Dry Reforming of Methane on Ni/LaZrO2 Catalyst under External Electric Fields: A Combined First-Principles and Microkinetic Modeling Study.

Dry reforming of methane (DRM) reaction has great potential in reducing the greenhouse effect and solving energy problems. Herein, the DRM reaction mechanism and activity on Ni16/LaZrO2 catalyst under electric fields were comprehensively investigated by combining density functional theory calculations with microkinetic modeling. The results showed that La doping increases the interaction between Ni and ZrO2 by Ni cluster transfer of more electrons. The adsorption strength of species followed the order Ni16/ZrO2 > Ni16/LaZrO2, which is consistent with the results for the d-band center but opposite to the metal-support interaction. The best DRM reaction path on Ni16/LaZrO2 was the CH2-O pathway, which is different from the CH-O pathway on Ni(111) and Ni16/ZrO2. Both positive and negative electric fields of strong and weak metal-support interactions reduced the energy barrier of DRM reaction. Importantly, our results showed that the more dispersed and smaller Ni12/LaZrO2 model by considering the dispersing effect induced by La doping, which displayed very different results from that of Ni16/LaZrO2: reduced the energy barrier for methane decomposition, thereby promoting DRM reaction activity. Microkinetic results showed that the carbon deposition behavior of DRM becomes weaker on Ni16/LaZrO2 due to the suppression of methane decomposition in the presence of La doping compared to Ni16/ZrO2, but the opposite result is obtained on Ni12/LaZrO2. The order of DRM reactivity was Ni16/LaZrO2 < Ni16/ZrO2 < Ni12/LaZrO2, which is consistent with the experiment observations. The conversion of methane and CO2 was higher in positive electric fields than in negative electric fields at low temperatures, but the results were opposite at high temperature. Negative electric fields can improve the carbon deposition resistance of Ni-based catalysts compared to positive electric fields. The degree of rate control analysis showed that CHx* oxidation also plays an important role in the DRM reaction. We envision that this study could provide a deeper understanding for guiding the widespread application of electric field catalysis.

Mechanisms of CH4 activation over oxygen-preadsorbed transition metals by ReaxFF and AIMD simulations.

The chemisorbed oxygen usually promotes the CH bond activation over less active metals like IB group metals but has no effect or even an inhibition effect over more active metals like Pd based on the static electronic structure study. However, the understanding in terms of dynamics knowledge is far from complete. In the present work, methane dissociation on the oxygen-preadsorbed transition metals including Au, Cu, Ni, Pt, and Pd is systemically studied by reactive force field (ReaxFF). The ReaxFF simulation results indicate that CH4 molecules mainly undergo the direct dissociation on Ni, Pt, and Pd surfaces, while undergo the oxygen-assisted dissociation on Au and Cu surfaces. Additionally, the ab initio molecular dynamics (AIMD) simulations with the umbrella sampling are employed to study the free-energy changes of CH4 dissociation, and the results further support the CH4 dissociation pathway during the ReaxFF simulations. The present results based on ReaxFF and AIMD will provide a deeper dynamic understanding of the effects of pre-adsorbed oxygen species on the CH bond activation compared to that of static DFT.

Comparative theoretical study of CO2 activation on clean and potassium-preadsorbed low index surfaces of transition metals.

CONTEXT: The efficient catalysis of CO2 adsorption and activation presents a formidable challenge due to its pronounced thermodynamic stability and kinetic inertia. Previous experiments have left gaps in understanding the promotional effects and underlying mechanism of potassium. In this study, we systematically investigate CO2 adsorption and activation on clean and potassium-preadsorbed low index surfaces of transition metals. Theoretical results reveal a substantial augmentation in CO2 binding strength when potassium is introduced, concomitant with a general reduction in activation energies. Notably, linear correlations are significant on close-packed metal surfaces without and with potassium additive. Through a comprehensive analysis encompassing geometric parameters, electronic structures, and energy decomposition, we discern the physical underpinnings of the potassium effect. This enhancement is primarily ascribed to direct electron transfer and dipole-dipole interactions. Furthermore, we scrutinize the impact of an external electric field, demonstrating that the application of a negative electric field accelerates CO2 activation, mirroring the effects observed with potassium. METHODS: All the periodic density function theory (DFT) calculations were performed by the Vienna Ab Initio Simulation package (VASP). The interaction between nucleus and valence electron was described using the pseudopotentials found in the projector augmented wave method (PAW). Throughout the entire work, the Bayesian error estimation functional (BEEF) was used.

Investigation of the oxygen coverage effect on the direct epoxidation of propylene over copper through DFT calculations.

The direct epoxidation of propylene is one of the most important selective oxidation reactions in industry. The development of high-performance copper-based catalysts is the key to the selective oxidation technology and scientific research of propylene. The mechanism of propylene's partial oxidation catalyzed by Cu(111) under different oxygen coverage conditions was studied using density functional theory calculations and microkinetic modeling. We report here in detail two parallel reaction pathways: dehydrogenation and epoxidation. The transition states and energy distributions of the intermediates and products were calculated. The present results showed that propylene oxide (PO) selectivity was high under low oxygen coverage, and increasing the oxygen coverage would decrease the PO selectivity but increase the PO activity, and there was an inverse relationship between PO selectivity and activity. Increasing oxygen coverage would reduce the energy barrier for the C-O bond formation of C3H5O due to the weaker adsorption strength of C3H5, thus decreasing the PO formation selectivity. On the other hand, increasing oxygen coverage would reduce the energy barrier for the possible reaction steps of propylene epoxidation in general, and thus increasing the catalytic activity. It might be proposed that the active site for propylene epoxidation is the metallic copper or partially oxidized copper in terms of the change of PO formation selectivity with oxygen coverage.

M supported on Al-defective Al2-δO3 (M = Fe, Co, Ni, Cu, Ag, Au) as catalysts for acetylene semi-hydrogenation: a theoretical perspective.

Semi-hydrogenation of acetylene is of great importance for both industry and academia. High prices and limited supplements of noble metals leave room for developing base metal catalysts. Experiments revealed the atomically dispersed Cu supported by Al2O3 with excellent long-term stability and high ethylene selectivity, but the physical nature has rarely been investigated theoretically. DFT calculations and microkinetic modeling revealed that the surface OH species could stabilize Cu1/Al2-δO3 and enhance its catalytic performance. The selectivity of ethylene formation decreases with increasing copper clusters (e.g., Cu1/Al2-δO3> Cu4/Al2-δO3> Cu8/Al2-δO3), meaning that the atomically dispersed copper may be a potential candidate for acetylene semi-hydrogenation. The structures of a series of single site catalysts M1/Al2-δO3 (M = Fe, Co, Ni, Ag, Au) are similar to that of Cu1/Al2-δO3, but their performances in catalyzing acetylene semi-hydrogenation are different. M1/Al2-δO3 (M = Ag, Au) shows higher selectivity than Cu1/Al2-δO3, while M1/Al2-δO3 (M = Fe, Co, Ni) demonstrates a higher turnover frequency (TOF) of ethylene than Cu1/Al2-δO3. Moreover, our results indicate that the Ni1-Cu1/Al2-δO3 alloy shows both high activity and ethylene selectivity. The present results show a compensation between the reactivity and the selectivity, suggesting that alloys of VIIIB metals with IB metals like Ni1-Cu1/Al2-δO3 may be efficient candidate catalysts in acetylene selective hydrogenation.

Theoretical insight into the promotion effect of potassium additive on the water-gas shift reaction over low-coordinated Au catalysts.

CONTEXT: How to elucidate the effect of alkali metal promoters on gold-catalyzed water-gas shift reaction intrinsically remains a challenging, because that the complex synergy effects such as strong metal-support interactions, interfacial effects, and charge transfer of supported metal catalysts makes people difficulty in the understanding the alkali promotion phenomenon in nature. Herein, we report a systematically study of whole water-gas shift reaction mechanism on pure and the K-modified defected-Au(211) (i.e., by removing one surface Au atom from perfect Au(211) and make one model with the Au-Au coordination number is six) by using the microkinetic modeling based on first principles. Our results indicate that the presence of K can increase the adsorption ability of oxygen-containing species via the attractive coulomb interaction, has no significant effect on the adsorption of H species, but inhibits the adsorption of CO due to the steric effect. K promoter stabilizes the water adsorption by ~0.3 eV, which results in one order increasing of whole reaction rate. Interestingly, the strong promotion effect of the K can be assigned to the significant direct space interaction between K and the adsorbate H2O* through the inducted electric field, which can be further confirmed by the posed negative electric field on the unpromoted D-Au(211). Microkinetic modeling results revealed that the carboxyl mechanism is the most likely to occur, redox mechanism is the next one, and the formate mechanism is the least likely to occur. For different kinds of alkali metal additives, the adsorption strength of water molecules gradually weakens from Li to Cs, but Na shows the best promoter behavior at the low temperature. By considering the effect of K contents on the reactivity of water-gas shift reaction, we found that the K with the medium coverage (~0.2~0.3 ML) has the strongest promoting effect. It is expected that the conclusion of this work can be extended to other WGSR catalytic systems like Cu(or Pt). METHODS: All calculations were performed by using the plane-wave based periodic method implemented in Vienna ab initio simulation package (VASP, version 5.4.4), where the ionic cores are described by the projector augmented wave (PAW) method. The exchange and correlation energies were computed using the Perdew, Burke and Ernzerhof functional with the vdw correction (PBE-D3). The transition states (TSs) were searched using the climbing image nudged elastic band (CI-NEB) method. Some electronic structure properties like work function was predicated by the DS-PAW software. Microkinetic simulation was carried out using MKMCXX software.

Multilayered Molybdate Microflowers Fabricated by One-Pot Reaction for Efficient Water Splitting.

The development of high-performance, low-cost and rapid-production bifunctional electrocatalysts towards overall water splitting still poses huge challenges. Herein, the authors utilize a facile hydrothermal method to synthesize a novel structure of Co-doped ammonium lanthanum molybdate on Ni foams (Co-ALMO@NF) as self-supported electrocatalysts. Owing to large active surfaces, lattice defect and conductive channel for rapid charge transport, Co-ALMO@NF exhibits good electrocatalytic performances which requires only 349/341 mV to achieve a high current density of 600 mA cm-2 for hydrogen evolution reaction (HER) and oxygen evolution reaction (OER), respectively. Besides, a low cell voltage of 1.52 V is required to reach the current density of 10 mA cm-2 in alkaline medium along with an excellent long-term stability for two-electrode configurations. Density functional theory calculations are performed to reveal the reaction mechanism on Co-ALMO@NF, which shows that the Mo site is the most favorable ones for HER, while the introduction of Co is beneficial to reduce the adsorption intensity on the surface of Co-ALMO@NF, thus accelerating OER process. This work highlighted the importance of the structural design for self-supporting electrocatalysts.

First-principles theoretical study on dry reforming of methane over perfect and boron-vacancy-containing h-BN sheet-supported Ni catalysts.

The entire reaction mechanism of the dry reforming of methane (DRM) as well as the competition processes over perfect and boron-vacancy-containing h-BN sheet-supported Ni-catalysts (labeled Ni2/h-BN and Ni2/h-BN-B-D) was studied by density functional theory calculations in the present work. Our calculation results show that B-defected h-BN strongly binds to the Ni2 active sites (i.e., shows a strong metal-support interaction (SMSI) character) due to the better electron transfer between Ni2 sites and the support. It was found that CH4 is easier to activate than molecular CO2. The activation of CO2 occurs on the surface of Ni2/h-BN through a direct route, whereas it is prone to follow a hydrogen-assisted path for Ni2/h-BN-B-D via the COOH* intermediate, and the results show that the oxidant O* is easily formed on the surface of Ni2/h-BN-B-D. It was also found that O* is the main oxidant agent for CHx* intermediates through the CH3-O oxidation mechanism. The reaction kinetic analysis indicated that the reverse water gas shift reaction (RWGS) is much more favorable than DRM (1.30 vs. 1.72 eV) over the Ni2/h-BN system, whereas the RWGS and DRM are comparable on Ni2/h-BN-B-D (1.77 vs. 1.66 eV), suggesting a high DRM activity on Ni2/h-BN-B-D. Moreover, neither methane cracking nor a Boudouard reaction to form C* species is thermodynamically and kinetically unfavorable over Ni2/h-BN-B-D; hence, Ni2/h-BN-B-D has strong resistance to carbon deposition. Compared to Ni(111), both Ni2/h-BN-B-D and Ni2/h-BN show strong resistance to carbon deposition. Our results provide a further mechanistic understanding of the DRM over an Ni-based catalyst through the SMSI characteristic and the SMSI favors strong resistance to carbon deposition.

Selective Oxidation of Propylene on Cu2O(111) and Cu2O(110) Surfaces: A Systematically DFT Study.

Density functional theory calculations with a Hubbard U correction were used to investigate the selective oxidation of propylene on Cu2O(111) and Cu2O(110) surfaces, and the mechanism for the selective oxidation of propylene was discussed. On both surfaces, acrolein can be generated by two H-stripping reactions in the allylic hydrogen stripping path, while propylene oxide (PO), propanal, and acetone can be created through the propylene oxametallacycle intermediates in the epoxidation path. Our calculation results indicated that Cu2O has a high crystal plane-controlled phenomenon for the selective oxidation of propylene. It was found that the formations of propanal and acetone are unfavorable kinetically and acrolein is the main product on the (111) surface. On the (110) surface, the activation barrier of acrolein formation is too high to produce and PO becomes the favored product, which is different from the case of the (111) surface. Moreover, energetic span model analysis was carried out to discuss the selective oxidation of propylene on these two surfaces and confirm the above calculations. The present study can help people to design the proper crystal plane catalyst to get the target product of PO with high selectivity and activity in the selective oxidation of propylene.

Enhanced Synergetic Catalytic Effect of Mo2C/NCNTs@Co Heterostructures in Dye-Sensitized Solar Cells: Fine-Tuned Energy Level Alignment and Efficient Charge Transfer Behavior.

A highly efficient and stable electrocatalyst with the novel heterostructure of Co-embedded and N-doped carbon nanotubes supported Mo2C nanoparticles (Mo2C/NCNTs@Co) is creatively constructed by adopting the one-step metal catalyzed carbonization-nitridation strategy. Systematic characterizations and density functional theory (DFT) calculations reveal the advanced structural and electronic properties of Mo2C/NCNTs@Co heterostructure, in which the Co-embedded and N-doped CNTs with tunable diameters present electron-donating effect and the work function is correspondingly regulated from 4.91 to 4.52 eV, and the size-controlled Mo2C nanoparticles exhibit Pt-like 4d electronic structure and the well matched work function (4.85 eV) with I-/I3- redox couples (4.90 eV). As a result, the conductive NCNTs@Co substrate with fine-tuned energy level alignment accelerates the electron transportation and the electron migration from NCNTs@Co to Mo2C, and the active Mo2C shows high affinity for I3- adsorption and high charge transfer ability for I3- reduction, which reach a decent synergetic catalytic effect in Mo2C/NCNTs@Co heterostructure. The DSSC with Mo2C/NCNTs@Co CE achieves a high photoelectric conversion efficiency of 8.82% and exceptional electrochemical stability with a residual efficiency of 7.95% after continuous illumination of 200 h, better than Pt-based cell. Moreover, the synergistic catalytic mechanism toward I3- reduction is comprehensively studied on the basis of structure-activity correlation and DFT calculations. The advanced heterostructure engineering and electronic modulation provide a new design principle to develop the efficient, stable, and economic hybrid catalysts in relevant electrocatalytic fields.

Sulfur-Deficient Bismuth Sulfide/Nitrogen-Doped Carbon Nanofibers as Advanced Free-Standing Electrode for Asymmetric Supercapacitors.

The use of free-standing carbon-based hybrids plays a crucial role to help fulfil ever-increasing energy storage demands, but is greatly hindered by the limited number of active sites for fast charge adsorption/desorption processes. Herein, an efficient strategy is demonstrated for making defect-rich bismuth sulfides in combination with surface nitrogen-doped carbon nanofibers (dr-Bi2 S3 /S-NCNF) as flexible free-standing electrodes for asymmetric supercapacitors. The dr-Bi2 S3 /S-NCNF composite exhibits superior electrochemical performances with an enhanced specific capacitance of 466 F g-1 at a discharge current density of 1 A g-1 . The high performance of dr-Bi2 S3 /S-NCNF electrodes originates from its hierarchical structure of nitrogen-doped carbon nanofibers with well-anchored defect-rich bismuth sulfides nanostructures. As modeled by density functional theory calculation, the dr-Bi2 S3 /S-NCNF electrodes exhibit a reduced OH- adsorption energy of -3.15 eV, compared with that (-3.06 eV) of defect-free bismuth sulfides/surface nitrogen-doped carbon nanofiber (df-Bi2 S3 /S-NCNF). An asymmetric supercapacitor is further fabricated by utilizing dr-Bi2 S3 /S-NCNF hybrid as the negative electrode and S-NCNF as the positive electrode. This composite exhibits a high energy density of 22.2 Wh kg-1 at a power density of 677.3 W kg-1 . This work demonstrates a feasible strategy to construct advanced metal sulfide-based free-standing electrodes by incorporating defect-rich structures using surface engineering principles.

Strategic Design of Vacancy-Enriched Fe1- xS Nanoparticles Anchored on Fe3C-Encapsulated and N-Doped Carbon Nanotube Hybrids for High-Efficiency Triiodide Reduction in Dye-Sensitized Solar Cells.

A new class of hybrids with the unique electrocatalytic nanoarchitecture of Fe1- xS anchored on Fe3C-encapsulated and N-doped carbon nanotubes (Fe1- xS/Fe3C-NCNTs) is innovatively synthesized through a facile one-step carbonization-sulfurization strategy. The efficient synthetic protocols on phase structure evolution and dynamic decomposition behavior enable the production of the Fe1- xS/Fe3C-NCNT hybrid with advanced structural and electronic properties, in which the Fe vacancy-contained Fe1- xS showed the 3d metallic state electrons and an electroactive Fe in +2/+3 valence, and the electronic structure of the CNT was effectively modulated by the incorporated Fe3C and N, with the work function decreased from 4.85 to 4.63 eV. The meticulous structural, electronic, and compositional control unveils the unusual synergetic catalytic properties for the Fe1- xS/Fe3C-NCNT hybrid when developed as counter electrodes (CEs) for dye-sensitized solar cells (DSSCs), in which the Fe3C- and N-incorporated CNTs with reduced work function and increased charge density provide a highway for electron transport and facilitate the electron migration from Fe3C-NCNTs to ultrahigh active Fe1- xS with the electron-donating effect, and the Fe vacancy-enriched Fe1- xS nanoparticles exhibit ultrahigh I3- adsorption and charge-transfer ability. As a consequence, the DSSC based on the Fe1- xS/Fe3C-NCNT CE delivers a high power conversion efficiency of 8.67% and good long-term stability with a remnant efficiency of 8.00% after 168 h of illumination, superior to those of traditional Pt. Furthermore, the possible catalytic mechanism toward I3- reduction is creatively proposed based on the structure-activity correlation. In this work, the structure engineering, electronic modulation, and composition control opens up new possibilities in constructing the novel electrocatalytic nanoarchitecture for highly efficient CEs in DSSCs.

Water dissociation on K2O-pre-adsorbed transition metals: a systematic theoretical study.

It is imperative to regulate O-H bond cleavage on metal surfaces with a pre-adsorbed K2O promoter in heterogeneous catalysis. Density functional theory (DFT) calculations have been performed to explore the adsorption and dissociation of water on K2O-pre-adsorbed transition metal surfaces (Au, Ag, Cu, Ni, Pt, Rh, Ir, Pd, Ru, Co and Fe) as compared with those on clean and K-pre-adsorbed metal surfaces. The calculation results indicate that the presence of K2O species significantly promotes water dissociation and the promoting effect depends on the adsorption strength of K2O, namely, the more strongly K2O binds to the metal surface, the less promoting effect it has on the water O-H bond cleavage. Based on geometrical and electronic analysis, the stronger promoting effect of K2O than K on water dissociation on the given metal surfaces can be attributed to stronger attractive electrostatic interactions between OH and the dissociating H of H2O at the TSs as well as between O of H2O and K of K2O at the ISs on K2O-pre-adsorbed surfaces compared with those on K-pre-covered surfaces. Moreover, the additional hydrogen bond interaction between H and Oad of K2O at the ISs on Cu/Ag/Au and Fe/Co/Ni metals would be responsible for the much greater promoting effect of K2O than K on these metal surfaces, while there is a slightly greater promoting effect of K2O on the remaining metal surfaces. From the above analysis, we expect our studies can provide profound understanding of the nature of the promoting effect of K2O on O-H bond scission.

Solvothermally Controlled Synthesis of Organic-Inorganic Hybrid Nanosheets as Efficient pH-Universal Hydrogen-Evolution Electrocatalysts.

Electrocatalysts with a high efficiency and durability for the hydrogen evolution reaction (HER) hold tremendous promise for next-generation energy conversion. Among the state-of-art catalysts for HER, organic-inorganic hybrid nanosheets exhibit a great potential with the merits of high activity, good durability, and low cost. Nevertheless, there is no general method for the synthesis of binary metal phosphide hybrid nanosheet HER catalysts with a tunable morphology and composition. Herein, we report a facile approach for the synthesis of nanosheets consisting of a binary cobalt nickel phosphide hybrid with a hierarchically porous nanostructures using an oxidation- phosphorization process. The as-optimized hybrid nanosheets annealed at 350 °C yield the highest pH-universal activity with overpotentials of 148, 111, and 173 mV in acidic, alkaline, and neutral media, respectively. Besides the promoted mass diffusion in the hierarchically porous structure, the extraordinary performance can be also attributed to the weakened adsorption of hydrogen as a result of the tunable composition of Co and Ni, which was revealed by first-principles calculations.

An Efficient, Visible-Light-Driven, Hydrogen Evolution Catalyst NiS/Znx Cd1-x S Nanocrystal Derived from a Metal-Organic Framework.

Photocatalytic water splitting for hydrogen production using sustainable sunlight is a promising alternative to industrial hydrogen production. However, the scarcity of highly active, recyclable, inexpensive photocatalysts impedes the development of photocatalytic hydrogen evolution reaction (HER) schemes. Herein, a metal-organic framework (MOF)-template strategy was developed to prepare non-noble metal co-catalyst/solid solution heterojunction NiS/Znx Cd1-x S with superior photocatalytic HER activity. By adjusting the doping metal concentration in MOFs, the chemical compositions and band gaps of the heterojunctions can be fine-tuned, and the light absorption capacity and photocatalytic activity were further optimized. NiS/Zn0.5 Cd0.5 S exhibits an optimal HER rate of 16.78 mmol g-1 h-1 and high stability and recyclability under visible-light irradiation (λ>420 nm). Detailed characterizations and in-depth DFT calculations reveal the relationship between the heterojunction and photocatalytic activity and confirm the importance of NiS in accelerating the water dissociation kinetics, which is a crucial factor for photocatalytic HER.

Identification of Fe and Zr oxide phases in an iron-zirconium binary oxide and arsenate complexes adsorbed onto their surfaces.

The Fe-Zr binary oxide adsorbents have higher arsenic adsorptive capacities than either iron oxide or zirconium oxide alone, indicating a strong synergistic effect exists between Fe and Zr oxides. However, no generally accepted in-depth explanations have been reached on the origin of this better performance. In the present study, the component phases, the active surface sites, the structure of the adsorbed As(V) surface species, and the mechanism of the synergistic effect, were investigated and elucidated using multiple advanced experimental techniques combined with quantum chemical calculations. Goethite and lepidocrocite were identified as the main Fe oxide components while amorphous zirconium hydroxide was the main Zr oxide component, respectively. A monodentate-mononuclear complex and a bidentate-binuclear complex were revealed to be dominant on the surface, respectively, when at lower and higher initial As(V) concentrations. Density functional theory calculations indicated that As(V) preferred to bind with Zr-OH rather than Fe-OH. This was verified with the As K-edge EXAFS results and XPS observations. The synergistic effect was due to a short-range ordering state, the enlarged contents of amorphous and poorly-crystalline fractions, and increased hydroxyl surface site density. These results lead to the realization that the above properties are preferred in future adsorbent preparations.

Ethanol synthesis from syngas over Cu(Pd)-doped Fe(100): a systematic theoretical investigation.

Although the reaction mechanism of syngas on Fe or Cu(Pd)-doped Fe has been studied extensively both experimentally and theoretically, the systematic prediction of the catalytic activity and selectivity for the formation of ethanol at the molecular level has not been reported to the best of our knowledge. In our present work, density functional theory calculations were performed to investigate the reaction mechanisms of the synthesis of ethanol, methanol, and methane from syngas over bimetallic Cu/Fe and Pd/Fe catalysts. Possible elementary steps involved in the formation of ethanol from syngas have been studied from thermodynamic and kinetic viewpoints. Our results show that an optimal route for the formation of ethanol on Cu/Fe and Pd/Fe catalysts starts with an initial process of the dissociation and hydrogenation of CO to produce CH3 species. Subsequently, the insertion of HCO groups into CH3 species leads to the formation of CH3CHO, followed by successive hydrogenation to form ethanol. The selectivity for ethanol is controlled by the formation of methyl species and the formation of C-C bonds between methyl species and CHO groups. Our kinetic model analysis shows that the selectivity for ethanol is highest on the Cu-Fe system, followed by Pd-Fe, and pure Fe (Cu) has the lowest selectivity. This is in close agreement with experimental findings in general. Possible reasons can be explained as follows: Fe sites favor the formation of CHx species, Cu and Pd sites are necessary to provide undissociated CO/HCO species, and Cu/Fe and Pd/Fe catalysts will provide dual active sites that are synergetic for chain propagation to generate precursors of C2 oxygenates by the insertion of CO/HCO groups into CHx species. The present results will further help the prediction of reaction activity and the design of efficient F-T catalysts for the formation of C2+ species to some extent.

Iridium-Based Multimetallic Porous Hollow Nanocrystals for Efficient Overall-Water-Splitting Catalysis.

The development of active and durable bifunctional electrocatalysts for overall water splitting is mandatory for renewable energy conversion. This study reports a general method for controllable synthesis of a class of IrM (M = Co, Ni, CoNi) multimetallic porous hollow nanocrystals (PHNCs), through etching Ir-based, multimetallic, solid nanocrystals using Fe3+ ions, as catalysts for boosting overall water splitting. The Ir-based multimetallic PHNCs show transition-metal-dependent bifunctional electrocatalytic activities for both the hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) in acidic electrolyte, with IrCo and IrCoNi PHNCs being the best for HER and OER, respectively. First-principles calculations reveal a ligand effect, induced by alloying Ir with 3d transition metals, can weaken the adsorption energy of oxygen intermediates, which is the key to realizing much-enhanced OER activity. The IrCoNi PHNCs are highly efficient in overall-water-splitting catalysis by showing a low cell voltage of only 1.56 V at a current density of 2 mA cm-2 , and only 8 mV of polarization-curve shift after a 1000-cycle durability test in 0.5 m H2 SO4 solution. This work highlights a potentially powerful strategy toward the general synthesis of novel, multimetallic, PHNCs as highly active and durable bifunctional electrocatalysts for high-performance electrochemical overall-water-splitting devices.

Periodic density functional theory analysis of direct methane conversion into ethylene and aromatic hydrocarbons catalyzed by Mo4C2/ZSM-5.

Mo/ZSM-5-catalyzed methane conversion into aromatic hydrocarbons is an important reaction to produce ethylene and benzene, but the detailed reaction mechanism has not been investigated due to its high complexity. In the present study, density functional theory combined with a periodic model was used to investigate the reaction mechanism of direct methane conversion into aromatic hydrocarbons catalyzed by Mo/ZSM-5. The calculation results show that the active phase for Mo is Mo4C2 instead of MoOx. The whole reaction processes processed via the following steps: the C-H bond in methane was first activated by Mo4C2 with an energy barrier of 1.01 eV and then converted into ethylene species via the coupling of two CH3 species as well as two successive dehydrogenation steps (2CH3 → C2H6 → C2H4 + 2H). The rate-controlling step for the processes to form ethylene is the coupling of two methyl species with a barrier of 1.22 eV. The produced ethylene species then react with each other to produce C6H8via the reaction of 3C2H4 → C3H8 + 2H2, and molecular benzene is formed by successive dehydrogenation of C6H8. The rate-limiting step for benzene formation from ethylene is the cyclization step of chain C6H8 with an energy barrier of 1.21 eV. Additionally, molecular propane (C3H8) is formed by the reaction of C2H4 + CH4 → C3H8, and the controlling step C3H7 + H → C3H8 has a barrier of 1.46 eV. Molecular C10H12 is produced via coupling of C6H8 and C2H4, where the limiting step is the dehydrogenation step of C8H12 with an energy barrier of 1.44 eV. Our present calculation results indicate that the selectivity of benzene was the largest among the possible products, that is, C2H4, C3H6, C6H6 and C10H12, based on the corresponding controlling step barrier. Importantly, the rate-controlling step for the whole reaction process from methane to benzene is the dissociative adsorption of methane (CH4 → CH3 + H) with an energy barrier of 1.83 eV when considering entropy contribution. The present study may help people design a good catalyst for the formation of benzene from methane; in other words, the catalyst should have a good ability to activate the C-H bond of molecular methane.

Oxygen-assisted water partial dissociation on copper: a model study.

It is essential to understand and control the O-H bond cleavage on metal surfaces with pre-adsorbed oxygen atoms in heterogeneous catalytic processes. The adsorption and dissociation of water on clean and oxygen-pre-adsorbed copper surfaces, including Cu(111), Cu(110), Cu(100), Cu(210), Cu(211), Cu(310) and Cu(110)-(1 × 2), as well as Cu-ad-row and Cu-ad-atom, have been investigated by the density functional theory-generalized gradient approximation (DFT-GGA) method. The calculation results indicate that the presence of oxygen species significantly promotes the water dissociation. It is found that the promotion effect depends both on the adsorption energy of the pre-adsorbed oxygen and the distance between the pre-adsorbed oxygen and the stripped hydrogen in water: the more strongly the oxygen atom binds to the metal surface, the less the promotion effect it has on the water O-H bond cleavage; the shorter the distance between pre-adsorbed oxygen and hydrogen in water, the greater is the promotion effect. Based on electronic analysis, physical origin of the promotion effect can be attributed to the strong interaction of acid-base pair sites on oxygen-metal systems.