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Rational screening of efficient supported metal catalysts is still a great challenge due to the complicated reaction mechanism for selective polyol oxidation. Exemplifying glycerol oxidation to glyceric acid as a model reaction, we perform a DFT assisted descriptor based microkinetic modeling to reveal the underlying mechanism. It is found that the addition/formation of OH− could polarize the metal surface (M‐OH*) to regulate the d‐band center of Pt accompanied by the electron transfer from OH− to metal atoms, thus promoting the adsorption of glycerol. Moreover, the linear chemisorption energy and transition state energy scaling relations are well established on the formation energies of adsorbed C and O. Activity map obtained from descriptor based microkinetic analysis demonstrates that Pt and Ir metals exhibit the highest catalytic activity. Meanwhile, further analysis of the desorption energy and CC bond cleavage activation energy of glyceric acid product shows that Au and Pt metals display the optimal glyceric acid selectivity. Satisfactorily, these results from microkinetic analysis are in good agreement with the comparative experimental results. The insights revealed here may open a new avenue for rational design of transition metal catalysts in the bio‐polyol oxidation system. [ABSTRACT FROM AUTHOR]

Simultaneous transformation of CO2 and H2O into syngas (CO and H2) using solar power is desirable for industrial applications. Herein, an efficient photocatalyst based on double‐shelled nanoboxes, with an outer shell of hydroxy‐rich nickel cobaltite nanosheets and an inner shell of Cu2S (Cu2S@ROH‐NiCo2O3), is prepared via a multistep templating strategy. The high performance of Cu2S@ROH‐NiCo2O3 (7.1 mmol g−1 h−1 for CO; 2.8 mmol g−1 h−1 for H2) is attributed to the hierarchical hollow geometry and p–n heterojunction to promote light absorption and charge separation. Spectroscopic and theoretical analyses elucidate that the ROH‐NiCo2O3 surface enhances *CO2 adsorption and lowers energy barriers for CO2‐to‐CO. Therefore, modulating the hydroxy contents of ROH‐NiCo2O3 can achieve broad CO/H2 ratios from 0.51 to 1.24. This work offers in‐depth insights into adjustable syngas photosynthesis and generalized concepts of selective heterogeneous CO2 photoreduction beyond cobalt‐based oxides. [ABSTRACT FROM AUTHOR]

Carbon monoxide (CO) is notorious for its strong adsorption to poison platinum group metal catalysts in the chemical industry. Here, we conceptually distinguish and quantify the effects of the occupancy and energy of d electrons, emerging as the two vital factors in d‐band theory, for CO poisoning of Pt nanocatalysts. The stepwise defunctionalization of carbon support is adopted to fine‐tune the 5d electronic structure of supported Pt nanoparticles. Excluding other promotional mechanisms, the increase of Pt 5d band energy strengthens the competitive adsorption of hydrogen against CO for the preferential oxidation of CO, affording the scaling relationship between Pt 5d band energy and CO/H2 adsorption energy difference. The decrease of Pt 5d band occupancy lowers CO site coverage to promote its association with oxygen for the total oxidation of CO, giving the scaling relationship between Pt 5d occupancy and activation energy. The above insights outline a molecular‐level understanding of CO poisoning. [ABSTRACT FROM AUTHOR]

Herein, we demonstrate a kinetics and a mechanistic strategy to disentangle the origins of the significantly improved activity and selectivity of Pt‐catalyzed glycerol oxidation. The unchanged reactant reaction orders and activation energies suggest the same kinetics despite variable Pt particle sizes, based on which a Michaelis–Menten kinetics treatment is conducted to individually quantify the number and activity of Pt active site. Together with multiple characterization results, the volcano‐shaped activity is mainly arising from the quantity change of Pt active site. Moreover, the atomic structure of bimetallic Pt─Sb catalyst is well elucidated by the formation of Pt─SbO interface along with partial Sb incorporation into Pt lattice, chelating with glycerol to poison Pt active sites for primary hydroxyl activation while creating interfacial site for second hydroxyl activation, further evidenced by kinetics shift. The kinetics strategy could be extended to other metal catalysts with simultaneously high activity and selectivity. [ABSTRACT FROM AUTHOR]

Main observation and conclusion: The catalytic properties of the CeO2 catalyst for propane dehydrogenation (PDH) are examined by employing the density functional theory calculations. Surface modifications and their effects on the surface reactivity are explored by creating the oxygen vacancy and single Pt atom doping. A comparative study between the binding energies of the different PDH reaction species reveals a considerable Lewis acid‐base interaction over the pristine and defective surfaces, which dominantly strengthens the bond formation between the adsorbates and the catalyst surface, resulting in the enhancement of surface reactivity. The creation of oxygen vacancy and doping the CeO2(111) surface with single Pt atoms changes the charge distribution over the surface on account of excess 4f electrons. This electronic change increases the bond formation abilities of the inactive Ce atom and hence increases the adsorption strength. Oxygen vacancy in the defective CeO2(111) surface migrates over the surface with the addition of an appropriate adsorbate. Moreover, it is revealed that the propylene is more strongly adsorbed on the single‐Pt‐atom‐doped CeO2(111) surface than the pristine and defective surfaces, which decreases the deep dehydrogenation energy barrier and ultimately results in the lowering of the selectivity. [ABSTRACT FROM AUTHOR]

[Display omitted] • In-doped amino-functionalized UiO-66 Zr-MOFs are synthesized by one-pot reaction. • Amino groups reduce band gap by lifting valence band maximum. • In doping facilities LMCT process by inducing oxygen vacancies. • aU(Zr/In) exhibits the excellent photoreduction activity of CO 2 to CO. Metal organic frameworks (MOFs) with high porosity and highly tunable physical/chemical properties can serve as heterogeneous catalysts for CO 2 photoreduction, but the application is hindered by the large band gap (E g) and insufficient ligand-to-metal charge transfer (LMCT). In this study, a simple one-pot solvothermal strategy is proposed to prepare an amino-functionalized MOF (aU(Zr/In)) featuring an amino-functionalizing ligand linker and In-doped Zr-oxo clusters, which enables efficient CO 2 reduction driven with visible light. The amino functionalization leads to a significant reduction of E g as well as a charge redistribution of the framework, allowing the absorption of visible light and the efficient separation of photogenerated carriers. Furthermore, the incorporation of In not only promotes the LMCT process by creating oxygen vacancies in Zr-oxo clusters, but also greatly lowers the energy barrier of the intermediates for CO 2 -to-CO conversion. With the synergistic effects of the amino groups and the In dopants, the optimized aU(Zr/In) exhibits a CO production rate of 37.58 ± 1.06 μmol g-1 h−1, outperforming the isostructural University of Oslo-66- and Material of Institute Lavoisier-125-based photocatalysts. Our work demonstrates the potential of modifying MOFs with ligands and heteroatom dopants in metal-oxo clusters for solar energy conversion. [ABSTRACT FROM AUTHOR]

[Display omitted] Developing efficient heterogeneous catalysts for the aerobic oxidation of C–H bonds using oxygen molecule as an oxidant to produce value–added aryl ketones is a challenging task. In this study, a series of cementite–iron–carbon composites (referred to as Fe–C–T, where T represents the pyrolysis temperature) were synthesized using a metal–organic–framework–mediated sacrificial template strategy. The Fe–C–T composites consist of highly dispersed Fe/(Fe 3 C or Fe 2 O 3) nanoparticles surrounded by graphitic carbon on porous carbon supports. Under mild reaction conditions (1 atm of O 2 pressure, 353 K, 12 h), with tert–butyl hydroperoxide (0.25 equiv.) as the initiator in a green solvent water, the prepared Fe–C–973 achieved a high conversion of 98.4 % for ethylbenzene and a selectivity of 98.7 % for acetophenone. This performance was markedly superior to the comparable Fe–C–873 and Fe–C–1073, as well as the commercially available Fe–based catalysts. Kinetic studies revealed that the catalytic system followed first–order kinetics for the substrate ethylbenzene, and the activation energy over Fe–C–973 was remarkably low of 40.4 kJ/mol. The highly distributed Fe 3 C nanoparticles embedded in the porous carbon framework were identified as the most active sites for the reaction. [ABSTRACT FROM AUTHOR]

G max : The highest reaction potential energy in the reaction path. [Display omitted] • Influence of Pt on the electronic properties of α-MoC-111 surface. • Inhibition effect of Pt on carbon deposition in WGS reaction. • Preventing surface oxidation by introducing Pt in α-MoC during WGS reaction. • Role of Pt in facilitating water dissociation. Pt/α-MoC is an outstanding catalyst for the low-temperature water gas shift (WGS, CO + H 2 O → H 2 + CO 2) reaction, exhibiting elevated activity, stability, and selectivity. In this study, three significant active site models (α-MoC-111, Pt-111, and Pt 1 /α-MoC-111) in Pt/α-MoC catalyst were established to investigate the promotion effect of Pt on the WGS reaction catalyzed by Pt/α-MoC. The results indicate that a synergistic effect at the metal-carbide interface enhances chemical activity compared to pure Pt-111 and α-MoC-111. Firstly, the surface of Pt 1 /α-MoC-111 exhibits strong metal-support interaction between Pt single atom and α-MoC-111 surface. Compared to the α-MoC-111 surface, the introduction of Pt strengthens the Mo−Mo bond while weakening the Mo−C bond. Secondly, adding a Pt atom significantly increases adsorption strength for CO and H 2 O, while decreasing it for products (CO 2), oxides (O atom), and by-products (C atom). The advantage of suppressing surface carbon deposition and oxidation is observed on the surface of Pt 1 /α-MoC-111. Furthermore, elementary reactions from the three mainstream reaction pathways of the WGS reaction are systematically calculated to evaluate catalytic performance among these three active sites. On the Pt 1 /α-MoC-111 surface, activation energy barriers for H 2 O dissociation and CO oxidation are reduced. This provides theoretical ideas for designing high-efficiency α-MoC based catalysts in the future. [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]

• 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]

• 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 dynamic nature of active sites on La-Fe-based perovskites in chemical looping methane oxidation has been studied. According to experimental observations, the reduction of the oxygen carrier is divided into three stages occurring at different active ensembles where the Fe cations are in different coordination environments. The Mars van Krevelen mechanism formulated by microkinetic analysis describes well the effect of oxygen vacancy on the catalytic performance of LaFeO 3. CO 2 is not produced by CO oxidation but rather is a primary product of methane oxidation, and the presence of surface oxygen vacancies would dramatically increase the overall energy barrier for total combustion, thus decreasing the selectivity toward CO 2. Hence, the Fe coordination environment (and hence the oxygen vacancy concentration) is the key parameter governing the catalyst selectivity, in the sense that methane oxidation can vary from total combustion on the O-rich surface to fully selective partial oxidation on the O-deficient surface. [Display omitted] • The dynamic nature of active sites for chemical looping methane oxidation. • The different active ensembles at different reaction stages are identified. • The Fe coordination environment is the key parameter governing the selectivity. • CO 2 is a primary product rather than produced by CO oxidation. • Controlling oxidation time is proposed to achieve methane partial oxidation. [ABSTRACT FROM AUTHOR]

Density functional theory calculationshave been performed to investigatethe recombinative desorption of N on terraced Fe(100) and Fe(110)as well as stepped Fe(111) and Fe(211) surfaces. The results showedthat the stepped surfaces, especially the Fe(111) surface, are moreactive than the terraced surfaces, which could be related to the presenceof so-called C7sites for the stepped surfaces. Carbonatoms were found to stabilize the thermodynamically unstable steppedsurfaces to be the energetically favored facets and thus facilitatethe preferential exposure. As these carbon atoms incorporated intothe stepped surfaces in the form of surface or subsurface carbon,the activation energy for the recombinative desorption of N was lowered,which was mainly ascribed to the decrease in the d band center ofsurface Fe atoms. In addition, a relation between the electronic andstructural properties of Fe catalysts in the absence or presence ofcarbon and ammonia decomposition activity was also correlated. [ABSTRACT FROM AUTHOR]

Fischer–Tropsch synthesis of light olefins plays a vital role in the production of major chemical building blocks from non-petroleum resources, having great academic and commercial importance. Herein, Na and S modulated FeMnO x catalysts were employed to systematically investigate the influence of additives, which not only enhanced the CO conversion but also facilitated the olefin formation and suppressed the undesired methane formation. Multiple characterizations confirmed that the existence of promoters would enhance the formation of active species of Fe 5 C 2 at FTO conditions because of the promoted carbon insertion into the iron species from the intermediates dissociation. Combined the steady-state isotopic transient kinetic analysis with dynamic calculation, it confirmed that the promoters indeed had the ability to lower CO activation energy, as well as increase the carbon chain growth activity and the energy barrier to hydrogenation. This study provides a practical strategy for exploring the highly active and stable FTO catalysts. [Display omitted] • Na and S additives over FeMnO x catalyst promoted both the CO conversion and the olefin formation. • Pomotes facilitated the Fe5C2 formation by suppressing the oxidation cycle of iron and enhancing the insertion of carbon. • The presence of promoters reduced the charge of iron and caused more compact bonds of Fe-C, lowing the CO activation energy. • Promoters indeed increased the carbon chain growth activity and the energy barrier to hydrogenation. [ABSTRACT FROM AUTHOR]

Abstract: Ni catalysts are widely used to catalyze ammonia decomposition. In this study, first-principles calculations are performed to investigate the preferred adsorption sites and the adsorption energies of NHx (x=0–3) and H, and the transition states, activation energies and rate constants of NH3 stepwise dehydrogenation and associative desorption of N on the stepped Ni(211) and the close-packed Ni(111) surfaces. The results show that the barrier of associative desorption of N, which is higher than those of NH3 stepwise dehydrogenation, on Ni(211) are 1.10eV higher than that on Ni(111), indicating that the associative desorption of N on Ni(211) is difficult to take place. Hence the strongly adsorbed N atoms would block some of the step sites of Ni(211). The N-blocking Ni(211) surface is constructed, and then NH3 decomposition on 2N–Ni(211) is investigated. The results indicate that Ni catalysts with too many or too few step sites, which can be associated with Ni particle sizes, show low ammonia decomposition activities. Therefore, different sized Ni-based catalysts are employed to catalyze ammonia decomposition, and TOFH2 as a function of Ni particle size is correlated. Finally, the structure sensitivity of ammonia decomposition over Ni catalysts is rationally interpreted. [Copyright &y& Elsevier]

The nanocrystallization kinetics of Zr41.2Ti13.8Cu12.5Ni10Be22.5 (at.%) bulk metallic glass was investigated by differential scanning calorimetry (DSC) in the mode of continuous heating and isothermal annealing. In the case of continuous heating, three exothermic crystallization peaks can be observed, and the peak temperatures display a strong dependence on the heating rates, which can be fitted by a first order decay equation. The activation energies for crystallization are estimated to be Ep1=166.83±8.85 kJ/mol, Ep2=256.15±9.34 kJ/mol, Ep3=174.36±12.56 kJ/mol, which correspond to peak temperatures of Tp1, Tp2, and Tp3, respectively, indicating the formation of different crystallization phases at different stages. In the case of isothermal annealing, the crystallization products under isothermal annealing were observed and determined by transmission electron microscopy (TEM). The precipitation phases of the sample heated at higher temperatures were identified by X-ray diffraction (XRD), showing that the body-centered tetragonal (bct) Zr2Cu and hexagonal ZrBe2 are the primary phases, in spite of the presence of other phases. These results are consistent with the complexity of the DSC curves obtained during the continuous heating and isothermal annealing. [Copyright &y& Elsevier]

• An ion exchange based strategy was used to synthesize the hierarchy structured mutimetal MOFs derived electrocatalyst. • This strategy prevents the collapse of well-designed MOF nanostructures during the air calcination process. • The unique electronic modulation of Co-Ni-Fe in spinel oxides can optimize the binding strength of OER intermediates. • CoNiFeO x -NC catalyst delivers highly efficient OER performance (η 50 = 265 mV). Metal-organic frameworks (MOFs) have recently emerged as promising precursors to construct efficient non-noble metal electrocatalyst for oxygen evolution reaction (OER). Herein, a Co-Ni-Fe spinel oxide-carbonitrides hybrids (CoNiFeO x -NC) electrocatalyst with hierarchical structure was synthesized from Fe-MIL-101-NH 2 through a unique ion-exchange based strategy. The ion exchange of Fe-MIL-101-NH 2 with both Ni and Co ions induced a hierarchically structured 2-D ternary metal MOF shell layer encapsulated 3-D octahedral MOF crystals as a core. This prevents the collapse of MOF frameworks during the air calcination process and affords highly porous structure and large surface area. Additionally, the unique combination of Co-Ni-Fe in spinel oxides derived from calcination of the hierarchically structured core-shell MOF provides a favorable electronic environment for the adsorption of OER intermediates, which was further verified by the XPS characterizations and DFT calculations. DFT study revealed the Ni-Co coordinated O h sites in the MFe 2 O 4 reverse spinel structures as the main active sites, which tuned the binding strength of oxygen species with a catalyst through electron transfer of Fe→Co→Ni, thereby lowered the energy barriers for OER. As a result, the rationally designed CoNiFeO x -NC catalyst manifests superior OER performance with a low overpotential of 265 mV at 50 mA cm−2 and a decent Tafel slope of 64.1 mV dec-1. The ion-exchange based strategy may serve as a versatile platform for rational design and synthesis of multi-metallic MOF derived electrocatalysts. [ABSTRACT FROM AUTHOR]

We successfully realized the directional construction of Pt-Mn 2 O 3 interfacial sites (by the combination of in-situ doping and impregnation methods) to boost selective oxidation of ethylene glycol under mild conditions. It is found that the pre-distribution of Mn 2 O 3 inside support unexpectedly induced the formation of Pt-Mn 2 O 3 interfacial active sites with strong electron coupling effect, leading to an unprecedented glycolic acid oxidation activity (turnover frequency: 3196.9 h−1) and glycolic acid yield (86.4 %). • Enhanced catalytic performance of ethylene glycol oxidation was achieved. • Strong electron coupling effect was revealed in the Pt-Mn interface. • Quantitative analysis of the intrinsic active sites was performed. • The promotion role of Pt-Mn interfacial on reaction mechanism was correlated. Rational design of desirable active sites is still a grand challenge for the efficient conversion of polyols to value-added products. Herein, we successfully constructed the Pt-Mn 2 O 3 interfacial sites rather than Pt-MnO x solid solution to boost selective oxidation of ethylene glycol to glycolic acid under mild conditions. X-ray absorption spectroscopy and high-resolution transmission electron microscope revealed that the pre-distribution of Mn 2 O 3 inside support unexpectedly induced the formation of Pt-Mn 2 O 3 interfacial active sites with strong electron coupling effect, leading to an unprecedented catalytic activity (turnover frequency: 3196.9 h−1) and glycolic acid yield (86.4 %). In addition, quantitative analysis of the intrinsic active sites was performed, and a "volcano-shape" relationship was established between initial reaction rate and Pt/Mn ratio. Moreover, the structure-dependent reaction kinetics and density functional theory calculation revealed that the synergistic effect between the Mn 2 O 3 redox cycle and Pt promotes the adsorption of ethylene glycol and the activation of C H bond, resulting in the lower activation energy of ethylene glycol oxidation. The outcome of this work offers a promising avenue for the direct construction of efficient Pt-based catalysts with desired active sites. [ABSTRACT FROM AUTHOR]

• The reaction mechanisms of each step evolve with the surface Cl/Cu ratios. • The origin of the K effect was explored by Van-der-Waals corrected DFT calculations. • Free energy analysis is consistent with the experimental observation. • KCl modifies the electronic structure of the surface. Potassium promoters are widely used in industrial catalysts of ethylene oxychlorination to achieve optimum performance. However, the origin of the promoter effect is not fully understood. Herein, we investigated the potassium promotion effect on CuCl 2 /γ-Al 2 O 3 catalyzed ethylene oxychlorination by kinetic experiments and DFT calculations. Kinetic experiments observed the effect of KCl on individual steps, and the evolution of the reaction mechanisms with Cl/Cu ratios. Further exploration via DFT found that KCl increases the formation energy of Cl vacancy (Δ E v) and thus inhibits the reduction activity, which is attributed to the shift-down of Bader charge of Cl. Δ E v boosts with the decline of Cl/Cu ratios; thus, ethylene can extract Cl atoms from the surface with a Cl/Cu ratio of 2, while it anchors to metal atoms at lower Cl/Cu ratios. The distinct adsorption modes reflect the evolution of reaction mechanisms with Cl/Cu ratios. KCl facilitates the adsorption of oxygen owing to the shift-up of the Bader charge of Cu atom. Potassium reduces the Gibbs free energy barrier of the oxidation step, which agrees with the experimental observation. It is concluded that the potassium promoter effect on the catalytic performance mainly results from the modification of the charge of surface atoms. [ABSTRACT FROM AUTHOR]

In this contribution, we combine density functional theory (DFT) calculations, experimental kinetic study and DFT-assisted analysis to elucidate the impact of the interface of monolayer Pt on the Ni surface on catalytic performance of steam methane reforming including carbon formation on core-shell (Ni@Pt) catalysts and compare it with Ni and Pt catalysts. We demonstrate that core-shell structured Ni@Pt significantly lowers the carbon formation without sacrificing much the activity. The DFT results demonstrate that the metal identity, core shell structure and support have significant impacts on the reaction mechanisms. The direct methane activation is energetically favorable reaction pathway on Ni, while the OH* assisted methane activation is the favorable pathway on Pt and Ni@Pt catalysts, where methane activation is the rate-determining step on all catalysts. We unambiguously reveal that the core-shell Ni@Pt catalyst modified the surface Pt electron density and shifted d -band center away from Fermi level compared to Ni(1 1 1) and Pt(1 1 1). It results in a strong basic surface OH* which actively reacts with CH x and thus enhances carbon formation resistance. Above all, Ni-core/Pt-shell particle could decouple the activity and carbon resistance to keep the activity and reduce carbon formation simultaneously in methane steam reforming. In addition, by taking into account the activation of steam on the support, the effective activation energy estimated from DFT-assisted analysis is well consistent with the experimental value on the both Ni and Ni@Pt catalysts, which could shed some light on building a bridge between experimental work and DFT-assisted kinetic study. [ABSTRACT FROM AUTHOR]

• High selectivity of core-shell alloy catalysts for propane dehydrogenation. • Linear scaling relations are established to identify the descriptor. • Microkinetic modeling is carried out to obtain turnover frequency. • Co@Pt is the best catalyst by making a compromise between activity and selectivity. Microkinetic analysis combined with the results obtained from density functional theory calculations has been performed to examine the catalytic activity and selectivity of Pt-based core-shell alloy catalysts for propane dehydrogenation. Calculated results indicate that substitution of 11 late transition metals for the core region of Pt nanoparticles would significantly modify the electronic structure of the surface Pt atoms through the strain effect and charge transfer. The core-shell catalysts are found to have less negative propylene adsorption energies and higher activation energies for the dehydrogenation reactions than Pt, thus giving rise to a lower catalytic activity and a higher selectivity toward propylene. Linear chemisorption energy and transition state energy scaling relations hold very well in the present work, and the adsorption energy of propylene is identified to be a good descriptor to represent the overall kinetics. The scaling relations also suggest that a higher catalyst selectivity toward propylene can only be achieved at the expense of a lower catalytic activity for propane dehydrogenation. If a compromise is made between catalytic activity and catalyst selectivity, Co@Pt is proposed to be the best core-shell catalyst for propane dehydrogenation. [ABSTRACT FROM AUTHOR]