated with the surface-dependent activity. Much higher activity of Ni(2 1 1) than Ni(1 1 1) and Ni(1 0 0) accompanied by decreased Ni(2 1 1) surface fraction results in reduced Ni activity as particle size increases. The activity of Ni(1 1 1) is limited by high free energy barriers, while that of Ni(1 0 0) is limited by site blockage by C* and CH*. This work offers a feasible approach to gain insight into size-dependent activity and to aid rational catalyst design for SMR in which preparing extremely small Ni particles (≤6 nm) might be a good strategy. [ABSTRACT FROM AUTHOR]

• Novel small-sized mesoporous TS-1 (STS-1) is synthesized by SAC method. • Cost-efficient TPABr is used as template for STS-1 synthesis. • The effect of TPABr concentration of STS-1 is investigated. • The Au/STS-1 catalyst has good performance for propene epoxidation with H 2 /O 2. Designing cost-effective titanium silicalite-1 (TS-1) with enhanced mass transfer ability is of prime scientific and industrial importance. In this work, a novel small-sized mesoporous TS-1 (STS-1) material is first synthesized in cheap TPABr system using steam-assisted crystallization method. Compared with cheap microporous TS-1 prepared by classical hydrothermal method (HTS-1) with particle size of 950 nm, STS-1 shows mesoporous character of 13 nm and reduced average particle size of 590 nm. Moreover, effect of TPABr concentration is systematically investigated, and both of insufficient and overmuch TPABr concentrations are unfavorable because of low crystallinity and exorbitant price, respectively. Importantly, the catalytic performance of cost-effective Au/STS-1 for direct propene epoxidation with H 2 and O 2 is much better than that of Au/HTS-1, and comparable to the performance of the expensive Au/TS-1. By multi-characterizations and activation energy analysis, the underlying mechanism for the enhanced performance is further discussed. This work sheds new light on the design and synthesis of highly effective and cost-efficient TS-1 catalysts. [ABSTRACT FROM AUTHOR]

• The "dimethylcyclopropane" pathway is dominant for 2-pentene isomerization. • The ring-opening step is the rate-determining step for the isomerization reaction. • Van der Waals interactions would change the scaling relations in zeolite catalysis. Periodic density functional theory (DFT) calculations have been performed to examine the monomolecular reaction mechanism for 2-pentene skeletal isomerization catalyzed by acidic zeolite Beta, Mordenite, and ZSM-5. The use of periodic models allows consideration and analysis of zeolite steric constraints that occur within zeolite microspores. Three different reaction pathways, the "dimethylcyclopropane" (DMCP), methyl shift, and ethyl shift mechanisms, have been considered. The DMCP mechanism which includes rearrangement of protonated cyclopropane is proposed as the dominant reaction pathway, and the ring-opening step determines the overall reaction rate. Comparison of the effective energy barriers for 2-pentene isomerization over the three different zeolites reveals that large 12-ring channels of Beta and MOR have little steric hindrance effect on 2-pentene isomerization while small 10-ring of ZSM-5 significantly increases the reaction activation energy. Calculated results also indicate that the adsorption heat of ammonia is a good descriptor for the reactivity of zeolites without taking into account long-range dispersive forces. In contrast, linear scaling relations cannot be obtained by using the BEEF-vdW functional because van der Waals interactions between zeolites framework and guest molecules affects the energetics of the isomerization reaction and changes the transition state energy scaling relation in zeolite catalysis. [ABSTRACT FROM AUTHOR]

• The reducibility and structural stability of LaMO 3 (M = Sc - Cu) are examined. • The first four LaMO 3 perovskites have very high oxygen vacancy formation energies. • The maximum possible oxygen deficiency in LaMO 3 (M = Mn - Ni) is 0.5. • LaCuO 3 can lose one lattice oxygen atom per formula unit before it is deactivated. Periodic density functional theory calculations have been performed to examine the effect of oxygen deficiency on the structural stability of Lanthanum-based perovskites (LaMO 3), where on-site Coulomb interactions have been addressed by an additional Hubbard-type term. Calculated results indicate that with the exception of LaFeO 3 , the oxygen vacancy formation energy (Δ E f o r m a t i o n , v a c ) of LaMO 3 (M = Sc - Cu) becomes less positive when moving across the first transition metal period. The first four LaMO 3 perovskites have very high oxygen vacancy formation energies and can hardly be reduced under mild conditions, while the other five perovskites exhibit a much greater reducibility. During the formation of the first oxygen vacancy in LaMO 3 (M = Mn - Cu), the nearest neighbor transition-metal cations serve as the primary acceptors of the electrons left behind. As oxygen atoms are further removed, square-based pyramidal and tetrahedral coordination geometries appear successively, and an abrupt increase in Δ E f o r m a t i o n , v a c is observed at a specific oxygen deficiency (δ), which defines the maximum possible δ in the perovskite structures. Under this definition, the M3+ cations (M = Mn - Ni) can be possibly reduced to M2+ while LaCuO 3 may lose at most one lattice oxygen atom per formula unit before it is deactivated. [ABSTRACT FROM AUTHOR]