The global energy-related CO_(2) emissions have rapidly increased as the world economy heavily relied on fossil fuels.This paper explores the pressing challenge of CO_(2) emissions and highlights the role of porous me...The global energy-related CO_(2) emissions have rapidly increased as the world economy heavily relied on fossil fuels.This paper explores the pressing challenge of CO_(2) emissions and highlights the role of porous metal oxide materials in the electrocatalytic reduction of CO_(2)(CO_(2)RR).The focus is on the development of robust and selective catalysts,particularly metal and metal-oxide-based materials.Porous metal oxides offer high surface area,enhancing the accessibility to active sites and improving reaction kinetics.The tunability of these materials allows for tailored catalytic behavior,targeting optimized reaction mechanisms for CO_(2)RR.The work also discusses the various synthesis strategies and identifies key structural and compositional features,addressing challenges like high overpotential,poor selectivity,and low stability.Based on these insights,we suggest avenues for future research on porous metal oxide materials for electrochemical CO_(2) reduction.展开更多
Electrochemical reduction of CO_(2)(CO_(2)RR)has become a research hot spot in recent years in the context of carbon neutrality.HCOOH is one of the most promising products obtained by electrochemical reduction of CO_(...Electrochemical reduction of CO_(2)(CO_(2)RR)has become a research hot spot in recent years in the context of carbon neutrality.HCOOH is one of the most promising products obtained by electrochemical reduction of CO_(2) due to its high energy value as estimated by market price per energy unit and wide application in chemical industry.Biomass is the most abundant renewable resource in the natural world.Coupling biomass oxidative conversion with CO_(2)RR driven by renewable electricity would well achieve carbon negativity.In this work,we comprehensively reviewed the current research progress on CO_(2)RR to produce HCOOH and coupled system for conversion of biomass and its derivatives to produce value-added products.Sn-and Bi-based electrocatalysts are discussed for CO_(2)RR with regards to the structure of the catalyst and reaction mechanisms.Electro-oxidation reactions of biomass derived sugars,alcohols,furan aldehydes and even polymeric components of lignocellulose were reviewed as alternatives to replace oxygen evolution reaction(OER)in the conventional electrolysis process.It was recommended that to further improve the efficiency of the coupled system,future work should be focused on the development of more efficient and stable catalysts,careful design of the electrolytic cells for improving the mass transfer and development of environment-friendly processes for recovering the formed formate and biomass oxidation products.展开更多
N-doped carbon materials,with their applications as electrocatalysts for the oxygen reduction reaction(ORR),have been extensively studied.However,a negletcted fact is that the operating potential of the ORR is higher ...N-doped carbon materials,with their applications as electrocatalysts for the oxygen reduction reaction(ORR),have been extensively studied.However,a negletcted fact is that the operating potential of the ORR is higher than the theoretical oxida-tion potential of carbon,possibly leading to the oxidation of carbon materials.Consequently,the infl uence of the structural oxidation evolution on ORR performance and the real active sites are not clear.In this study,we discover a two-step oxida-tion process of N-doped carbon during the ORR.The fi rst oxidation process is caused by the applied potential and bubbling oxygen during the ORR,leading to the oxidative dissolution of N and the formation of abundant oxygen-containing functional groups.This oxidation process also converts the reaction path from the four-electron(4e)ORR to the two-electron(2e)ORR.Subsequently,the enhanced 2e ORR generates oxidative H_(2)O_(2),which initiates the second stage of oxidation to some newly formed oxygen-containing functional groups,such as quinones to dicarboxyls,further diversifying the oxygen-containing functional groups and making carboxyl groups as the dominant species.We also reveal the synergistic eff ect of multiple oxygen-containing functional groups by providing additional opportunities to access active sites with optimized adsorption of OOH*,thus leading to high effi ciency and durability in electrocatalytic H_(2)O_(2) production.展开更多
Atomically-dispersed metal-based materials represent an emerging class of photocatalysts attributed to their high catalytic activity,abundant surface active sites,and efficient charge separation.Nevertheless,the roles...Atomically-dispersed metal-based materials represent an emerging class of photocatalysts attributed to their high catalytic activity,abundant surface active sites,and efficient charge separation.Nevertheless,the roles of different forms of atomically-dispersed metals(i.e.,single-atoms and atomic clusters)in photocatalytic reactions remain ambiguous.Herein,we developed an ethylenediamine(EDA)-assisted reduction method to controllably synthesize atomically dispersed Au in the forms of Au single atoms(Au_(SA)),Au clusters(Au_(C)),and a mixed-phase of Au_(SA)and Au_(C)(Au_(SA+C))on CdS.In addition,we elucidate the synergistic effect of Au_(SA)and Au_(C)in enhancing the photocatalytic performance of CdS substrates for simultaneous CO_(2)reduction and aryl alcohol oxidation.Specifically,Au_(SA)can effectively lower the energy barrier for the CO_(2)→*COOH conversion,while Au_(C)can enhance the adsorption of alcohols and reduce the energy barrier for dehydrogenation.As a result,the Au_(SA)and Au_(C)co-loaded CdS show impressive overall photocatalytic CO_(2)conversion performance,achieving remarkable CO and BAD production rates of 4.43 and 4.71 mmol g^(−1)h^(−1),with the selectivities of 93%and 99%,respectively.More importantly,the solar-to-chemical conversion efficiency of Au_(SA+C)/CdS reaches 0.57%,which is over fivefold higher than the typical solar-to-biomass conversion efficiency found in nature(ca.0.1%).This study comprehensively describes the roles of different forms of atomically-dispersed metals and their synergistic effects in photocatalytic reactions,which is anticipated to pave a new avenue in energy and environmental applications.展开更多
The electrochemical CO_(2)reduction reaction to produce multi-carbon(C_(2+)) hydrocarbons or oxygenate compounds is a promising route to obtain a renewable fuel of high energy density.However,producing C_(2+)at high c...The electrochemical CO_(2)reduction reaction to produce multi-carbon(C_(2+)) hydrocarbons or oxygenate compounds is a promising route to obtain a renewable fuel of high energy density.However,producing C_(2+)at high current densities is still a challenge.Herein,we develop a Cu-Zn alloy/Cu-Zn aluminate oxide composite electrocatalytic system for enhanced conversion of CO_(2)to C_(2+)products.The Cu-Zn-Al-Layered Double Hydroxide(LDH) is used as a precursor to decompose into uniform Cu-Zn oxide/Cu-Zn aluminate pre-catalyst.Under electrochemical reduction,Cu-Zn oxide generates Cu-Zn alloy while Cu-Zn aluminate oxide remains unchanged.The alloy and oxide are closely stacked and arranged alternately,and the aluminate oxide induces the strong electron interaction of Cu,Zn and Al,creating a large number of highly active reaction interfaces composed of 0 to+3 valence metal sites.With the help of the interface effect,the optimized Cu_(9)Zn_(1)/Cu_(0.8)Zn_(0.2)Al_(2)O_(4)catalyst achieves a Faradaic efficiency of 88.5% for C_(2+)products at a current density of 400 mA cm^(-2)at-1.15 V versus reversible hydrogen electrode.The in-situ Raman and attenuate total reflectance-infrared absorption spectroscopy(ATR-IRAS) spectra show that the aluminate oxide at the interface significantly enhances the adsorption and activation of CO_(2)and the dissociation of H2O and strengthens the adsorption of CO intermediates,and the alloy promotes the C-C coupling to produce C_(2+)products.This work provides an efficient strategy to construct highly active reaction interfaces for industrial-scale electrochemical CO_(2)RR.展开更多
Electrochemical nitrate reduction to ammonia(NRA) can realize the green synthesis of ammonia(NH3) at ambient conditions, and also remove nitrate contamination in water. However, the current catalysts for NRA still fac...Electrochemical nitrate reduction to ammonia(NRA) can realize the green synthesis of ammonia(NH3) at ambient conditions, and also remove nitrate contamination in water. However, the current catalysts for NRA still face relatively low NH3yield rate and poor stability. We present here a core-shell heterostructure comprising cobalt oxide anchored on copper oxide nanowire arrays(CuO NWAs@Co_(3)O_(4)) for efficient NRA. The CuO NWAs@Co_(3)O_(4)demonstrates significantly enhanced NRA performance in alkaline media in comparison with plain CuO NWAs and Co_(3)O_(4)flocs. Especially, at-0.23 V vs. RHE, NH_(3) yield rate of the CuO NWAs@Co_(3)O_(4)reaches 1.915 mmol h^(-1)cm^(-2),much higher than those of CuO NWAs(1.472 mmol h^(-1)cm^(-2)), Co_(3)O_(4)flocs(1.222 mmol h^(-1)cm^(-2)) and recent reported Cu-based catalysts.It is proposed that the synergetic effects of the heterostructure combing atom hydrogen adsorption and nitrate reduction lead to the enhanced NRA performance.展开更多
The electrochemical carbon dioxide reduction reaction(CO_(2)RR),which can produce value-added chemical feedstocks,is a proton-coupled-electron process with sluggish kinetics.Thus,highly efficient,cheap catalysts are u...The electrochemical carbon dioxide reduction reaction(CO_(2)RR),which can produce value-added chemical feedstocks,is a proton-coupled-electron process with sluggish kinetics.Thus,highly efficient,cheap catalysts are urgently required.Transition metal oxides such as CoO_(x),FeO_(x),and NiO_(x)are low-cost,low toxicity,and abundant materials for a wide range of electrochemical reactions,but are almost inert for CO_(2)RR.Here,we report for the first time that nitrogen doped carbon nanotubes(N-CNT)have a surprising activation effect on the activity and selectivity of transition metal-oxide(MO_(x)where M=Fe,Ni,and Co)nanoclusters for CO_(2)RR.MO_(x)supported on N-CNT,MO_(x)/N-CNT,achieves a CO yield of 2.6–2.8 mmol cm−2 min−1 at an overpotential of−0.55 V,which is two orders of magnitude higher than MO_(x)supported on acid treated CNTs(MO_(x)/O-CNT)and four times higher than pristine N-CNT.The faraday efficiency for electrochemical CO_(2)-to-CO conversion is as high as 90.3%at overpotential of 0.44 V.Both in-situ XAS measurements and DFT calculations disclose that MO_(x)nanoclusters can be hydrated in CO_(2)saturated KHCO_(3),and the N defects of N-CNT effectively stabilize these metal hydroxyl species under carbon dioxide reduction reaction conditions,which can split the water molecules and provide local protons to inhibit the poisoning of active sites under carbon dioxide reduction reaction conditions.展开更多
The growth of electrochemically inert segregation layers on the surface of solid oxide fuel cell cathodes has become a bottleneck restricting the development of perovskite-structured oxygen reduction catalysts.Here,we...The growth of electrochemically inert segregation layers on the surface of solid oxide fuel cell cathodes has become a bottleneck restricting the development of perovskite-structured oxygen reduction catalysts.Here,we report a new discovery in which enriched Ba and Fe ions on the near-surface of Nd_(1/2)Ba_(1/2)Co_(1/3)Fe_(1/3)Mn_(1/3)O_(3-δ)spontaneously agglomerate into dispersed Ba_(5)Fe_(2)O_(8) nanoparticles and maintain a highly active and durable perovskite structure on the surface.This unique surface selfcleaning phenomenon is related to the low average potential energy of Ba_(5)Fe_(2)O_(8),which is grown on the near-surface layer.The electrochemically inert Ba_(5)Fe_(2)O_(8) segregation layer on the near-surface of the perovskite catalyst achieves self-cleaning by regulating the formation energy of enriched metal oxides.This self-cleaned perovskite surface exhibits an ultrafast oxygen exchange rate,high catalytic activity for the oxygen reduction reaction,and good adaptability to the actual working conditions of solid oxide fuel cell stacks.This study paves a new way for overcoming the stubborn problem of perovskite catalyst surface deactivation and enriches the scientific knowledge of surface catalysis.展开更多
Mixed metal oxide(MMO) represents a critical class of materials that can allow for obtaining a dynamic interface between its components:reduced metal and its metal oxide counterpart during an electrocatalytic reaction...Mixed metal oxide(MMO) represents a critical class of materials that can allow for obtaining a dynamic interface between its components:reduced metal and its metal oxide counterpart during an electrocatalytic reaction.Here,a synthetic method utilizing a MOF-derived micro/mesoporous carbon as a template to prepare sub-2 nm MMO catalysts for CO_(2) electro reduction is reported.Starting from the zeolite imidazolate framework(ZIF-8),the pyrolyzed derivatives were used to synthesize sub-2 nm Pd-Ni MMO with different compositions.The Ni-rich(Pd_(20)-Ni_(80)/ZC) catalyst exhibits unexpectedly superior performance for CO production with an improved Faradaic efficiency(FE) of 95.3% at the current density of 200 mA cm^(-2) at-0.56 V vs.reversible hydrogen electrode(RHE) compared to other Pd-Ni compositions.X-ray photoelectron spectroscopy(XPS) analysis confirms the presence of Ni^(2+) and Pd^(2+) in all compositions,demonstrating the presence of MMO.Density functional theory(DFT) calculation reveals that the lower CO binding energy on the surface of the Pd_(20)-Ni_(80) cluster eases CO desorption,thus increasing its production.This work provides a general synthetic strategy for MMO electrocatalysts and can pave a new way for screening multimetallic catalysts with a dynamic electrochemical interface.展开更多
Metal-air batteries face a great challenge in developing efficient and durable low-cost oxygen reduction reaction(ORR)electrocatalysts.Single-atom iron catalysts embedded into nitrogen doped carbon(Fe-N-C)have emerged...Metal-air batteries face a great challenge in developing efficient and durable low-cost oxygen reduction reaction(ORR)electrocatalysts.Single-atom iron catalysts embedded into nitrogen doped carbon(Fe-N-C)have emerged as attractive materials for potential replacement of Pt in ORR,but their catalytic performance was limited by the symmetrical electronic structure distribution around the single-atom Fe site.Here,we report our findings in significantly enhancing the ORR performance of Fe-N-C by moderate Fe_(2)O_(3) integration via the strong electronic interaction.Remarkably,the optimized catalyst(M-Fe_(2)O_(3)/Fe_(SA)@NC)exhibits excellent activity,durability and good tolerance to methanol,outperforming the benchmark Pt/C catalyst.When M-Fe_(2)O_(3)/Fe_(SA)@NC catalyst was used in a practical zinc-air battery assembly,peak power density of 155 mW cm^(-2)and specific capacity of 762 mA h g_(Zn)^(-1)were achieved and the battery assembly has shown superior cycling stability over a period of 200 h.More importantly,theoretical studies suggest that the introduction of Fe_(2)O_(3) can evoke the crystal field alteration and electron redistribution on single Fe atoms,which can break the symmetric charge distribution of Fe-N_(4) and thereby optimize the corresponding adsorption energy of intermediates to promote the O_(2)reduction.This study provides a new pathway to promote the catalytic performance of single-atom catalysts.展开更多
Electrochemical carbon dioxide(CO_(2))reduction(ECR)is a promising technology to produce valuable fuels and feedstocks from CO_(2).Despite large efforts to develop ECR catalysts,the investigation of the catalytic perf...Electrochemical carbon dioxide(CO_(2))reduction(ECR)is a promising technology to produce valuable fuels and feedstocks from CO_(2).Despite large efforts to develop ECR catalysts,the investigation of the catalytic performance and electrochemical behavior of complex metal oxides,especially perovskite oxides,is rarely reported.Here,the inorganic perovskite oxide Ag-doped(La_(0.8)Sr_(0.2))_(0.95)Ag_(0.05)MnO_(3-δ)(LSA0.05M)is reported as an efficient electrocatalyst for ECR to CO for the first time,which exhibits a Faradaic efficiency(FE)of 84.3%,a remarkable mass activity of 75Ag^(-1)(normalized to the mass of Ag),and stability of 130 h at a moderate overpotential of 0.79 V.The LSA0.05M catalyst experiences structure reconstruction during ECR,creating the in operando-formed interface between the perovskite and the evolved Ag phase.The evolved Ag is uniformly distributed with a small particle size on the perovskite surface.Theoretical calculations indicate the reconstruction of LSA0.05M during ECR and reveal that the perovskite-Ag interface provides adsorption sites for CO_(2) and accelerates the desorption of the*CO intermediate to enhance ECR.This study presents a novel high-performance perovskite catalyst for ECR andmay inspire the future design of electrocatalysts via the in operando formation of metal-metal oxide interfaces.展开更多
Digesting aluminum-bearing minerals and converting ferric oxide to magnetite simultaneously in Bayer digestion process is crucially important to deal with high-iron diasporic bauxite economically for alumina productio...Digesting aluminum-bearing minerals and converting ferric oxide to magnetite simultaneously in Bayer digestion process is crucially important to deal with high-iron diasporic bauxite economically for alumina production.The reaction behaviors of hydrothermal reduction of ferric oxide in alkali solution were studied by both thermodynamic calculation and experimental investigation.The thermodynamic calculation indicates that Fe3O4 can be formed by the conversion of Fe2O3 at proper redox potentials in alkaline solution.The experimental results show that the formation ratio of Fe3O4 either through the reaction of Fe and Fe2O3 or through the reaction of Fe and H2O in alkaline aqueous solution increases remarkably with raising the temperature and alkali concentration,suggesting that Fe(OH)3- and Fe(OH)4- form by dissolving Fe and Fe2O3,respectively,in alkaline aqueous solution and further react to form Fe3O4.Moreover,aluminate ions have little influence on the hydrothermal reduction of Fe2O3 in alkaline aqueous solution,and converting iron minerals to magnetite can be realized in the Bayer digestion process of diasporic bauxite.展开更多
The structure and catalytic desulfurization characteristics of CeO2-TiO2 mixed oxides were investigated by means ofX-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS) and catalytic activity tests. Acco...The structure and catalytic desulfurization characteristics of CeO2-TiO2 mixed oxides were investigated by means ofX-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS) and catalytic activity tests. According to the results, a CeO2-TiO2solid solution is formed when the mole ratio of cerium to titanium n(Ce):n(Ti) is 5:5 or greater, and the most suitable n(Ce):n(Ti) isdetermined as 7:3, over which the conversion rate of SO2 and the yield of sulfur at 500℃ reach 93% and 99%, respectively.According to the activity testing curve, Ce0.7Ti0.3O2 (n(Ce):n(Ti)=7:3) without any pretreatment can be gradually activated by reagentgas after about 10 min, and reaches a steady activation status 60 min later. The XPS results of Ce0.7Ti0.3O2 after different time ofSO2+CO reaction show that CeO2 is the active component that offers the redox couple Ce4+/Ce3+ and the labile oxygen vacancies, andTiO2 only functions as a catalyst structure stabilizer during the catalytic reaction process. After 48 h of catalytic reaction at 500℃,Ce0.7Ti0.3O2 still maintains a stable structure without being vulcanized, demonstrating its good anti-sulfur poisoning performance.展开更多
The extraction of manganese from low-grade manganese oxide ores using Ca S derived from Ca SO4 as reductant was investigated. The effects of mass ratio of Ca S to ore, reduction temperature, reduction time, liquid to ...The extraction of manganese from low-grade manganese oxide ores using Ca S derived from Ca SO4 as reductant was investigated. The effects of mass ratio of Ca S to ore, reduction temperature, reduction time, liquid to solid ratio(L/S ratio), stirring speed, leaching temperature, leaching time and H2SO4 concentration on the leaching rates of Mn and Fe during the reduction–acid leaching process were discussed. The leaching rates of 96.47% for Mn and 19.24% for Fe were obtained under the optimized conditions of mass ratio of Ca S to manganese oxide ore 1:6.7, L/S ratio 5:1, stirring speed 300 r/min, reduction temperature of 95 °C for 2.0 h in the reduction process and leaching stirring speed of 200 r/min, H2SO4 concentration of 1.5 mol/L, leaching temperature of 80 °C for 5 min in the leaching process. In addition, this process can be employed in the recovery of manganese from various manganese oxide ores, and Mn leaching rate above 95% is obtained.展开更多
Dealloying by which the transition metal is partially or completely leached from an alloy precursor is an effective way to optimize the fundamental effects for further enhancing the electrocatalysis of a catalyst.Here...Dealloying by which the transition metal is partially or completely leached from an alloy precursor is an effective way to optimize the fundamental effects for further enhancing the electrocatalysis of a catalyst.Herein,to address the deficiencies associated with the commonly used dealloying methods,for example,electrochemical and sulfuric acid/nitric acid treatment,we report an acetic acid-assisted mild strategy to dealloy Cu atoms from the outer surface layers of CuPd alloy nanoparticles to achieve high-efficiency electrocatalysis for oxygen reduction and ethanol oxidation in an alkaline electrolyte.The leaching of Cu atoms by acetic acid exerts an additional compressive strain effect on the surface layers and exposes more active Pd atoms,which is beneficial for boosting the catalytic performance of a dealloyed catalyst for the oxygen reduction reaction(ORR)and the ethanol oxidation reaction(EOR).In particular,for ORR,the CuPd nanoparticles with a Pd/Cu molar ratio of 2:1 after acetic dealloying show a half-wave potential of 0.912 V(vs.RHE)and a mass activity of 0.213 AmgPd^(-1) at 0.9 V,respectively,while for EOR,the same dealloyed sample has a mass activity and a specific activity of 8.4 Amg^(-1) and 8.23 mA cm^(-2),respectively,much better than their dealloyed counterparts at other temperatures and commercial Pd/C as well as a Pt/C catalyst.展开更多
The unique characteristics of nanofibers in rational electrode design enable effec-tive utilization and maximizing material properties for achieving highly efficient and sustainable CO_(2) reduction reactions( CO_(2)R...The unique characteristics of nanofibers in rational electrode design enable effec-tive utilization and maximizing material properties for achieving highly efficient and sustainable CO_(2) reduction reactions( CO_(2)RRs)in solid oxide elec-trolysis cells(SOECs).However,practical appli-cation of nanofiber-based electrodes faces chal-lenges in establishing sufficient interfacial contact and adhesion with the dense electrolyte.To tackle this challenge,a novel hybrid nanofiber electrode,La_(0.6)Sr_(0.4)Co_(0.15)Fe_(0.8)Pd_(0.05)O_(3-δ)(H-LSCFP),is developed by strategically incorporating low aspect ratio crushed LSCFP nanofibers into the excess porous interspace of a high aspect ratio LSCFP nanofiber framework synthesized via electrospinning technique.After consecutive treatment in 100% H_(2) and CO_(2) at 700°C,LSCFP nanofibers form a perovskite phase with in situ exsolved Co metal nanocatalysts and a high concentration of oxygen species on the surface,enhancing CO_(2) adsorption.The SOEC with the H-LSCFP electrode yielded an outstanding current density of 2.2 A cm^(-2) in CO_(2) at 800°C and 1.5 V,setting a new benchmark among reported nanofiber-based electrodes.Digital twinning of the H-LSCFP reveals improved contact adhesion and increased reaction sites for CO_(2)RR.The present work demonstrates a highly catalytically active and robust nanofiber-based fuel electrode with a hybrid structure,paving the way for further advancements and nanofiber applications in CO_(2)-SOECs.展开更多
Electrocatalysis enables the industrial transition to sustainable production of chemicals using abundant precursors and electricity from renewable sources.De-centralized production of hydrogen peroxide(H_(2)O_(2))from...Electrocatalysis enables the industrial transition to sustainable production of chemicals using abundant precursors and electricity from renewable sources.De-centralized production of hydrogen peroxide(H_(2)O_(2))from water and oxygen of air is highly desirable for daily life and industry.We report an effective electrochemical refinery(e-refinery)for H_(2)O_(2)by means of electrocatalysis-controlled comproportionation reaction(2_(H)O+o→2HO),feeding pure water and oxygen only.Mesoporous nickel(Ⅱ)oxide(NiO)was used as electrocatalyst for oxygen evolution reaction(OER),producing oxygen at the anode.Conducting polymer poly(3,4-ethylenedioxythiophene):poly(styrene sulfonate)(PEDOT:PSS)drove the oxygen reduction reaction(ORR),forming H_(2)O_(2)on the cathode.The reactions were evaluated in both half-cell and device configurations.The performance of the H_(2)O_(2)e-refinery,assembled on anion-exchange solid electrolyte and fed with pure water,was limited by the unbalanced ionic transport.Optimization of the operation conditions allowed a conversion efficiency of 80%.展开更多
Although metal oxide-zeolite hybrid materials have long been known to achieve enhanced catalytic activity and selectivity in NO_(x)removal reactions through the inter-particle diffusion of intermediate species,their s...Although metal oxide-zeolite hybrid materials have long been known to achieve enhanced catalytic activity and selectivity in NO_(x)removal reactions through the inter-particle diffusion of intermediate species,their subsequent reaction mechanism on acid sites is still unclear and requires investigation.In this study,the distribution of Brønsted/Lewis acid sites in the hybrid materials was precisely adjusted by introducing potassium ions,which not only selectively bind to Brønsted acid sites but also potentially affect the formation and diffusion of activated NO species.Systematic in situ diffuse reflectance infrared Fourier transform spectroscopy analyses coupled with selective catalytic reduction of NO_(x)with NH_(3)(NH_(3)-SCR)reaction demonstrate that the Lewis acid sites over MnO_(x)are more active for NO reduction but have lower selectivity to N_(2)than Brønsted acids sites.Brønsted acid sites primarily produce N_(2),whereas Lewis acid sites primarily produce N_(2)O,contributing to unfavorable N_(2)selectivity.The Brønsted acid sites present in Y zeolite,which are stronger than those on MnO_(x),accelerate the NH_(3)-SCR reaction in which the nitrite/nitrate species diffused from the MnO_(x)particles rapidly convert into the N_(2).Therefore,it is important to design the catalyst so that the activated NO species formed in MnO_(x)diffuse to and are selectively decomposed on the Brønsted acid sites of H-Y zeolite rather than that of MnO_(x)particle.For the physically mixed H-MnO_(x)+H-Y sample,the abundant Brønsted/Lewis acid sites in H-MnO_(x)give rise to significant consumption of activated NO species before their inter-particle diffusion,thereby hindering the enhancement of the synergistic effects.Furthermore,we found that the intercalated K+in K-MnO_(x)has an unexpected favorable role in the NO reduction rate,probably owing to faster diffusion of the activated NO species on K-MnO_(x)than H-MnO_(x).This study will help to design promising metal oxide-zeolite hybrid catalysts by identifying the role of the acid sites in two different constituents.展开更多
A series of meso‐microporous copper‐supporting chabazite molecular sieve(CuSAPO‐34) catalysts with excellent performance in low‐temperature ammonia selective catalytic reduction(NH3‐SCR)have been synthesized ...A series of meso‐microporous copper‐supporting chabazite molecular sieve(CuSAPO‐34) catalysts with excellent performance in low‐temperature ammonia selective catalytic reduction(NH3‐SCR)have been synthesized via a one‐pot hydrothermal crystallization method. The physicochemical properties of the catalysts were characterized by scanning electron microscopy, transmission electron microscopy, N2 adsorption‐desorption measurements, X‐ray diffraction, 27 Al magic angle spinning nuclear magnetic resonance, diffuse reflectance ultraviolet‐visible spectroscopy, inductively coupled plasma‐atomic emission spectroscopy, X‐ray photoelectron spectroscopy, temperature‐programmed reduction measurements, and electron paramagnetic resonance analysis. The formation of micro‐mesopores in the Cu‐SAPO‐34 catalysts decreases diffusion resistance and greatly improves the accessibility of reactants to catalytic active sites. The main active sites for NH3‐SCR reaction are the isolated Cu^2+ species displaced into the ellipsoidal cavity of the Cu‐SAPO‐34 catalysts.展开更多
Studies have extensively addressed the development of electrocatalytic technologies for energy storage and conversion,fuel production,and environmental protection.Electrode processes such as different oxidation and re...Studies have extensively addressed the development of electrocatalytic technologies for energy storage and conversion,fuel production,and environmental protection.Electrode processes such as different oxidation and reduction reactions play a vital and significant role in these technologies.In this regard,efficient,inexpensive,and stable electrocatalysts capable can significantly promote electrochemical reactions.Unique features of metal–organic frameworks(MOFs)such as their high porosity,tunable structure,size,and pore shape,high surface area,and redox properties have introduced them as an ideal electrocatalyst candidate.This review is thus aimed at elucidating the role of MOF-based materials(pristine,derivatives and composites)as efficient electrocatalysts in energy and sensing-related oxidation and reduction reactions such as oxygen reduction reaction(ORR),hydrogen oxidation reaction(HOR),carbon dioxide reduction reaction(CO_(2)RR),urea oxidation reaction(UOR),alcohol oxidation reaction(AOR),nitrogen reduction reaction(NRR),and glucose oxidation reaction(GOR)in advanced energy and sensing devices.Also,the structure–property relationship of the electrocatalyst was elaborated for each electrocatalytic reaction.Finally,perspectives on the potential research topics for practical use of MOF-based electrocatalysts are addressed.The present review can improve the interest in MOF-based electrocatalysts to study different oxidation and reduction reactions in energy and sensing systems.展开更多
基金funded by the National Natural Science Foundation of China,China (Nos.52272303 and 52073212)the General Program of Municipal Natural Science Foundation of Tianjin,China (Nos.17JCYBJC22700 and 17JCYBJC17000)the State Scholarship Fund of China Scholarship Council,China (Nos.201709345012 and 201706255009)。
文摘The global energy-related CO_(2) emissions have rapidly increased as the world economy heavily relied on fossil fuels.This paper explores the pressing challenge of CO_(2) emissions and highlights the role of porous metal oxide materials in the electrocatalytic reduction of CO_(2)(CO_(2)RR).The focus is on the development of robust and selective catalysts,particularly metal and metal-oxide-based materials.Porous metal oxides offer high surface area,enhancing the accessibility to active sites and improving reaction kinetics.The tunability of these materials allows for tailored catalytic behavior,targeting optimized reaction mechanisms for CO_(2)RR.The work also discusses the various synthesis strategies and identifies key structural and compositional features,addressing challenges like high overpotential,poor selectivity,and low stability.Based on these insights,we suggest avenues for future research on porous metal oxide materials for electrochemical CO_(2) reduction.
基金supported by the National Key R&D Program of China(2022YFA2105900)the National Natural Science Foundation of China(No.22178197)。
文摘Electrochemical reduction of CO_(2)(CO_(2)RR)has become a research hot spot in recent years in the context of carbon neutrality.HCOOH is one of the most promising products obtained by electrochemical reduction of CO_(2) due to its high energy value as estimated by market price per energy unit and wide application in chemical industry.Biomass is the most abundant renewable resource in the natural world.Coupling biomass oxidative conversion with CO_(2)RR driven by renewable electricity would well achieve carbon negativity.In this work,we comprehensively reviewed the current research progress on CO_(2)RR to produce HCOOH and coupled system for conversion of biomass and its derivatives to produce value-added products.Sn-and Bi-based electrocatalysts are discussed for CO_(2)RR with regards to the structure of the catalyst and reaction mechanisms.Electro-oxidation reactions of biomass derived sugars,alcohols,furan aldehydes and even polymeric components of lignocellulose were reviewed as alternatives to replace oxygen evolution reaction(OER)in the conventional electrolysis process.It was recommended that to further improve the efficiency of the coupled system,future work should be focused on the development of more efficient and stable catalysts,careful design of the electrolytic cells for improving the mass transfer and development of environment-friendly processes for recovering the formed formate and biomass oxidation products.
基金We acknowledge the National Natural Science Foundation of China(No.22275134)for fi nancial support.
文摘N-doped carbon materials,with their applications as electrocatalysts for the oxygen reduction reaction(ORR),have been extensively studied.However,a negletcted fact is that the operating potential of the ORR is higher than the theoretical oxida-tion potential of carbon,possibly leading to the oxidation of carbon materials.Consequently,the infl uence of the structural oxidation evolution on ORR performance and the real active sites are not clear.In this study,we discover a two-step oxida-tion process of N-doped carbon during the ORR.The fi rst oxidation process is caused by the applied potential and bubbling oxygen during the ORR,leading to the oxidative dissolution of N and the formation of abundant oxygen-containing functional groups.This oxidation process also converts the reaction path from the four-electron(4e)ORR to the two-electron(2e)ORR.Subsequently,the enhanced 2e ORR generates oxidative H_(2)O_(2),which initiates the second stage of oxidation to some newly formed oxygen-containing functional groups,such as quinones to dicarboxyls,further diversifying the oxygen-containing functional groups and making carboxyl groups as the dominant species.We also reveal the synergistic eff ect of multiple oxygen-containing functional groups by providing additional opportunities to access active sites with optimized adsorption of OOH*,thus leading to high effi ciency and durability in electrocatalytic H_(2)O_(2) production.
文摘Atomically-dispersed metal-based materials represent an emerging class of photocatalysts attributed to their high catalytic activity,abundant surface active sites,and efficient charge separation.Nevertheless,the roles of different forms of atomically-dispersed metals(i.e.,single-atoms and atomic clusters)in photocatalytic reactions remain ambiguous.Herein,we developed an ethylenediamine(EDA)-assisted reduction method to controllably synthesize atomically dispersed Au in the forms of Au single atoms(Au_(SA)),Au clusters(Au_(C)),and a mixed-phase of Au_(SA)and Au_(C)(Au_(SA+C))on CdS.In addition,we elucidate the synergistic effect of Au_(SA)and Au_(C)in enhancing the photocatalytic performance of CdS substrates for simultaneous CO_(2)reduction and aryl alcohol oxidation.Specifically,Au_(SA)can effectively lower the energy barrier for the CO_(2)→*COOH conversion,while Au_(C)can enhance the adsorption of alcohols and reduce the energy barrier for dehydrogenation.As a result,the Au_(SA)and Au_(C)co-loaded CdS show impressive overall photocatalytic CO_(2)conversion performance,achieving remarkable CO and BAD production rates of 4.43 and 4.71 mmol g^(−1)h^(−1),with the selectivities of 93%and 99%,respectively.More importantly,the solar-to-chemical conversion efficiency of Au_(SA+C)/CdS reaches 0.57%,which is over fivefold higher than the typical solar-to-biomass conversion efficiency found in nature(ca.0.1%).This study comprehensively describes the roles of different forms of atomically-dispersed metals and their synergistic effects in photocatalytic reactions,which is anticipated to pave a new avenue in energy and environmental applications.
基金supported by the National Natural Science Foundation of China (NSFC)(22075201)the National Key Research and Development Program of China (2022YFB4101800)。
文摘The electrochemical CO_(2)reduction reaction to produce multi-carbon(C_(2+)) hydrocarbons or oxygenate compounds is a promising route to obtain a renewable fuel of high energy density.However,producing C_(2+)at high current densities is still a challenge.Herein,we develop a Cu-Zn alloy/Cu-Zn aluminate oxide composite electrocatalytic system for enhanced conversion of CO_(2)to C_(2+)products.The Cu-Zn-Al-Layered Double Hydroxide(LDH) is used as a precursor to decompose into uniform Cu-Zn oxide/Cu-Zn aluminate pre-catalyst.Under electrochemical reduction,Cu-Zn oxide generates Cu-Zn alloy while Cu-Zn aluminate oxide remains unchanged.The alloy and oxide are closely stacked and arranged alternately,and the aluminate oxide induces the strong electron interaction of Cu,Zn and Al,creating a large number of highly active reaction interfaces composed of 0 to+3 valence metal sites.With the help of the interface effect,the optimized Cu_(9)Zn_(1)/Cu_(0.8)Zn_(0.2)Al_(2)O_(4)catalyst achieves a Faradaic efficiency of 88.5% for C_(2+)products at a current density of 400 mA cm^(-2)at-1.15 V versus reversible hydrogen electrode.The in-situ Raman and attenuate total reflectance-infrared absorption spectroscopy(ATR-IRAS) spectra show that the aluminate oxide at the interface significantly enhances the adsorption and activation of CO_(2)and the dissociation of H2O and strengthens the adsorption of CO intermediates,and the alloy promotes the C-C coupling to produce C_(2+)products.This work provides an efficient strategy to construct highly active reaction interfaces for industrial-scale electrochemical CO_(2)RR.
基金the financial support from National Natural Science Foundation of China (No. 21972102)National Key Research and Development Program of China (2021YFA0910400)+3 种基金Natural Science Foundation of Jiangsu Province (BK20200991)Suzhou Science and Technology Planning Project (SS202016)the USTS starting fund (No.332012104)the Natural Science Foundation of Suzhou University of Science and Technology (No.342134401)。
文摘Electrochemical nitrate reduction to ammonia(NRA) can realize the green synthesis of ammonia(NH3) at ambient conditions, and also remove nitrate contamination in water. However, the current catalysts for NRA still face relatively low NH3yield rate and poor stability. We present here a core-shell heterostructure comprising cobalt oxide anchored on copper oxide nanowire arrays(CuO NWAs@Co_(3)O_(4)) for efficient NRA. The CuO NWAs@Co_(3)O_(4)demonstrates significantly enhanced NRA performance in alkaline media in comparison with plain CuO NWAs and Co_(3)O_(4)flocs. Especially, at-0.23 V vs. RHE, NH_(3) yield rate of the CuO NWAs@Co_(3)O_(4)reaches 1.915 mmol h^(-1)cm^(-2),much higher than those of CuO NWAs(1.472 mmol h^(-1)cm^(-2)), Co_(3)O_(4)flocs(1.222 mmol h^(-1)cm^(-2)) and recent reported Cu-based catalysts.It is proposed that the synergetic effects of the heterostructure combing atom hydrogen adsorption and nitrate reduction lead to the enhanced NRA performance.
基金Y.C.and J.C.are contributed equally to the paper.Project supported by the National Natural Science Foundation of China (U19A2017)the Fundamental Research Funds for the Central South University and the Australian Research Council (DP180100731 and DP180100568)。
文摘The electrochemical carbon dioxide reduction reaction(CO_(2)RR),which can produce value-added chemical feedstocks,is a proton-coupled-electron process with sluggish kinetics.Thus,highly efficient,cheap catalysts are urgently required.Transition metal oxides such as CoO_(x),FeO_(x),and NiO_(x)are low-cost,low toxicity,and abundant materials for a wide range of electrochemical reactions,but are almost inert for CO_(2)RR.Here,we report for the first time that nitrogen doped carbon nanotubes(N-CNT)have a surprising activation effect on the activity and selectivity of transition metal-oxide(MO_(x)where M=Fe,Ni,and Co)nanoclusters for CO_(2)RR.MO_(x)supported on N-CNT,MO_(x)/N-CNT,achieves a CO yield of 2.6–2.8 mmol cm−2 min−1 at an overpotential of−0.55 V,which is two orders of magnitude higher than MO_(x)supported on acid treated CNTs(MO_(x)/O-CNT)and four times higher than pristine N-CNT.The faraday efficiency for electrochemical CO_(2)-to-CO conversion is as high as 90.3%at overpotential of 0.44 V.Both in-situ XAS measurements and DFT calculations disclose that MO_(x)nanoclusters can be hydrated in CO_(2)saturated KHCO_(3),and the N defects of N-CNT effectively stabilize these metal hydroxyl species under carbon dioxide reduction reaction conditions,which can split the water molecules and provide local protons to inhibit the poisoning of active sites under carbon dioxide reduction reaction conditions.
基金financially supported by the National Natural Science Foundation of China (U2032157)the Natural Science Foundation of Jiangsu Province (BK20201425)。
文摘The growth of electrochemically inert segregation layers on the surface of solid oxide fuel cell cathodes has become a bottleneck restricting the development of perovskite-structured oxygen reduction catalysts.Here,we report a new discovery in which enriched Ba and Fe ions on the near-surface of Nd_(1/2)Ba_(1/2)Co_(1/3)Fe_(1/3)Mn_(1/3)O_(3-δ)spontaneously agglomerate into dispersed Ba_(5)Fe_(2)O_(8) nanoparticles and maintain a highly active and durable perovskite structure on the surface.This unique surface selfcleaning phenomenon is related to the low average potential energy of Ba_(5)Fe_(2)O_(8),which is grown on the near-surface layer.The electrochemically inert Ba_(5)Fe_(2)O_(8) segregation layer on the near-surface of the perovskite catalyst achieves self-cleaning by regulating the formation energy of enriched metal oxides.This self-cleaned perovskite surface exhibits an ultrafast oxygen exchange rate,high catalytic activity for the oxygen reduction reaction,and good adaptability to the actual working conditions of solid oxide fuel cell stacks.This study paves a new way for overcoming the stubborn problem of perovskite catalyst surface deactivation and enriches the scientific knowledge of surface catalysis.
基金supported by the National Research Foundation of Korea (NRF) Grant funded by the Korean Government (MSIT) (RS-2023-00210114)supported by the National Research Foundation of Korea (NRF) grant funded by the Korea government (MSIT) (NRF-2021R1C1C1004264 and NRF2021R1A4A1032114)+1 种基金supported by the National Research Foundation of Korea (NRF) Grant funded by the Korean Government (MSIT) (NRF-2022R1A4A1019296)supported by the National R&D Program through the National Research Foundation of Korea (NRF), funded by the Ministry of Science and ICT (2021M3D1A2051636)。
文摘Mixed metal oxide(MMO) represents a critical class of materials that can allow for obtaining a dynamic interface between its components:reduced metal and its metal oxide counterpart during an electrocatalytic reaction.Here,a synthetic method utilizing a MOF-derived micro/mesoporous carbon as a template to prepare sub-2 nm MMO catalysts for CO_(2) electro reduction is reported.Starting from the zeolite imidazolate framework(ZIF-8),the pyrolyzed derivatives were used to synthesize sub-2 nm Pd-Ni MMO with different compositions.The Ni-rich(Pd_(20)-Ni_(80)/ZC) catalyst exhibits unexpectedly superior performance for CO production with an improved Faradaic efficiency(FE) of 95.3% at the current density of 200 mA cm^(-2) at-0.56 V vs.reversible hydrogen electrode(RHE) compared to other Pd-Ni compositions.X-ray photoelectron spectroscopy(XPS) analysis confirms the presence of Ni^(2+) and Pd^(2+) in all compositions,demonstrating the presence of MMO.Density functional theory(DFT) calculation reveals that the lower CO binding energy on the surface of the Pd_(20)-Ni_(80) cluster eases CO desorption,thus increasing its production.This work provides a general synthetic strategy for MMO electrocatalysts and can pave a new way for screening multimetallic catalysts with a dynamic electrochemical interface.
基金supported by the Australian Research Council Australian Laureate Fellowship(No.FL200100049)the support of Natural Science Foundation for Young Scholars of Jiangsu Province(No.BK20220879)+1 种基金National Natural Science Foundation for Young Scholars of China(No.22209072)Monash University for a PhD scholarship as part of the university support for establishment of the ARC Research Hub for Energy-efficient Separation(H170100009)。
文摘Metal-air batteries face a great challenge in developing efficient and durable low-cost oxygen reduction reaction(ORR)electrocatalysts.Single-atom iron catalysts embedded into nitrogen doped carbon(Fe-N-C)have emerged as attractive materials for potential replacement of Pt in ORR,but their catalytic performance was limited by the symmetrical electronic structure distribution around the single-atom Fe site.Here,we report our findings in significantly enhancing the ORR performance of Fe-N-C by moderate Fe_(2)O_(3) integration via the strong electronic interaction.Remarkably,the optimized catalyst(M-Fe_(2)O_(3)/Fe_(SA)@NC)exhibits excellent activity,durability and good tolerance to methanol,outperforming the benchmark Pt/C catalyst.When M-Fe_(2)O_(3)/Fe_(SA)@NC catalyst was used in a practical zinc-air battery assembly,peak power density of 155 mW cm^(-2)and specific capacity of 762 mA h g_(Zn)^(-1)were achieved and the battery assembly has shown superior cycling stability over a period of 200 h.More importantly,theoretical studies suggest that the introduction of Fe_(2)O_(3) can evoke the crystal field alteration and electron redistribution on single Fe atoms,which can break the symmetric charge distribution of Fe-N_(4) and thereby optimize the corresponding adsorption energy of intermediates to promote the O_(2)reduction.This study provides a new pathway to promote the catalytic performance of single-atom catalysts.
基金Australian Centre for Neutron ScatteringAustralian Nuclear Science and Technology Organisation,Grant/Award Number:MI8046+1 种基金Max Planck-POSTECH-Hsinchu Center for Complex Phase MaterialsHigh-Performance Computing Center of Nanjing Tech University。
文摘Electrochemical carbon dioxide(CO_(2))reduction(ECR)is a promising technology to produce valuable fuels and feedstocks from CO_(2).Despite large efforts to develop ECR catalysts,the investigation of the catalytic performance and electrochemical behavior of complex metal oxides,especially perovskite oxides,is rarely reported.Here,the inorganic perovskite oxide Ag-doped(La_(0.8)Sr_(0.2))_(0.95)Ag_(0.05)MnO_(3-δ)(LSA0.05M)is reported as an efficient electrocatalyst for ECR to CO for the first time,which exhibits a Faradaic efficiency(FE)of 84.3%,a remarkable mass activity of 75Ag^(-1)(normalized to the mass of Ag),and stability of 130 h at a moderate overpotential of 0.79 V.The LSA0.05M catalyst experiences structure reconstruction during ECR,creating the in operando-formed interface between the perovskite and the evolved Ag phase.The evolved Ag is uniformly distributed with a small particle size on the perovskite surface.Theoretical calculations indicate the reconstruction of LSA0.05M during ECR and reveal that the perovskite-Ag interface provides adsorption sites for CO_(2) and accelerates the desorption of the*CO intermediate to enhance ECR.This study presents a novel high-performance perovskite catalyst for ECR andmay inspire the future design of electrocatalysts via the in operando formation of metal-metal oxide interfaces.
基金Project(51374239)supported by the National Natural Science Foundation of China
文摘Digesting aluminum-bearing minerals and converting ferric oxide to magnetite simultaneously in Bayer digestion process is crucially important to deal with high-iron diasporic bauxite economically for alumina production.The reaction behaviors of hydrothermal reduction of ferric oxide in alkali solution were studied by both thermodynamic calculation and experimental investigation.The thermodynamic calculation indicates that Fe3O4 can be formed by the conversion of Fe2O3 at proper redox potentials in alkaline solution.The experimental results show that the formation ratio of Fe3O4 either through the reaction of Fe and Fe2O3 or through the reaction of Fe and H2O in alkaline aqueous solution increases remarkably with raising the temperature and alkali concentration,suggesting that Fe(OH)3- and Fe(OH)4- form by dissolving Fe and Fe2O3,respectively,in alkaline aqueous solution and further react to form Fe3O4.Moreover,aluminate ions have little influence on the hydrothermal reduction of Fe2O3 in alkaline aqueous solution,and converting iron minerals to magnetite can be realized in the Bayer digestion process of diasporic bauxite.
文摘The structure and catalytic desulfurization characteristics of CeO2-TiO2 mixed oxides were investigated by means ofX-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS) and catalytic activity tests. According to the results, a CeO2-TiO2solid solution is formed when the mole ratio of cerium to titanium n(Ce):n(Ti) is 5:5 or greater, and the most suitable n(Ce):n(Ti) isdetermined as 7:3, over which the conversion rate of SO2 and the yield of sulfur at 500℃ reach 93% and 99%, respectively.According to the activity testing curve, Ce0.7Ti0.3O2 (n(Ce):n(Ti)=7:3) without any pretreatment can be gradually activated by reagentgas after about 10 min, and reaches a steady activation status 60 min later. The XPS results of Ce0.7Ti0.3O2 after different time ofSO2+CO reaction show that CeO2 is the active component that offers the redox couple Ce4+/Ce3+ and the labile oxygen vacancies, andTiO2 only functions as a catalyst structure stabilizer during the catalytic reaction process. After 48 h of catalytic reaction at 500℃,Ce0.7Ti0.3O2 still maintains a stable structure without being vulcanized, demonstrating its good anti-sulfur poisoning performance.
基金Project(21376273)supported by the National Natural Science Foundation of ChinaProject(2010FJ1011)supported by the Key Program of Science and Technology of Hunan Province,China
文摘The extraction of manganese from low-grade manganese oxide ores using Ca S derived from Ca SO4 as reductant was investigated. The effects of mass ratio of Ca S to ore, reduction temperature, reduction time, liquid to solid ratio(L/S ratio), stirring speed, leaching temperature, leaching time and H2SO4 concentration on the leaching rates of Mn and Fe during the reduction–acid leaching process were discussed. The leaching rates of 96.47% for Mn and 19.24% for Fe were obtained under the optimized conditions of mass ratio of Ca S to manganese oxide ore 1:6.7, L/S ratio 5:1, stirring speed 300 r/min, reduction temperature of 95 °C for 2.0 h in the reduction process and leaching stirring speed of 200 r/min, H2SO4 concentration of 1.5 mol/L, leaching temperature of 80 °C for 5 min in the leaching process. In addition, this process can be employed in the recovery of manganese from various manganese oxide ores, and Mn leaching rate above 95% is obtained.
基金the financial support provided by the National Natural Science Foundation of China(22075290,21972068,52164028)the Beijing Natural Science Foundation(Z200012)+3 种基金the State Key Laboratory of Multiphase Complex Systemsthe Institute of Process Engineeringthe Chinese Academy of Sciences(MPCS-2021-A-05)the Nanjing IPE Institute of Green Manufacturing Industry(E0010725).
文摘Dealloying by which the transition metal is partially or completely leached from an alloy precursor is an effective way to optimize the fundamental effects for further enhancing the electrocatalysis of a catalyst.Herein,to address the deficiencies associated with the commonly used dealloying methods,for example,electrochemical and sulfuric acid/nitric acid treatment,we report an acetic acid-assisted mild strategy to dealloy Cu atoms from the outer surface layers of CuPd alloy nanoparticles to achieve high-efficiency electrocatalysis for oxygen reduction and ethanol oxidation in an alkaline electrolyte.The leaching of Cu atoms by acetic acid exerts an additional compressive strain effect on the surface layers and exposes more active Pd atoms,which is beneficial for boosting the catalytic performance of a dealloyed catalyst for the oxygen reduction reaction(ORR)and the ethanol oxidation reaction(EOR).In particular,for ORR,the CuPd nanoparticles with a Pd/Cu molar ratio of 2:1 after acetic dealloying show a half-wave potential of 0.912 V(vs.RHE)and a mass activity of 0.213 AmgPd^(-1) at 0.9 V,respectively,while for EOR,the same dealloyed sample has a mass activity and a specific activity of 8.4 Amg^(-1) and 8.23 mA cm^(-2),respectively,much better than their dealloyed counterparts at other temperatures and commercial Pd/C as well as a Pt/C catalyst.
基金This work was supported by the National Research Foundation of Korea(NRF)grant funded by the Korean Government(MSIT)(2019M3E6A1103944,2020R1A2C2010690).
文摘The unique characteristics of nanofibers in rational electrode design enable effec-tive utilization and maximizing material properties for achieving highly efficient and sustainable CO_(2) reduction reactions( CO_(2)RRs)in solid oxide elec-trolysis cells(SOECs).However,practical appli-cation of nanofiber-based electrodes faces chal-lenges in establishing sufficient interfacial contact and adhesion with the dense electrolyte.To tackle this challenge,a novel hybrid nanofiber electrode,La_(0.6)Sr_(0.4)Co_(0.15)Fe_(0.8)Pd_(0.05)O_(3-δ)(H-LSCFP),is developed by strategically incorporating low aspect ratio crushed LSCFP nanofibers into the excess porous interspace of a high aspect ratio LSCFP nanofiber framework synthesized via electrospinning technique.After consecutive treatment in 100% H_(2) and CO_(2) at 700°C,LSCFP nanofibers form a perovskite phase with in situ exsolved Co metal nanocatalysts and a high concentration of oxygen species on the surface,enhancing CO_(2) adsorption.The SOEC with the H-LSCFP electrode yielded an outstanding current density of 2.2 A cm^(-2) in CO_(2) at 800°C and 1.5 V,setting a new benchmark among reported nanofiber-based electrodes.Digital twinning of the H-LSCFP reveals improved contact adhesion and increased reaction sites for CO_(2)RR.The present work demonstrates a highly catalytically active and robust nanofiber-based fuel electrode with a hybrid structure,paving the way for further advancements and nanofiber applications in CO_(2)-SOECs.
基金the competence centre Fun Mat-II funded by the Swedish Agency for Innovation Systems(Vinnova,grant no 2016-05156)Swedish Energy Agency(project no 42022-1)+3 种基金Swedish Research Council(VR 2021-04427,VR 2019-05577,VR 2016–05990)the Centre in Nanoscience and Technology(CeNano,Linkoping Institute of Technology(LiTH),Linkoping University,2020,2021)the Swedish Government Strategic Research Area in Materials Science on Advanced Functional Materials at Linkoping University(Faculty Grant SFO-Mat-Li U No.2009-00971)the Knut and Alice Wal enberg Foundation(H2O2,KAW 2018.0058),for support
文摘Electrocatalysis enables the industrial transition to sustainable production of chemicals using abundant precursors and electricity from renewable sources.De-centralized production of hydrogen peroxide(H_(2)O_(2))from water and oxygen of air is highly desirable for daily life and industry.We report an effective electrochemical refinery(e-refinery)for H_(2)O_(2)by means of electrocatalysis-controlled comproportionation reaction(2_(H)O+o→2HO),feeding pure water and oxygen only.Mesoporous nickel(Ⅱ)oxide(NiO)was used as electrocatalyst for oxygen evolution reaction(OER),producing oxygen at the anode.Conducting polymer poly(3,4-ethylenedioxythiophene):poly(styrene sulfonate)(PEDOT:PSS)drove the oxygen reduction reaction(ORR),forming H_(2)O_(2)on the cathode.The reactions were evaluated in both half-cell and device configurations.The performance of the H_(2)O_(2)e-refinery,assembled on anion-exchange solid electrolyte and fed with pure water,was limited by the unbalanced ionic transport.Optimization of the operation conditions allowed a conversion efficiency of 80%.
文摘Although metal oxide-zeolite hybrid materials have long been known to achieve enhanced catalytic activity and selectivity in NO_(x)removal reactions through the inter-particle diffusion of intermediate species,their subsequent reaction mechanism on acid sites is still unclear and requires investigation.In this study,the distribution of Brønsted/Lewis acid sites in the hybrid materials was precisely adjusted by introducing potassium ions,which not only selectively bind to Brønsted acid sites but also potentially affect the formation and diffusion of activated NO species.Systematic in situ diffuse reflectance infrared Fourier transform spectroscopy analyses coupled with selective catalytic reduction of NO_(x)with NH_(3)(NH_(3)-SCR)reaction demonstrate that the Lewis acid sites over MnO_(x)are more active for NO reduction but have lower selectivity to N_(2)than Brønsted acids sites.Brønsted acid sites primarily produce N_(2),whereas Lewis acid sites primarily produce N_(2)O,contributing to unfavorable N_(2)selectivity.The Brønsted acid sites present in Y zeolite,which are stronger than those on MnO_(x),accelerate the NH_(3)-SCR reaction in which the nitrite/nitrate species diffused from the MnO_(x)particles rapidly convert into the N_(2).Therefore,it is important to design the catalyst so that the activated NO species formed in MnO_(x)diffuse to and are selectively decomposed on the Brønsted acid sites of H-Y zeolite rather than that of MnO_(x)particle.For the physically mixed H-MnO_(x)+H-Y sample,the abundant Brønsted/Lewis acid sites in H-MnO_(x)give rise to significant consumption of activated NO species before their inter-particle diffusion,thereby hindering the enhancement of the synergistic effects.Furthermore,we found that the intercalated K+in K-MnO_(x)has an unexpected favorable role in the NO reduction rate,probably owing to faster diffusion of the activated NO species on K-MnO_(x)than H-MnO_(x).This study will help to design promising metal oxide-zeolite hybrid catalysts by identifying the role of the acid sites in two different constituents.
基金supported by the National Natural Science Foundation of China(2137626121173270)+4 种基金the National High Technology Research and Development Program of China(863 Program2015AA034603)the Beijing Natural Science Foundation(2142027)the China University of Petroleum Fund(201300071100072462015QZDX04)~~
文摘A series of meso‐microporous copper‐supporting chabazite molecular sieve(CuSAPO‐34) catalysts with excellent performance in low‐temperature ammonia selective catalytic reduction(NH3‐SCR)have been synthesized via a one‐pot hydrothermal crystallization method. The physicochemical properties of the catalysts were characterized by scanning electron microscopy, transmission electron microscopy, N2 adsorption‐desorption measurements, X‐ray diffraction, 27 Al magic angle spinning nuclear magnetic resonance, diffuse reflectance ultraviolet‐visible spectroscopy, inductively coupled plasma‐atomic emission spectroscopy, X‐ray photoelectron spectroscopy, temperature‐programmed reduction measurements, and electron paramagnetic resonance analysis. The formation of micro‐mesopores in the Cu‐SAPO‐34 catalysts decreases diffusion resistance and greatly improves the accessibility of reactants to catalytic active sites. The main active sites for NH3‐SCR reaction are the isolated Cu^2+ species displaced into the ellipsoidal cavity of the Cu‐SAPO‐34 catalysts.
文摘Studies have extensively addressed the development of electrocatalytic technologies for energy storage and conversion,fuel production,and environmental protection.Electrode processes such as different oxidation and reduction reactions play a vital and significant role in these technologies.In this regard,efficient,inexpensive,and stable electrocatalysts capable can significantly promote electrochemical reactions.Unique features of metal–organic frameworks(MOFs)such as their high porosity,tunable structure,size,and pore shape,high surface area,and redox properties have introduced them as an ideal electrocatalyst candidate.This review is thus aimed at elucidating the role of MOF-based materials(pristine,derivatives and composites)as efficient electrocatalysts in energy and sensing-related oxidation and reduction reactions such as oxygen reduction reaction(ORR),hydrogen oxidation reaction(HOR),carbon dioxide reduction reaction(CO_(2)RR),urea oxidation reaction(UOR),alcohol oxidation reaction(AOR),nitrogen reduction reaction(NRR),and glucose oxidation reaction(GOR)in advanced energy and sensing devices.Also,the structure–property relationship of the electrocatalyst was elaborated for each electrocatalytic reaction.Finally,perspectives on the potential research topics for practical use of MOF-based electrocatalysts are addressed.The present review can improve the interest in MOF-based electrocatalysts to study different oxidation and reduction reactions in energy and sensing systems.