Precisely Control Relationship between Sulfur Vacancy and H Absorption for Boosting Hydrogen Evolution Reaction

Ef fective and robust catalyst is the core of water splitting to produce hydrogen.Here, we report an anionic etching method to tailor the sulfur vacancy(VS) of NiS_(2) to further enhance the electrocatalytic performance for hydrogen evolution reaction(HER). With the VS concentration change from 2.4% to 8.5%, the H* adsorption strength on S sites changed and NiS_(2)-VS 5.9% shows the most optimized H* adsorption for HER with an ultralow onset potential(68 m V) and has long-term stability for 100 h in 1 M KOH media. In situ attenuated-total-reflection Fourier transform infrared spectroscopy(ATR-FTIRS) measurements are usually used to monitor the adsorption of intermediates. The S-H* peak of the Ni S_(2)-VS 5.9% appears at a very low voltage, which is favorable for the HER in alkaline media. Density functional theory calculations also demonstrate the Ni S_(2)-VS 5.9% has the optimal |ΔG^(H*)| of 0.17 e V. This work offers a simple and promising pathway to enhance catalytic activity via precise vacancies strategy.

Boosting Hydrogen Storage Performance of MgH_(2) by Oxygen Vacancy-Rich H-V_(2)O_(5) Nanosheet as an Excited H-Pump

MgH_(2) is a promising high-capacity solid-state hydrogen storage material,while its application is greatly hindered by the high desorption temperature and sluggish kinetics.Herein,intertwined 2D oxygen vacancy-rich V_(2)O_(5) nanosheets(H-V_(2)O_(5))are specifically designed and used as catalysts to improve the hydrogen storage properties of MgH_(2).The as-prepared MgH_(2)-H-V_(2)O_(5) composites exhibit low desorption temperatures(Tonset=185℃)with a hydrogen capacity of 6.54 wt%,fast kinetics(Ea=84.55±1.37 kJ mol^(-1) H_(2) for desorption),and long cycling stability.Impressively,hydrogen absorption can be achieved at a temperature as low as 30℃ with a capacity of 2.38 wt%within 60 min.Moreover,the composites maintain a capacity retention rate of~99%after 100 cycles at 275℃.Experimental studies and theoretical calculations demonstrate that the in-situ formed VH_(2)/V catalysts,unique 2D structure of H-V_(2)O_(5) nanosheets,and abundant oxygen vacancies positively contribute to the improved hydrogen sorption properties.Notably,the existence of oxygen vacancies plays a double role,which could not only directly accelerate the hydrogen ab/de-sorption rate of MgH_(2),but also indirectly affect the activity of the catalytic phase VH_(2)/V,thereby further boosting the hydrogen storage performance of MgH_(2).This work highlights an oxygen vacancy excited“hydrogen pump”effect of VH_(2)/V on the hydrogen sorption of Mg/MgH_(2).The strategy developed here may pave a new way toward the development of oxygen vacancy-rich transition metal oxides catalyzed hydride systems.

Unsaturated bi-heterometal clusters in metal-vacancy sites of 2D MoS2 for efficient hydrogen evolution

The valence states and coordination structures of doped heterometal atoms in two-dimensional(2D)nanomaterials lack predictable regulation strategies.Hence,a robust method is proposed to form unsaturated heteroatom clusters via the metal-vacancy restraint mechanism,which can precisely regulate the bonding and valence state of heterometal atoms doped in 2D molybdenum disulfide.The unsaturated valence state of heterometal Pt and Ru cluster atoms form a spatial coordination structure with Pt–S and Ru–O–S as catalytically active sites.Among them,the strong binding energy of negatively charged suspended S and O sites for H+,as well as the weak adsorption of positively charged unsaturated heterometal atoms for H*,reduces the energy barrier of the hydrogen evolution reaction proved by theoretical calculation.Whereupon,the electrocatalytic hydrogen evolution performance is markedly improved by the ensemble effect of unsaturated heterometal atoms and highlighted with an overpotential of 84 mV and Tafel slope of 68.5 mV dec^(−1).In brief,this metal vacancy-induced valence state regulation of heterometal can manipulate the coordination structure and catalytic activity of heterometal atoms doped in the 2D atomic lattice but not limited to 2D nanomaterials.

Regulation of the selective hydrogenation performance of sulfur-doped carbon-supported palladium on chloronitrobenzene

The overall performance of metal catalysts can be efficiently adjusted by modifying carbon carriers with different valence sulfur precursors.The wet impregnation technique successfully prepared carbon material carriers doped with varying sources of sulfur(Na_(2)SO_(4),NaHSO_(3),Na_(2)S·9H_(2)O).Palladium carbon catalysts doped with different sulfur precursors had been prepared with the aid of the liquid-phase reduction method of the selective hydrogenation of o-chloronitrobenzene(o-CNB)to o-chloroaniline(o-CAN).The catalyst prepared for Na_(2)S·9H_(2)O as a precursor has excellent performance,and the selectivity for o-CAN is more than 99.9%at 100%conversion.In addition,the characterization results show that with the decrease of S valence,the electronic effect between S and Pd increases,and the outer electron shift of Pd increases,which reduces the adsorption and dissociation ability of Pd to hydrogen,resulting in excellent selectivity.The effects provided a good idea for the hydrogenation of o-CNB and a different point of view on sulfur doping in a variety of hydrogenation reactions.

Anchoring Ni single atoms on sulfur-vacancy-enriched ZnIn_(2)S_(4) nanosheets for boosting photocatalytic hydrogen evolution

Structure manipulation of photocatalysts at an atomic scale is a promising way to improve its photocatalytic performance.Herein,we realize the anchoring of single Ni atoms on the ZnIn_(2)S_(4) nanosheets with rich sulfur vacancies.Experimental results demonstrate that single Ni atoms induce the formation of NiO-M(Zn/In) atomic interface,which can efficiently promote the carriers separation and prolong the carrier life time.In addition,in situ electron spin resonance spectroscopy(ESR) confirms that the single Ni atoms act as an electron trapping center for protons reduction.As a result,the single Ni atoms decorated ZnIn_(2)S_(4) nanosheets with rich sulfur vacancies(Ni/ZnIn_(2)S_(4)-RVs) shows a hydrogen evolution rate up to 89.4 μmol h^(-1), almost 5.7 and 2.3 times higher compared to that of ZnIn_(2)S_(4) nanosheets with poor sulfur vacancies and rich sulfur vacancies(denoted as ZnIn_(2)S_(4)-PVs and ZnIn_(2)S_(4)-RVs).This work opens up a new perspective manipulating the single-atom cocatalyst and sulfur vacancy on sulfide supports for improving photocatalytic hydrogen evolution.

Engineering oxygen vacancies on Tb-doped ceria supported Pt catalyst for hydrogen production through steam reforming of long-chain hydrocarbon fuels

Steam reforming of long-chain hydrocarbon fuels for hydrogen production has received great attention for thermal management of the hypersonic vehicle and fuel-cell application.In this work,Pt catalysts supported on CeO_(2)and Tb-doped CeO_(2)were prepared by a precipitation method.The physical structure and chemical properties of the as-prepared catalysts were characterized by powder X-ray diffraction,scanning electron microscopy,transmission electron microscopy,Raman spectroscopy,H_(2)temperature programmed reduction,and X-ray photoelectron spectroscopy.The results show that Tb-doped CeO_(2)supported Pt possesses abundant surface oxygen vacancies,good inhibition of ceria sintering,and strong metal-support interaction compared with CeO_(2)supported Pt.The catalytic performance of hydrogen production via steam reforming of long-chain hydrocarbon fuels(n-dodecane)was tested.Compared with 2Pt/CeO_(2),2Pt/Ce_(0.9)Tb_(0.1)O_(2),and 2Pt/Ce_(0.5)Tb_(0.5)O_(2),the 2Pt/Ce_(0.7)Tb_(0.3)O_(2)has higher activity and stability for hydrogen production,on which the conversion of n-dodecane was maintained at about 53.2%after 600 min reaction under 700℃at liquid space velocity of 9 ml·g^(-1)·h^(-1).2Pt/CeO_(2)rapidly deactivated,the conversion of n-dodecane was reduced to only 41.6%after 600 min.

Atomic-level coupled RuO_(2)/BaRuO_(3) heterostructure for efficient alkaline hydrogen evolution reaction

The slow water dissociation is the rate-determining step that slows down the reaction rate in alkaline hydrogen evolution reaction(HER).Optimizing the surface electronic structure of the catalyst to lower the energy barrier of water dissociation and regulating the binding strength of adsorption intermediates are crucial strategy for boosting the catalytic performance of HER.In this study,RuO_(2)/BaRuO_(3)(RBRO)heterostructures with abundant oxygen vacancies and lattice distortion were in-situ constructed under a low temperature via the thermal decomposition of gel-precursor.The RBRO heterostructures obtained at 550℃ exhibited the highest HER activity in 1 M KOH,showing an ultra-low overpotential of 16 mV at 10 mA cm^(-2)and a Tafel slope of 33.37 m V dec^(-1).Additionally,the material demonstrated remarkable durability,with only 25 mV of degradation in overpotential after 200 h of stability testing at 10 mA cm^(-2).Density functional theory calculations revealed that the redistribution of charges at the heterojunction interface can optimize the binding energies of H*and OH*and effectively lower the energy barrier of water dissociation.This research offers novel perspectives on surpassing the water dissociation threshold of alkaline HER catalysts by means of a systematic design of heterogeneous interfaces.

Pd^(0)-O v-Ce^(3+) Interfacial Sites with Charge Redistribution for Enhanced Hydrogenation of Methyl Oleate to Methyl Stearate

Improving the efficiency of metal/reducible metal oxide interfacial sites for hydrogenation reactions of unsaturated groups(e.g.,C=C and C=O)is a promising yet challenging endeavor.In our study,we developed a Pd/CeO_(2) catalyst by enhancing the oxygen vacancy(O V)concentration in CeO_(2) through high-temperature treatment.This process led to the formation of an interface structure ideal for supporting the hydrogenation of methyl oleate to methyl stearate.Specifi cally,metal Pd^(0) atoms bonded to the O V in defective CeO_(2) formed Pd^(0)-O v-Ce^(3+)interfacial sites,enabling strong electron transfer from CeO_(2) to Pd.The interfacial sites exhibit a synergistic adsorption eff ect on the reaction substrate.Pd^(0) sites promote the adsorption and activation of C=C bonds,while O V preferably adsorbs C=O bonds,mitigating competition with C=C bonds for Pd^(0) adsorption sites.This synergy ensures rapid C=C bond activation and accelerates the attack of active H*species on the semi-hydrogenated intermediate.As a result,our Pd/CeO_(2)-500 catalyst,enriched with Pd^(0)-O v-Ce^(3+)interfacial sites,dem-onstrated excellent hydrogenation activity at just 30℃.The catalyst achieved a Cis-C18:1 conversion rate of 99.8% and a methyl stearate formation rate of 5.7 mol/(h·g metal).This work revealed the interfacial sites for enhanced hydrogenation reactions and provided ideas for designing highly active hydrogenation catalysts.

Increased Oxygen Vacancies in CuO-ZnO Snowflake-like Composites Drive the Hydrogenation of CO_(2) to Methanol

Cu/ZnO is widely used in the hydrogenation of carbon dioxide (CO_(2)) to methanol (CH_(3)OH) to improve the lowconversion rate and selectivity generally observed. In this work, a series of In, Zr, Co, and Ni-doped CuO-ZnO catalysts wassynthesized via a hydrothermal method. By introducing a second metal element, the activity and dispersion of the activesites can be adjusted and the synergy between the metal and the carrier can be enhanced, forming an abundance of oxygenvacancies. Oxygen vacancies not only adsorb CO_(2) but also activate the intermediates in methanol synthesis, playing a keyrole in the entire reaction. Co3O4-CuO-ZnO had the best catalytic performance (a CO_(2) conversion rate of 9.17%;a CH_(3)OHselectivity of 92.77%). This study describes a typical strategy for multi-component doping to construct a catalyst with anabundance of oxygen vacancies, allowing more effective catalysis to synthesize CH_(3)OH from CO_(2).

Formation and Oxidation of Hydrogen Molybdenum Bronze on Platinum Electrode in Sulfuric Acid Solution

Hydrogen molybdenum bronze (HxMoO3) can be electrodeposited on platinum and oxidized in two steps to the hydrogen molybdenum bronze with less amount of hydrogen HyMoO3 (y<x) and MoO3 when platinum electrode is cycled from -0.2 to 1.3V (vs. SCE) in 0.05 mol/L Na2MoO4 + 0.5 mol/L H2SO4 solution. During the formation of HxMoO3, the electrochemical reduction of molybdate existing in the form of polymolydate is reversible and is about a five-electron transfer reaction.

Adsorption and desorption of hydrogen on/from single-vacancy and double-vacancy graphenes

Adsorption and desorption of hydrogen on/from single-vacancy and double-vacancy graphenes were studied by means of first-principles calculations. The structure and stability of continuous hydrogenation in single vacancy were investigated. Several new stable structures were found, along with their corresponding energy barriers. In double-vacancy graphene, the preferred sites of H atoms were identified, and H2 molecule desorption and adsorption of from/on were calculated from the energy barriers. This work provides a systematic and comprehensive understanding of hydrogen behavior on defected graphene.

Oxygen Vacancy-Rich 2D TiO_(2) Nanosheets:A Bridge Toward High Stability and Rapid Hydrogen Storage Kinetics of Nano-Confined MgH_(2)

MgH_(2) has attracted intensive interests as one of the most promising hydrogen storage materials.Nevertheless,the high desorption temperature,sluggish kinetics,and rapid capacity decay hamper its commercial application.Herein,2D TiO_(2) nanosheets with abundant oxygen vacancies are used to fabricate a flower-like MgH_(2)/TiO_(2) heterostructure with enhanced hydrogen storage performances.Particularly,the onset hydrogen desorption temperature of the MgH_(2)/TiO_(2) heterostructure is lowered down to 180℃(295℃ for blank MgH_(2)).The initial desorption rate of MgH_(2)/TiO_(2) reaches 2.116 wt% min^(-1) at 300℃,35 times of the blank MgH_(2) under the same conditions.Moreover,the capacity retention is as high as 98.5% after 100 cycles at 300℃,remarkably higher than those of the previously reported MgH_(2)-TiO_(2) composites.Both in situ HRTEM observations and ex situ XPS analyses confirm that the synergistic effects from multi-valance of Ti species,accelerated electron transportation caused by oxygen vacancies,formation of catalytic Mg-Ti oxides,and stabilized MgH_(2) NPs confined by TiO_(2) nanosheets contribute to the high stability and kinetically accelerated hydrogen storage performances of the composite.The strategy of using 2D substrates with abundant defects to support nano-sized energy storage materials to build heterostructure is therefore promising for the design of high-performance energy materials.

Conversion of Catalytically Inert 2D Bismuth Oxide Nanosheets for Effective Electrochemical Hydrogen Evolution Reaction Catalysis via Oxygen Vacancy Concentration Modulation

Oxygen vacancies(Vo)in electrocatalysts are closely correlated with the hydrogen evo-lution reaction(HER)activity.The role of vacancy defects and the effect of their concentration,how-ever,yet remains unclear.Herein,Bi2O3,an unfavorable electrocata-lyst for the HER due to a less than ideal hydrogen adsorption Gibbs free energy(ΔGH*),is utilized as a perfect model to explore the func-tion of Vo on HER performance.Through a facile plasma irradia-tion strategy,Bi2O3 nanosheets with different Vo concentrations are fabricated to evaluate the influence of defects on the HER process.Unexpectedly,while the generated oxygen vacancies contribute to the enhanced HER performance,higher Vo concentrations beyond a saturation value result in a significant drop in HER activity.By tunning the Vo concentration in the Bi_(2)O_(3)nanosheets via adjusting the treatment time,the Bi2O3 catalyst with an optimized oxygen vacancy concentration and detectable charge carrier concentration of 1.52×10^(24)cm^(−3)demonstrates enhanced HER performance with an overpotential of 174.2 mV to reach 10 mA cm^(−2),a Tafel slope of 80 mV dec−1,and an exchange current density of 316 mA cm−2 in an alkaline solution,which approaches the top-tier activity among Bi-based HER electrocatalysts.Density-functional theory calculations confirm the preferred adsorption of H*onto Bi2O3 as a function of oxygen chemical potential(ΔμO)and oxygen partial potential(PO2)and reveal that high Vo concentrations result in excessive stability of adsorbed hydrogen and hence the inferior HER activity.This study reveals the oxygen vacancy concentration-HER catalytic activity relationship and provides insights into activating catalytically inert materials into highly efficient electrocatalysts.

Selenium vacancy-rich and heteroatom-doped CoSe/Mo_(2)CTx MXene prepared using ionic liquid dopants for pH-universal hydrogen evolution and flexible supercapacitors

Vacancy engineering is a useful methodology in the development of catalysts and electrode materials.Herein,we report the introduction of Se-vacancy pairs in heteroatom-doped(N,B,and F)CoSe/Mo_(2)CT_(x) MXene(NBF-CoSe/Mo_(2)CT_(x))to enhance the hydrogen evolution reaction(HER)and supercapacitor activities via an ionic liquid-mediated method.Se vacancy pairs and heteroatom doping enable the reallocation of local electron states and add active sites,improving the electrochemical activity of NBF-CoSe/Mo_(2)CT_(x) with high HER activities over a broad range of pH.At a current density of 10 mA cm^(-2),overvoltages of 70 and 81 mV are respectively produced in 0.5 M H_(2)SO_(4)and 1 M KOH.The optimal structure also exhibits outstanding electrochemical performance in an asymmetric supercapacitor with an energy density of 34.2 Wh kg^(-1)at a power density of 15989.6Wkg^(-1).This study opens new avenues for the introduction of Se vacancies and heteroatom doping to improve the application performance.

Synergistic effect of the metal-support interaction and interfacial oxygen vacancy for CO_(2) hydrogenation to methanol over Ni/In_(2)O_(3) catalyst:A theoretical study

Indium oxide supported nickel catalyst has been experimentally confirmed to be highly active for CO_(2) hydrogenation towards methanol.In this work,the reaction mechanism for CO_(2) hydrogenation to methanol has been investigated on a model Ni/In_(2)O_(3) catalyst,i.e.,Ni_(4)/In_(2)O_(3),via the density functional theory(DFT)study.Three possible reaction pathways,i.e.,the formate pathway,CO hydrogenation and the reverse water-gas-shift(RWGS)pathways,have been examined on this model catalyst.It has been demonstrated that the RWGS pathway is the most theoretically-favored for CO_(2) hydrogenation to methanol.The complete RWGS pathway follows CO_(2)+6 H→COOH+5 H→CO+H_(2)O+4 H→HCO+H_(2)O+3 H→H_(2)CO+H_(2)O+2 H→H_(3)CO+H_(2)O+H→H_(3)COH+H_(2) O.Furthermore,it has been also proved that the interfacial oxygen vacancy can serve as the active site for boosting the CO_(2) adsorption and charge transfer between the nickel species and indium oxide,which synergistically promotes the consecutive CO_(2) hydrogenation towards methanol.

Sulfur dioxide-hydrogen peroxide relationships and acidification of precipitation in Guiyang area-a case study

-The concentrations of gas phase SO2, O3 and chemical composition of sequential rainwater samples were measured on 6/11/88 to 6/28/88 at some sites of Guiyang area. S (IV) was present in great excess of H2O2 in rainwater samples collected at residential sites of the city corresponding to high level of gas phase SO2. Considerable H2O2 in rainwater samples was observed in background air at suburbs. The evidence that clean rainwater samples were collected at 20km away from the city in 6/18/88 precipitation event revealed that the major process of acidification of the rain in the high polluted areas was below-cloud scavenging of trace gases. From a simulation calculation it was found that the rate of oxidation of S(IV) by O3 and by Mn2+, Fe3+ catalytic in high pH rainwater is significant, but for low pH the major SO42- is produced by the reaction of S (IV) with H2O2.

Hierarchical CoNi-LDH nanosheet array with hydrogen vacancy for high-performance aqueous battery cathode

Aqueous rechargeable multiple metal-ion storage battery (ARSB) has a large potential in energy storage devices due to their safe usage, low cost and high rate capability. Nevertheless, the performance of practical ARSB is largely restricted by low capacity and limited cathode materials. Herein, we demonstrate an efficient cathode material based on Co Ni-layered double hydroxide (LDH) nanosheets arrays with abundant hydrogen vacancy induced by electrochemical activation process for high performance of cations storage. Consequently, the electrochemical activated Co Ni-LDH (ECA-Co Ni-LDH) nanosheets arrays exhibit high metal ion (Li^(+), Na^(+), Zn^(2+), Mg^(2+) and Ca^(2+)) storage capacities, which is 9 times and 3 times higher that of unactivated Co Ni-LDH arrays and ECA-Co Ni-LDH without hierarchical structure, respectively.Moreover, the ECA-Co Fe-LDH also shows the possibility for practical applications in actual batteries.By coupling with a Fe_(2)O_(3)/C anode, the assembled aqueous battery delivered a large energy density of 184.4 Wh kg^(-1)at power density of 4 Wh kg^(-1) in high voltage range of 0–2 V. To our best knowledge, such high energy density and large working window of our assembled aqueous battery is exceeded other LDH-based aqueous battery or supercapacitor, and the energy density almost comparable than that of commercial Li-ion batteries. Moreover, almost no measurable capacitance losses can be detected even after 10000 cycles. In addition, this work also provides a strategy to develop a high energy density cathode for multiple metal-ion storage batteries.

Study on Deactivation by Sulfur and Regeneration of Pd/C Catalyst in Hydrogenation of N-（3-nitro-4-methoxyphenyl） Acetamide

Deactivation of Pd/C catalyst often occurs in liquid hydrogenation using industrial materials. For in-stance, the Pd/C catalyst is deactivated severely in the hydrogenation of N-(3-nitro-4-methoxyphenyl) acetamide. In this study, the chemisorption of sulfur on the surface of deactivated Pd/C was detected by energy dispersive spec-trometer and X-ray photoelectron spectroscopy. Sulfur compounds poison the Pd/C catalyst and increase the forma-tion of azo deposit, reducing the activity of catalyst. We report a mild method to regenerate the Pd/C catalyst: wash the deposit by N,N-dimethylformamide and oxidize the chemisorbed sulfur by hot air. The regenerated Pd/C cata-lyst can be reused at least ten runs with stable activity.

SULFUR-RESISTANT BIMETALLIC NOBLE METAL CATALYSTS FOR AROMATIC HYDROGENATION OF DIESEL FUEL

Y zeolite supporting noble metal catalysts, as the important industrial catalysts for aromatics hydrogenation, have received increasing attention in recent years. Pd M/Y bimetallic catalysts, where M is non noble metal element, were prepared to investigate the effects of the addition of a second metal. Pd M/Y catalysts were evaluated under the following conditions: H 2 pressure 4.2 MPa, MHSV 4.0 h -1 , sulfur content in feed 3000 μg/g. The microreactor results indicated that the second metal remarkably affects the hydrogenation activity of Pd/Y catalysts. Among them, Cr and W improve the sulfur resistance of Pd/Y, but La, Mn, Mo and Ag make the sulfur resistance worse and the second metals have no evident influence on product selectivity and acidic properties of the catalysts.

Bio-templated formation of defect-abundant VS2 as a bifunctional material toward high-performance hydrogen evolution reactions and lithium-sulfur batteries

Transition metal chalcogenides have nowadays garnered burgeoning interest owing to their fascinating electronic and catalytic properties,thus possessing great implications for energy conversion and storage applications.In this regard,their controllable synthesis in a large scale at low cost has readily become a focus of research.Herein we report diatomite-template generic and scalable production of VS2 and other transition metal sulfides targeting emerging energy conversion and storage applications.The conformal growth of VS2over diatomite template would endow them with defect-abundant features.Throughout detailed experimental investigation in combination with theoretical simulation,we reveal that the enriched active sites/sulfur vacancies of thus-derived VS2 architectures would pose positive impacts on the catalytic performance such in electrocatalytic hydrogen evolution reactions.We further show that the favorable electrical conductivity and highly exposed sites of VS2 hold promise for serving as sulfur host in the realm of Li-S batteries.Our work offers new insights into the templated and customized synthesis of defect-rich sulfides in a scalable fashion to benefit multifunctional energy applications.