Boosting electrochemical oxygen reduction to hydrogen peroxide coupled with organic oxidation.

The electrochemical oxygen reduction reaction (ORR) to produce hydrogen peroxide (H2O2) is appealing due to its sustainability. However, its efficiency is compromised by the competing 4e- ORR pathway. In this work, we report a hierarchical carbon nanosheet array electrode with a single-atom Ni catalyst synthesized using organic molecule-intercalated layered double hydroxides as precursors. The electrode exhibits excellent 2e- ORR performance under alkaline conditions and achieves H2O2 yield rates of 0.73 mol gcat-1 h-1 in the H-cell and 5.48 mol gcat-1 h-1 in the flow cell, outperforming most reported catalysts. The experimental results show that the Ni atoms selectively adsorb O2, while carbon nanosheets generate reactive hydrogen species, synergistically enhancing H2O2 production. Furthermore, a coupling reaction system integrating the 2e- ORR with ethylene glycol oxidation significantly enhances H2O2 yield rate to 7.30 mol gcat-1 h-1 while producing valuable glycolic acid. Moreover, we convert alkaline electrolyte containing H2O2 directly into the downstream product sodium perborate to reduce the separation cost further. Techno-economic analysis validates the economic viability of this system.

Facilitating the dry reforming of methane with interfacial synergistic catalysis in an Ir@CeO2-x catalyst.

The dry reforming of methane provides an attractive route to convert greenhouse gases (CH4 and CO2) into valuable syngas, so as to resolve the carbon cycle and environmental issues. However, the development of high-performance catalysts remains a huge challenge. Herein, we report a 0.6% Ir/CeO2-x catalyst with a metal-support interface structure which exhibits high CH4 (~72%) and CO2 (~82%) conversion and a CH4 reaction rate of ~973 µmolCH4 gcat-1 s-1 which is stable over 100 h at 700 °C. The performance of the catalyst is close to the state-of-the-art in this area of research. A combination of in situ spectroscopic characterization and theoretical calculations highlight the importance of the interfacial structure as an intrinsic active center to facilitate the CH4 dissociation (the rate-determining step) and the CH2* oxidation to CH2O* without coke formation, which accounts for the long-term stability. The catalyst in this work has a potential application prospect in the field of high-value utilization of carbon resources.

Rational Design and Precise Synthesis of Single-Atom Alloy Catalysts for the Selective Hydrogenation of Nitroarenes.

Single-atom alloys (SAAs) have gained increasing prominence in the field of selective hydrogenation reactions due to their uniform distribution of active sites and the unique host-guest metal interactions. Herein, 15 SAAs are constructed to comprehensively elucidate the relationship between host-guest metal interaction and catalytic performance in the selective hydrogenation of 4-nitrostyrene (4-NS) by density functional theory (DFT) calculations. The results demonstrate that the SAAs with strong host-guest metal interactions exhibit a preference for N─O bond cleavage, and the reaction energy barrier of the hydrogenation process is primarily influenced by the host metal. Among them, Ir1Ni SAA stands out as the prime catalyst candidate, showcasing exceptional activity and selectivity. Furthermore, the Ir1Ni SAA is subsequently prepared through precise synthesis techniques and evaluated in the selective hydrogenation of 4-NS to 4-aminostyrene (4-AS). As anticipated, the Ir1Ni SAA demonstrates extraordinary catalytic performance (yield > 96%). In situ FT-IR experiments and DFT calculations further confirmed that the unique host-guest metal interaction at the Ir-Ni interface site of Ir1Ni SAA endows it with excellent 4-NS selective hydrogenation ability. This work provides valuable insights into enhancing the performance of SAAs catalysts in selective hydrogenation reactions by modulating the host-guest metal interactions.

Highly Selective Hydrogenation of Unsaturated Aldehydes in Aqueous Phase.

Chemoselective hydrogenation of carbonyl in unsaturated aldehydes is a significant process in the chemical industry, in which the development of aqueous-phase reaction systems as a substitution to organic ones is challenging. Herein, we report Ir atomic cluster catalysts anchored onto WO3-x nanorods via a reduction treatment at various temperatures (denoted as Ir/WOx-T, T = 200, 300, 400, and 500 °C), which accelerates the chemoselective hydrogenation of carbonyl groups in aqueous solutions. The optimal catalyst Ir/WOx-300 exhibits exceptional activity (TOF value: 1313.7 min-1) and chemoselectivity toward cinnamaldehyde (CAL) hydrogenation to cinnamyl alcohol (COL) (yield: ∼98.0%) in water medium, which is, to the best of our knowledge, the highest level compared with previously reported heterogeneous catalysts in liquid-phase reaction. Ac-HAADF-STEM, XAFS, and XPS verify the formation of interface structure (Irδ+-Ov-W5+ (0 ≤ δ ≤ 4); Ov denotes oxygen vacancy) induced by metal-support interaction and the largest concentration of interfacial Ir (Irδ+) in Ir/WOx-300. In situ studies (Raman, FT-IR), isotopic labeling measurements combined with DFT calculations substantiate that the hydrogenation of the C=O group consists of two pathways: water-mediated hydrogenation (predominant) and direct hydrogenation via H2 dissociation (secondary). In the former case, W5+-Ov site accelerates the activation adsorption of H2O, while Ir0 site facilitates the H-H bond cleavage of H2 and Irδ+ promotes the CAL adsorption. H2O molecule, as the source of hydrogen species, participates directly in the hydrogenation of the carbonyl group through a hydrogen-bonded network, with a largely reduced energy barrier relative to the H2 dissociation path. This work demonstrates a green catalytic route that breaks the activity-selectivity trade-off toward the selective hydrogenation of unsaturated aldehydes, which shows great potential in heterogeneous catalysis.

Highly Stable Pt/CeO2 Catalyst with Embedding Structure toward Water-Gas Shift Reaction.

Strong metal-support interaction (SMSI) has been extensively studied in heterogeneous catalysis because of its significance in stabilizing active metals and tuning catalytic performance, but the origin of SMSI is not fully revealed. Herein, by using Pt/CeO2 as a model catalyst, we report an embedding structure at the interface between Pt and (110) plane of CeO2, where Pt clusters (∼1.6 nm) are embedded into the lattice of ceria within 3-4 atomic layers. In contrast, this phenomenon is absent in the CeO2(100) support. This unique geometric structure, as an effective motivator, triggers more significant electron transfer from Pt clusters to CeO2(110) support accompanied by the formation of interfacial structure (Ptδ+-Ov-Ce3+), which plays a crucial role in stabilizing Pt nanoclusters. A comprehensive investigation based on experimental studies and theoretical calculations substantiates that the interfacial sites serve as the intrinsic active center toward water-gas shift reaction (WGSR), featuring a moderate strength CO activation adsorption and largely decreased energy barrier of H2O dissociation, accounting for the prominent catalytic activity of Pt/CeO2(110) (a reaction rate of 15.76 molCO gPt-1 h-1 and a turnover frequency value of 2.19 s-1 at 250 °C). In addition, the Pt/CeO2(110) catalyst shows a prominent durability within a 120 h time-on-stream test, far outperforming the Pt/CeO2(100) one, which demonstrates the advantages of this embedding structure for improving catalyst stability.

Designing Cu0-Cu+ dual sites for improved C-H bond fracture towards methanol steam reforming.

Copper-based catalysts serve as the predominant methanol steam reforming material although several fundamental issues remain ambiguous such as the identity of active center and the aspects of reaction mechanism. Herein, we prepare Cu/Cu(Al)Ox catalysts with amorphous alumina-stabilized Cu2O adjoining Cu nanoparticle to provide Cu0-Cu+ sites. The optimized catalyst exhibits 99.5% CH3OH conversion with a corresponding H2 production rate of 110.8 µmol s-1 gcat-1 with stability over 300 h at 240 °C. A binary function correlation between the CH3OH reaction rate and surface concentrations of Cu0 and Cu+ is established based on kinetic studies. Intrinsic active sites in the catalyst are investigated with in situ spectroscopy characterization and theoretical calculations. Namely, we find that important oxygen-containing intermediates (CH3O* and HCOO*) adsorb at Cu0-Cu+ sites with a moderate adsorption strength, which promotes electron transfer from the catalyst to surface species and significantly reduces the reaction barrier of the C-H bond cleavage in CH3O* and HCOO* intermediates.

Phosphorescent-Dye-Sensitized Quantum-Dot Light-Emitting Diodes with 37% External Quantum Efficiency.

Exciton harvesting is of paramount importance for quantum-dot light-emitting diodes (QLEDs). Direct exciton harvesting by the quantum dots (QDs) emitting layer suffers from poor hole injection due to the low conduction bands and valence bands of QDs, leading to unbalanced electron-hole injection and recombination. To address this issue, here, an exciton sensitizing approach is reported, where excitons form on a phosphorescent-dye-doped layer, which then transfer their energies to adjacent QDs layer for photon emission. Due to the very efficient exciton formation and energy-transfer processes, higher device performance can be achieved. To demonstrate the above strategy, red QLEDs with a phosphorescent dye, iridium (III) bis(2-methyldibenzo-[f,h]quinoxaline) (acetylacetonate), Ir(MDQ)2 (acac), doped hole-transporting layer are fabricated and studied. At a doping concentration of 10 wt%, the best device achieves record high current efficiency, power efficiency, and external quantum efficiency (EQE) of 37.3 cd A-1 , 41 lm W-1 , and 37%, respectively. Simultaneously, the efficiency roll-off characteristic is greatly improved, in that 35% EQE can be well retained at a high luminance level of 450 000 cd m-2 . Moreover, the devices also exhibit good stability and reproducibility.

Metal-Acid Interface Engineering in Pd-WOx Bifunctional Catalysts for the Hydroalkylation Tandem Reaction of Benzene.

The hydroalkylation tandem reaction of benzene to cyclohexylbenzene (CHB) provides an atom economy route for conversion and utilization of benzene; yet, it presents significant challenges in activity and selectivity control. In this work, we report a metal-support synergistic catalyst prepared via calcination of W-precursor-containing montmorillonite (MMT) followed by Pd loading (denoted as Pd-mWOx/MMT, m = 5, 15, and 25 wt %), which shows excellent catalytic performance for hydroalkylation of benzene. A combination study (X-ray diffraction (XRD), hydrogen-temperature programmed reduction (H2-TPR), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), UV-vis, Raman, and density functional theory (DFT) calculations) confirms the formation of interfacial sites Pd-(WOx)-H, whose concentration is dependent on the interaction between Pd and WOx. The optimized catalyst (Pd-15WOx/MMT) exhibits a CHB yield of up to 45.1% under a relatively low hydrogen pressure, which stands at the highest level among state-of-the-art catalysts. Investigations on the structure-property correlation based on in situ FT-IR and control experiments further verify that the Pd-(WOx)-H structure serves as the dual-active site: the interfacial Pd site accelerates benzene hydrogenation to cyclohexene (CHE), while the interfacial Bronsted (B) acid site in Pd-(WOx)-H boosts the alkylation of benzene and CHE to CHB. This study offers a new strategy for the design and preparation of metal-acid bifunctional catalysts, which shows potential application in the hydroalkylation reaction of benzene.

A strong bimetal-support interaction in ethanol steam reforming.

The metal-support interaction (MSI) in heterogeneous catalysts plays a crucial role in reforming reaction to produce renewable hydrogen, but conventional objects are limited to single metal and support. Herein, we report a type of RhNi/TiO2 catalysts with tunable RhNi-TiO2 strong bimetal-support interaction (SBMSI) derived from structure topological transformation of RhNiTi-layered double hydroxides (RhNiTi-LDHs) precursors. The resulting 0.5RhNi/TiO2 catalyst (with 0.5 wt.% Rh) exhibits extraordinary catalytic performance toward ethanol steam reforming (ESR) reaction with a H2 yield of 61.7%, a H2 production rate of 12.2 L h-1 gcat-1 and a high operational stability (300 h), which is preponderant to the state-of-the-art catalysts. By virtue of synergistic catalysis of multifunctional interface structure (Rh-Niδ--Ov-Ti3+; Ov denotes oxygen vacancy), the generation of formate intermediate (the rate-determining step in ESR reaction) from steam reforming of CO and CHx is significantly promoted on 0.5RhNi/TiO2 catalyst, accounting for its ultra-high H2 production.

Theoretical Calculations on Metal Catalysts Toward Water-Gas Shift Reaction: a Review.

Water-gas shift (WGS) reaction offers a dominating path to hydrogen generation from fossil fuel, in which heterogeneous metal catalysts play a crucial part in this course. This review highlights and summarizes recent developments on theoretical calculations of metal catalysts developed to date, including surface structure (e. g., monometallic and polymetallic systems) and interface structure (e. g., supported catalysts and metal oxide composites), with special emphasis on the characteristics of crystal-face effect, alloying strategy, and metal-support interaction. A systematic summarization on reaction mechanism was performed, including redox mechanism, associative mechanism as well as hybrid mechanism; the development on chemical kinetics (e. g., molecular dynamics, kinetic Monte Carlo and microkinetic simulation) was then introduced. At the end, challenges associated with theoretical calculations on metal catalysts toward WGS reaction are discussed and some perspectives on the future advance of this field are provided.

Irradiance penetration distribution and flashing light frequency simultaneously affected with microalgal cell absorption and CO2 bubble scattering in a raceway pond.

In order to investigate light penetration and flashing light frequency for microalgal cell-CO2 bubble culture system in a raceway pond, user-defined function for CO2 mass transfer and bubble scattering models coupled with discrete ordinates radiation model were adopted to clarify simultaneous effects of microalgal cell absorption and CO2 bubble scattering. Light intensity along the microalgal suspension depth attenuated more rapidly with increased biomass concentration, decreased bubble generation diameter, increased CO2 gas content and incident light intensity. Ratio of light zone decreased from 81.13 % to 20.00 % when biomass concentration increased from 0 to 0.4 g/L because of light absorption and shading effects of microalgae. When bubble generation diameter increased from 0.1 to 1.6 mm, ratio of light zone increased from 37.95 % to 42.64 %, while microalgal flashing light cycle first decreased to a valley of 1.81 s at 0.8 mm and then increased. Local light intensity in the upper layers was more enhanced due to lots of CO2 bubbles gathering and reflecting more light with decreased bubble diameter and increased gas content. Light attenuated more rapidly in microalgal suspension with decreased bubble generation diameter and increased CO2 gas content because of increased bubble diffraction coefficient and contact area. When initial CO2 volume fraction increased from 0.02 to 0.2, flashing light frequency of microalgal cells decreased from 0.55 to 0.29 Hz and light zone time ratio φ decreased from 36.90 % to 18.40 %. At a biomass concentration of 0.1 g/L and a bubble flow rate of 0.1 m/s, the maximum light penetration and microalgal growth rate was achieved when bubble diameter, incident light intensity and gas content were optimally at 0.8 mm, 200 W/m2 and 0.02, respectively. This work provides data support and theoretical guidance for photobioreactor design and optimization of light energy utilization.

A genome-wide association study provides insights into fatty acid synthesis and metabolism in Malus fruits.

As a precursor of aromatic compounds, fatty acids play important roles in apple fruit quality; however, the genetic and molecular basis underlying fatty acid synthesis and metabolism is largely unknown. In this study, we conducted a genome-wide association study (GWAS) of seven fatty acids using genomic data of 149 Malus accessions and identified 232 significant signals (-log10P>5) associated with 99 genes from GWAS of four fatty acids across 2 years. Among these, a significant GWAS signal associated with linoleic acid was identified in the transcriptional regulator SUPERMAN-like (SUP) MD13G1209600 at chromosome 13 of M. × domestica. Transient overexpression of MdSUP increased the contents of linoleic and linolenic acids and of three aromatic components in the fruit. Our study provides genetic and molecular information for improving the flavor and nutritional value of apple.

Metal-Acid Bifunctional Catalysts toward Tandem Reaction: One-Step Hydroalkylation of Benzene to Cyclohexylbenzene.

The one-step hydroalkylation of benzene to cyclohexylbenzene (CHB) is a technically challenging and economically interesting reaction with great industrial importance, where bifunctional catalysts play a crucial role in such a tandem reaction. In this work, we report H3PW12O40 (HPW) modified Ni nanoparticles (NPs) supported on mixed metal oxides (Ni/MMOs), which are featured by HPW species localized on the surface of Ni NPs (denoted as HPW-Ni/MMOs). The optimal catalyst (0.3HPW-Ni/MMOs) exhibits a satisfactory catalytic performance toward benzene hydroalkylation to CHB with a CHB yield of up to 41.2%, which is the highest standard among previously reported catalysts to date. A combination investigation based on HR-TEM, XPS, XANES, and in situ FT-IR verified the electron transfer from the W atom to the adjacent Ni atom, which facilitated the formation and desorption of cyclohexene (CHE) from Ni followed by the alkylation reaction of benzene and CHE at the interfacial Brønsted (B) acid sites of HPW, accounting for the significantly enhanced catalytic behavior. It is proposed that the HPW-Ni interface structure in xHPW-Ni/MMOs samples provides unique adsorption sites for benzene and CHE with a moderate adsorption strength, which serve as the intrinsic active center for this reaction: the Ni site promotes the hydrogenation of benzene to CHE, while the B acid site in HPW facilitates the alkylation of CHE and benzene to produce CHB. This work provides a fundamental understanding of the metal-acid synergistic catalysis toward the hydroalkylation reaction, which can be extended to the design and preparation of high-performance catalysts used in tandem reactions.

Nocardioides nematodiphilus sp. nov., isolated from rhizosphere of Arabidopsis thaliana.

An actinobacterial strain, designated R-N-C8T, was isolated from the rhizosphere soil of Arabidopsis thaliana collected in Yunnan Province, south-west China. Based on the results of 16S rRNA gene sequence analysis, strain R-N-C8T had highest similarity to Nocardioides terrae CGMCC 1.7056T (96.5%), Nocardioides opuntiae KCTC 19804T (96.3%) and Nocardioides currus IB-3T (96.1%), and lower than 96.0 % similarity to other members of the genus Nocardioides. Phylogenetic trees based on 16S rRNA gene sequences indicated that strain R-N-C8T formed an isolated branch with N. terrae CGMCC 1.7056T and N. opuntiae KCTC 19804T. The polar lipids contained phosphatidylglycerol, diphosphatidylglycerol, one unidentified phosphoglycolipid and four unidentified phospholipids in the cellular membrane. The major fatty acids were identified as iso-C16 : 0, anteiso-C17 : 0, iso-C17 : 0, summed feature 9 (iso-C17 : 1 ω9c and/or C16 : 0 10-methyl) and iso-C15 : 0. The predominant respiratory quinone was MK-8(H4) and ll-diaminopimelic acid was the diagnostic diamino acid in the cell-wall peptidoglycan. The genomic DNA G+C content was 70.9 mol%. The orthologous average nucleotide identiy values between N. terrae CGMCC 1.7056T, N. currus IB-3T and strain R-N-C8T were 77.1 and 75.1 %, respectively. DNA-DNA hybridization values between N. terrae CGMCC 1.7056T, N. currus IB-3T and strain R-N-C8T were 20.7 and 19.9 % respectively. Data from phenotypic and genotypic analyses supported that strain R-N-C8T represents a new species of Nocardioides, for which the name Nocardioides nematodiphilus sp. nov. is proposed. The type strain is R-N-C8T (=CGMCC 1.18723T= KCTC 49528T).

Highly-efficient RuNi single-atom alloy catalysts toward chemoselective hydrogenation of nitroarenes.

The design and exploitation of high-performance catalysts have gained considerable attention in selective hydrogenation reactions, but remain a huge challenge. Herein, we report a RuNi single atom alloy (SAA) in which Ru single atoms are anchored onto Ni nanoparticle surface via Ru-Ni coordination accompanied with electron transfer from sub-surface Ni to Ru. The optimal catalyst 0.4% RuNi SAA exhibits simultaneously improved activity (TOF value: 4293 h-1) and chemoselectivity toward selective hydrogenation of 4-nitrostyrene to 4-aminostyrene (yield: >99%), which is, to the best of our knowledge, the highest level compared with reported heterogeneous catalysts. In situ experiments and theoretical calculations reveal that the Ru-Ni interfacial sites as intrinsic active centers facilitate the preferential cleavage of N-O bond with a decreased energy barrier by 0.28 eV. In addition, the Ru-Ni synergistic catalysis promotes the formation of intermediates (C8H7NO* and C8H7NOH*) and accelerates the rate-determining step (hydrogenation of C8H7NOH*).

Machine-Learning-Assisted Catalytic Performance Predictions of Single-Atom Alloys for Acetylene Semihydrogenation.

Selective semihydrogenation of acetylene for the production of polymer-grade ethylene is a significant chemical industrial process. Facile activization of acetylene and weak adsorption of ethylene are critical requirements for high-performance catalysis. Single-atom alloys (SAAs) have strong binding effect on acetylene and weak effect on ethylene, which have been regarded as the superior catalysts for acetylene semihydrogenation. Herein, we established a pioneering machine learning (ML) assisted approach to investigate the reaction activity and selectivity of 70 SAA catalysts for acetylene semihydrogenation. As the most desirable ML model, the gradient boosting regression (GBR) algorithm has been extended to predict the energy barrier of *C2Hn (n = 2-4) hydrogenation with a root-mean-square error (RMSE) of only 0.02 eV. Notably, five candidate SAAs with excellent activity and selectivity for acetylene semihydrogenation are screened out via accessible descriptors. These data of ML prediction have been verified by DFT calculation with a high-accuracy (error less than 0.07 eV). This work demonstrates the potential of ML-assisted approach for predicting the energy barrier of transition state and simultaneously provides a convenient approach for the rational design of efficient catalysts.

Metal-support interaction induced ZnO overlayer in Cu@ZnO/Al2O3 catalysts toward low-temperature water-gas shift reaction.

The water-gas shift reaction (WGSR) plays a pivotal role in many important industrial processes as well as in the elimination of residual CO in feed gas for fuel cells. The development of a high-efficiency low-temperature WGSR (LT-WGSR) catalyst has attracted considerable attention. Herein, we report a ZnO-modified Cu-based nanocatalyst (denoted as Cu@ZnO/Al2O3) obtained via an in situ topological transformation from a Cu2Zn1Al-layered double hydroxide (Cu2Zn1Al-LDH) precursor at different reduction temperatures. The optimal Cu@ZnO/Al2O3-300R catalyst with appropriately abundant Cu@ZnO interface structure shows superior catalytic performance toward the LT-WGSR with a reaction rate of up to 19.47 µmolCO gcat -1 s-1 at 175 °C, which is ∼5 times larger than the commercial Cu/ZnO/Al2O3 catalyst. High-resolution transmission electron microscopy (HRTEM) proves that the reduction treatment results in the coverage of Cu nanoparticles by ZnO overlayers induced by a strong metal-support interaction (SMSI). Furthermore, the generation of the coating layers of ZnO structure is conducive to stabilize Cu nanoparticles, accounting for long-term stability under the reaction conditions and excellent start/stop cycle of the Cu@ZnO/Al2O3-300R catalyst. This study provides a high-efficiency and low-cost Cu-based catalyst for the LT-WGSR and gives a concrete example to help understand the role of Cu@ZnO interface structure in dominating the catalytic activity and stability toward WGSR.

Spatial and temporal distribution and influencing factor analysis of the malignant tumor mortality rate around the mining area.

Mining activities can threaten residents' health even lives. Integrating spatial empirical Bayesian smoothing, joinpoint regression and spatiotemporal scanning methods, we analyzed aggregations and possible factors of four tumor mortality rates at township and village scales from 2012 to 2016 in Suxian district of Hunan Province, China. Results indicate: (1) Mortality rates were ranked: lung cancer > liver cancer > gastric cancer > colorectal cancer. (2) Lung cancer had a higher five-year mortality rate in the middle; relative risk (RR) of death from lung cancer from 2012 to 2015 in Xujiadong Village was 7.48. Liver cancer had a higher five-year mortality rate in the Middle West; RR in areas centered on Nanta Street with a radius of 9.87 km from 2015 to 2016, was 1.83. Gastric cancer had a higher five-year mortality rate in the east; RR in Xujiadong Village from 2012 to 2014 was 6.9. Five-year mortality rate of colorectal cancer was higher in the northwest; RR in regions centered on Huangcao Village with a radius of 12.11 km in 2016, was 2.88. (3) Pollution from ore mining and smelting, heavy metal and non-metallic, and mine transportation were the main possible factors. This research provides a method reference for studying spatiotemporal patterns of disease in China even the world.

Mechanism Investigations on Water Gas Shift Reaction over Cu(111), Cu(100), and Cu(211) Surfaces.

Cu-based catalysts are commonly applied in low-temperature water gas shift (WGS) reactions, owing to their low cost and high catalytic activity. The influence of different Cu surfaces on catalytic activity and mechanism over the WGS reaction remains unclear. In this work, the effect of different structures of surfaces on the WGS mechanism is studied using density functional theory (DFT). Three surface terminations (Cu(100), Cu(111), and Cu(211)) of Cu are considered, and the coordination number (CN) of the active Cu site is in the range from 7 to 9. The most stable surface is Cu(211). Then, d-band center values are calculated, which decrease in the following sequence: Cu(211) > Cu(100) > Cu(111). This shows that d-band center values decrease with increasing coordination number. The increase in the centers of the d-band leads to an increase in the adsorption strength of CO and H2O adsorbates, which is in line with the theory of the d-band center. In addition, the further calculated mechanism for WGS reaction over three different Cu surfaces illustrates that the carboxyl path is the most favorable mechanism, and the rate-determining step is H2O dissociation. Cu(211) shows excellent WGS catalytic performance, better than the Cu(100) and Cu(111) surfaces. This work provides theoretical insights into the rational design of highly active Cu-based catalysts toward WGS reaction.

Metal-Support Synergistic Catalysis in Pt/MoO3-x Nanorods toward Ammonia Borane Hydrolysis with Efficient Hydrogen Generation.

Ammonia borane (NH3BH3, AB) serves as a promising material for chemical storage of hydrogen owing to its high hydrogen density and superior stability, in which the development of highly efficient heterogeneous catalysts toward AB hydrolysis plays a crucial role. Herein, we report Pt atomic clusters supported on MoO3-x nanorods using a two-step process: MoO3-x nanorods were synthesized at various calcination temperatures, followed by a further deposition-precipitation approach to obtain Pt/MoO3-x catalysts (denoted as Pt/MoO3-x-T, T = 300, 400, 500, and 600 °C). The optimized Pt/MoO3-x-500 catalyst exhibits a prominent catalytic performance toward hydrolytic dehydrogenation of AB for H2 generation, with a turnover frequency value of 2268.6 min-1, which stands at the top level among the reported catalysts. Moreover, the catalyst shows a remarkable stability with 90% activity remaining after five cycles. A combination investigation including HR-TEM, ac-HAADF-STEM, XPS, in situ CO-IR, XANES, and Bader charge analysis verifies the formation of Pt2+-Ov-Mo5+ (Ov represents oxygen vacancy), whose concentration is dependent on the strength of the metal-support interaction. Studies on the structure-property correlation based on an isotopic kinetic experiment, in situ FT-IR, and DFT calculations further reveal that the Mo5+-Ov sites accelerate the dissociation of H2O molecules (rate-determining step), while the adjacent Pt2+ species facilitates the cleavage of the B-H bond in the AB molecule to produce H2. This work provides a fundamental and systematic understanding on the metal-support synergistic catalysis toward robust H2 production, which is constructive for hydrogen storage and energy catalysis.