Metal nanoparticle(NP_S)catalysts exhibit desirable activities in various catalytic reactions.However,the sintering of metal NPs at high-temperatures even in reducing atmospheres limits its practical application.In th...Metal nanoparticle(NP_S)catalysts exhibit desirable activities in various catalytic reactions.However,the sintering of metal NPs at high-temperatures even in reducing atmospheres limits its practical application.In this work,we successfully synthesized TPA-ZSM-5 with pit-type defects by treating the ZSM-5 with tetrahydroxy ammonium hydroxide(TPAOH),which was then used as a support to prepare Ag-based and Cu-based catalysts.Stability testing results show that the Ag/TPA-ZSM-5 catalyst treated at 800℃with H_(2) could maintain the high performance in NH_(3)-SCO and the Cu/TPA-ZSM-5 catalyst treated at 900℃ with N_(2) could maintained its excellent activity in NH_(3)-SCR,however,the activities of Ag/ZSM-5 and Cu/ZSM-5 were drastically decreased or even deactivated after high-temperature treatment.In addition,a series of characterization analyses revealed that the excellent thermal stability is attribute to the presence of pit-type defects in the TPA-ZSM-5 as physical barriers to slow down or even inhibit the Ag NPs and Cu NPs sintering process.The strategy of using the pit-type defects to inhibit the sintering of metal NPs and improve the thermal stability can greatly enhance the practical application of catalysts.展开更多
The CO_(2) reduction reaction(CO_(2)RR)is notable for itsmultiple advantages,such as mild reaction conditions,controllable product output,and ease of operation.The chemistry of CO_(2)RR to producemulticarbon products ...The CO_(2) reduction reaction(CO_(2)RR)is notable for itsmultiple advantages,such as mild reaction conditions,controllable product output,and ease of operation.The chemistry of CO_(2)RR to producemulticarbon products involvesmultiple electron-proton transfer steps,in which the adsorption of CO intermediates is usually the key rate-determining step of the reaction.Currently,Cu is the only metal catalyst known to efficiently reduce CO_(2) tomulticarbon products,mainly due to its appropriate adsorption energy for CO intermediates.However,single Cu catalysts often face challenges such as excessively high overpotentials and poor selectivity,which limit their potential application in CO_(2) reduction.In recent years,electrochemical CO_(2) reduction using copper-based tandem catalysts has become an effective strategy to enhance the overall performance of CO_(2)RR and a hot topic in the research field.Here we review recent research advances in the field of electrochemical CO_(2)RR where tandemmethods have been applied.Themajor points are the following:(1)the tandem process allows for more precise control of the electrochemical reduction pathway,thereby increasing the yield of the target product while reducing the generation of by-products;(2)Mass transportation of *CO intermediates and spatial management is important for the generation of multicarbon products;(3)a variety of tandem means for upgrading the product to a deeply reduced product are reviewed.展开更多
The need to secure environmentally sustainable sources of clean fuel has led to intensive research into the catalytic conversion of CO_(2)into valuable C_(2)+compounds.However,the intrinsically sluggish reduction kine...The need to secure environmentally sustainable sources of clean fuel has led to intensive research into the catalytic conversion of CO_(2)into valuable C_(2)+compounds.However,the intrinsically sluggish reduction kinetics and competing reaction pathways present challenges in achieving high product selectivity and efficiency.Herein,we focus on the transformation of CO_(2)into C_(2)+products,particularly emphasizing advances in non-copper-based catalytic systems,which have emerged as promising alternatives that present unique electronic structures and adsorption properties.Unlike conventional copper catalysts,these systems offer distinct advantages in selectivity and stability,particularly through the modulation of surface defect engineering.We systematically analyze the main reaction pathways leading to C_(2)+products,including ethylene formation and higher hydrocarbon(C_(2)-4)alcohols and oxygenates,while critically assessing the mechanistic insights that differentiate non-copper catalysts from their Cu-based counterparts.By summarizing recent developments,the key challenges,and optimization strategies,we provide a comprehensive overview of how non-copper catalysts can enable efficient and scalable CO_(2)reduction reactions,with an aim of assisting researchers in their design of novel catalysts that may reach industrial applications.展开更多
The nano ZrO2-supported copper-based catalysts for methane combustion were investigated by means of N2 adsorption, TEM, XRD, H2-TPR techniques and the test of methane oxidation. Two kinds of ZrO2 were used as support,...The nano ZrO2-supported copper-based catalysts for methane combustion were investigated by means of N2 adsorption, TEM, XRD, H2-TPR techniques and the test of methane oxidation. Two kinds of ZrO2 were used as support, one （ZrO2-1） was obtained from the commercial ZrO2 and the other （ZrO2-2） was issued from the thermal decomposition of zirconium nitrate. It was found that the CuO/ZrO2-2 catalyst was more active than CuO/ZrO2-1. N2 adsorption, H2-TPR and XRD measurements showed that larger surface area, better reduction property, presence of tetragonal ZrO2 and higher dispersion of active component for CuO/ZrO2-2 than that of CuO/ZrO2-1. These factors could be the dominating reasons for its higher activity for methane combustion.展开更多
Various Cu/ZnO/Al2O3 catalysts have been synthesized by different aluminum emulsions as aluminum sources and their pertormances tor methanol synthesis from syngas have been investigated. The influences of preparation ...Various Cu/ZnO/Al2O3 catalysts have been synthesized by different aluminum emulsions as aluminum sources and their pertormances tor methanol synthesis from syngas have been investigated. The influences of preparation methods of aluminum emulsions on physicochemical and catalytic properties of catalysts were studied by XRD, SEM, XPS,N2 adsorption-desorption techniques and methanol synthesis from syngas. The preparation methods of aluminum emulsions were found to influence the catalytic activity, CuO crystallite size, surface area and Cu0 surface area and reduction process. The results show that the catalyst CN using the aluminum source prepared by addition the ammonia into the aluminum nitrate （NP） exhibited the best catalytic performance for methanol synthesis from syngas.展开更多
Nitrogen is essential for life and ecosystems.The nitrogen cycle is fundamental to all life on earth and has been implicated in his-torical mass extinction events,where disruptions to its stability have played a criti...Nitrogen is essential for life and ecosystems.The nitrogen cycle is fundamental to all life on earth and has been implicated in his-torical mass extinction events,where disruptions to its stability have played a critical role[1].Moreover,the nitrogen cycle's response to climate change could critically influence atmo-spheric CO_(2) levels and the trajectory of global warming[2].However,improper management of anthropogenic nitrogen-containing wastewater,including domestic sewage,agricultural runoff,and industrial effluents,has pushed the nitrogen cycle to the brink of imbalance[1].展开更多
To date,copper-based catalysts are one of the most prominent catalysts that can electrochemically reduce CO_(2)towards highvalue fuels or chemicals,such as ethylene,ethanol,and acetic acid.However,the chemically activ...To date,copper-based catalysts are one of the most prominent catalysts that can electrochemically reduce CO_(2)towards highvalue fuels or chemicals,such as ethylene,ethanol,and acetic acid.However,the chemically active feature of Cu-based catalysts hinders the understanding of the intrinsic catalytic active sites during the initial and the operative processes of electrochemical CO_(2)reduction(CO_(2)RR).The identification and engineering of active sites during the dynamic evolution of catalysts are thereby vital to further improve the activity,selectivity,and durability of Cu-based catalysts for high-performance CO_(2)RR.In this regard,four triggers for the dynamic evolution of catalysts were introduced in detail.Afterward,three typical active-site theories during the dynamic reconstruction of catalysts were discussed.In addition,the strategies in catalyst design were summarized according to the latest reports of Cu-based catalysts for CO_(2)RR,including the tuning of electronic structure,controlling of the external potential,and regulation of local catalytic environment.Finally,the conclusions and perspectives were provided to inspire more investigations and studies on the intrinsic active sites during the dynamic evolution of catalysts,which could promote the optimization of the catalyst system to further improve the performance of CO_(2)RR.展开更多
Aiming at the problems of insufficient activity and selectivity of Cu-based catalysts in CO_(2)hydrogenation to methanol,Al_(2)O_(3),ZrO_(2)and CeO_(2)modified Cu-ZnO catalysts by the co-precipitation method were prep...Aiming at the problems of insufficient activity and selectivity of Cu-based catalysts in CO_(2)hydrogenation to methanol,Al_(2)O_(3),ZrO_(2)and CeO_(2)modified Cu-ZnO catalysts by the co-precipitation method were prepared,and the influence mechanism of additives on the structure-performance relationship of the catalysts was systematically explored.Through a variety of characterization methods such as XRD,N2 physical adsorption-desorption,TEM,H_(2)-TPR,CO_(2)-TPD and XPS,combined with catalytic performance evaluation experiments,the correlation between the microstructure of catalysts and the reaction performance of CO_(2)hydrogenation to methanol was analyzed in depth.The results show that metal additives significantly improve the performance of catalysts.After the introduction of additives,the specific surface area and pore volume of the catalysts increase,the grain size of Cu decreases,and its dispersion improves.The Ce-modified CZC catalyst exhibited the best performance,with the grain size of CuO as small as 11.41 nm,and the surface oxygen vacancy concentration(OⅡ/OⅠ=3.15)was significantly higher than that of other samples.The reaction performance test shows that under the conditions of 2.8 MPa,8000 h−1 and 280℃,the CO_(2)conversion of the CZC catalyst reached 18.83%,the methanol selectivity was 68.40%,and the methanol yield was 12.88%,all of which are superior to other catalysts.Its excellent performance can be attributed to the fact that CeO_(2)enhances the metal-support interaction,increases the surface basicity,promotes the adsorption and activation of CO_(2),and simultaneously inhibits the reverse water-gas shift side reaction.This study clarifies the structure-activity regulation mechanism of additive modification on Cu-ZnO catalysts,providing a theoretical basis and technical reference for the development of efficient catalysts for CO_(2)hydrogenation to methanol.展开更多
Under the backdrop of“Carbon Peak and Carbon Neutrality”(dual carbon)goal in China,the methane-carbon dioxide reforming reaction has attracted considerable attention due to its environmental benefits of converting t...Under the backdrop of“Carbon Peak and Carbon Neutrality”(dual carbon)goal in China,the methane-carbon dioxide reforming reaction has attracted considerable attention due to its environmental benefits of converting two greenhouse gases(methane and carbon dioxide)into syngas and its promising industrial applications.Nickel(Ni)-based catalysts,with high catalytic activity,low cost,and abundant resources,are considered ideal candidates for industrial applications.In this article,three reaction kinetic models were briefly introduced,namely the Power-Law(PL)model,the Eley-Rideal(ER)model,and the Langmuir-Hinshelwood-Hougen-Watson(LHHW)model.Based on the LHHW model,the reaction kinetics and mechanisms of different catalytic systems were systematically discussed,including the properties of supports,the doping of noble metals and transition metals,the role of promoters,and the influence of the geometric and electronic structures of Ni on the reaction mechanism.Furthermore,the kinetics of carbon deposition and elimination on various catalysts were analyzed.Based on the reaction rate expressions for carbon elimination,the reasons for the high activity of transition metal iron(Fe)-doped catalysts and core-shell structured catalysts in carbon elimination were explained.Based on the detailed collation and comparative analysis of the reaction mechanisms and kinetic characteristics across diverse Ni-based catalytic systems,a theoretical guidance for the designing of high-performance catalysts was provided in this work.展开更多
Electrochemical water splitting represents a sustainable technology for hydrogen(H_(2))production.However,its large-scale implementation is hindered by the high overpotentials required for both the cathodic hydrogen e...Electrochemical water splitting represents a sustainable technology for hydrogen(H_(2))production.However,its large-scale implementation is hindered by the high overpotentials required for both the cathodic hydrogen evolution reaction(HER)and the anodic oxygen evolution reaction(OER).Transition metal-based catalysts have garnered significant research interest as promising alternatives to noble-metal catalysts,owing to their low cost,tunable composition,and noble-metal-like catalytic activity.Nevertheless,systematic reviews on their application as bifunctional catalysts for overall water splitting(OWS)are still limited.This review comprehensively outlines the principal categories of bifunctional transition metal electrocatalysts derived from electrospun nanofibers(NFs),including metals,oxides,phosphides,sulfides,and carbides.Key strategies for enhancing their catalytic performance are systematically summarized,such as heterointerface engineering,heteroatom doping,metal-nonmetal-metal bridging architectures,and single-atom site design.Finally,current challenges and future research directions are discussed,aiming to provide insightful perspectives for the rational design of high-performance electrocatalysts for OWS.展开更多
CO_(2)reduction technology can promote the resource utilization of carbon and help alleviate global warming and energy supply pressure.It is an effective way to achieve energy conversion and utilization.Covalent organ...CO_(2)reduction technology can promote the resource utilization of carbon and help alleviate global warming and energy supply pressure.It is an effective way to achieve energy conversion and utilization.Covalent organic frameworks(COFs)are porous crystalline materials formed by connecting organic monomers through covalent bonds.They have the characteristics of functional diversity and rich chemical properties.Their advantages,such as high porosity,a wide range of visible light absorption,and excellent charge separation efficiency,give them good potential in CO_(2)capture,separation,and conversion.Currently,Cu is a key metal in the catalytic CO_(2)reduction reaction(CO_(2)RR)for the preparation of high-value-added chemicals.The preparation of highly stable and large-pore Cu-based COFs using COFs as an ideal sacrificial template for loading Cu can be used to develop high-performance electrocatalysts and photocatalysts.In this review,we discuss the latest advancements in this field,including the development of various Cu-based COFs and their applications as catalysts for CO_(2)RR.Here,we mainly introduce the synthesis strategies,some important characterization information,and the applications of electrocatalytic and photocatalytic CO_(2)conversion using these previously reported Cu-based COFs.展开更多
Catalysts are key for olefin polymerization reactions and are also ubiquitous in catalysis science.Multinuclear metal catalysts have witnessed enhanced performances in catalytic reactions relative to mononuclear catal...Catalysts are key for olefin polymerization reactions and are also ubiquitous in catalysis science.Multinuclear metal catalysts have witnessed enhanced performances in catalytic reactions relative to mononuclear catalysts,but which substantially involve multi-step,tedious,and difficult synthesis.Herein,this study reports an intriguing approach to construct multi-nuclear catalysts for the milestoneα-diimine nickel catalysts using an oligomeric strategy.A polymerizable norbornene unit is incorporated into theα-diimine ligand backbone,leading to the formation of the monomeric nickel catalyst Ni_(1)and its corresponding oligomeric nickel catalysts(Ni_(3)and Ni_(5))with varying degrees of polymerization(DP=3 and 5).Notably,the oligomeric catalyst Ni_(5)was facilely scaled up(50 g-level),showed enhanced thermal stability,exhibited 4.6 times higher activity,and yielded polyethylene elastomer with a 379%increased molecular weight in ethylene polymerization,compared to the monomeric catalyst Ni_(1).Catalytic performance enhancements of oligomeric catalysts were found to be DP-dependent.The kilogram-scale polyethylene,produced using Ni_(5)in a 20 L reactor,presented a highly branched all-hydrocarbon structure,which demonstrated typical elastic properties(tensile strength:4 MPa,elastic recovery:SR=72%)along with great processability(MFI=3.0 g/10 min),insulating characteristics(volume resistivity=2×10^(16)Ω/m),and hydrophobicity(water vapor permeability:0.03 g/m^(2)/day),suggesting potentially practical applications.展开更多
Seawater zinc-air batteries are promising energy storage devices due to their high energy density and utilization of seawater electrolytes.However,their efficiency is hindered by the sluggish oxygen reduction reaction...Seawater zinc-air batteries are promising energy storage devices due to their high energy density and utilization of seawater electrolytes.However,their efficiency is hindered by the sluggish oxygen reduction reaction(ORR)and chlorideinduced degradation over conventional catalysts.In this study,we proposed a universal synthetic strategy to construct heteroatom axially coordinated Fe–N_(4) single-atom seawater catalyst materials(Cl–Fe–N_(4) and S–Fe–N_(4)).X-ray absorption spectroscopy confirmed their five-coordinated square pyramidal structure.Systematic evaluation of catalytic activities revealed that compared with S–Fe–N_(4),Cl–Fe–N_(4) exhibits smaller electrochemical active surface area and specific surface area,yet demonstrates higher limiting current density(5.8 mA cm^(−2)).The assembled zinc-air batteries using Cl–Fe–N_(4) showed superior power density(187.7 mW cm^(−2) at 245.1 mA cm^(−2)),indicating that Cl axial coordination more effectively enhances the intrinsic ORR activity.Moreover,Cl–Fe–N_(4) demonstrates stronger Cl−poisoning resistance in seawater environments.Chronoamperometry tests and zinc-air battery cycling performance evaluations confirmed its enhanced stability.Density functional theory calculations revealed that the introduction of heteroatoms in the axial direction regulates the electron center of Fe single atom,leading to more active reaction intermediates and increased electron density of Fe single sites,thereby enhancing the reduction in adsorbed intermediates and hence the overall ORR catalytic activity.展开更多
In this paper,the research progress of Cu-based catalyst and the activity enhancement strategies in the hydrogenation of dimethyl oxalate(DMO)to ethylene glycol(EG)was reviewed.As a green and economical ethylene glyco...In this paper,the research progress of Cu-based catalyst and the activity enhancement strategies in the hydrogenation of dimethyl oxalate(DMO)to ethylene glycol(EG)was reviewed.As a green and economical ethylene glycol production path,the core of DMO hydrogenation of EG lies in the rational design and optimization of catalysts.This paper first introduces the background of the DMO hydrogenation system EG significance and the important effect of Cu-based catalyst in the reaction,particularly emphasizing the coordination with the Cu^(+)-Cu^(0) species catalytic effect.Then,many factors affecting the activity of Cu-based catalysts were analyzed in detail,including the equilibrium effect between Cu^(0) and Cu+species,the surface dispersion of Cu species,the interaction between metal and support,and the morphology effect of the catalyst.Regarding strategies for improving catalyst performance,this paper summarized effective measures such as optimizing support structure,adding promoters and optimizing preparation methods,and demonstrated the practical application effects of these strategies through representative catalyst examples.In addition,this paper also discusses the complex relationship between the influencing factors and catalyst performance.It points out the key directions for future research,with in-depth exploration of the correlation between catalyst structure and performance,the development of new catalysts,and the application of machine learning and big data technology in the catalyst research and development.In summary,this paper provides comprehensive theoretical guidance and practical reference for the performance optimization of Cu-based catalysts for DMO hydrogenation to EG.展开更多
Lithium-sulfur(Li-S)batteries boast a theoretical energy density as high as 2600 Wh·kg^(−1),positioning them as a highly attractive option for future advanced energy storage systems.Challenges such as slow transf...Lithium-sulfur(Li-S)batteries boast a theoretical energy density as high as 2600 Wh·kg^(−1),positioning them as a highly attractive option for future advanced energy storage systems.Challenges such as slow transformation kinetics and shuttle effects associated with lithium polysulfides(LiPSs)have seriously hindered their practical applications.In this paper,we present a new method for the synthesis of hollow carbon-sphere-supported Co monatomic catalysts(Co-N-C).This new synthesis method achieves pyrolytic coordination using a precursor rich in imide(-RC=N-)polymers.This synthesis method not only improves the adsorbability and catalytic activity of LiPS but also significantly weakens the shuttle effect and generates Co-N-C with superior conductivity,abundant hollow structures,and a high specific surface area,thus efficiently capturing and restricting the movement of LiPS intermediates.The dispersed Co monoatomic catalysts(Co SACs)were anchored to a highly conductive nitrogen-doped carbon framework and exhibited symmetric N-coordination active sites(Co-N_(4))to ensure fast redox kinetics of LiPS and Li_(2)S_(2)/Li_(2)S solid-state products.The lithium-sulfur battery with Co-N-C as the sulfur carrier showed excellent discharging capacity of 1146.6 mAh·g^(−1) at a discharge rate of 0.5 C and maintained excellent performance at a high discharge rate of 2 C.The capacity decay rate in 500 cycles was only 0.086%per cycle,reflecting excellent long-term cycle stability.This study highlights the key role of the synergistic effect between single-atom cobalt catalysts and hollow carbon spheres in enhancing the efficiency of lithium-sulfur(Li-S)batteries.It also provides valuable insights into the construction and fabrication of highly active monatomic catalysts.The catalytic conversion efficiency of lithium polysulfides is significantly enhanced when embedded in hollow carbon architectures,which serves as a critical strategy for optimizing the electrochemical behavior of next-generation Li-S batteries.展开更多
High‐entropy amorphous catalysts(HEACs)integrate multielement synergy with structural disorder,making them promising candidates for water splitting.Their distinctive features—including flexible coordination environm...High‐entropy amorphous catalysts(HEACs)integrate multielement synergy with structural disorder,making them promising candidates for water splitting.Their distinctive features—including flexible coordination environments,tunable electronic structures,abundant unsaturated active sites,and dynamic structural reassembly—collectively enhance electrochemical activity and durability under operating conditions.This review summarizes recent advances in HEACs for hydrogen evolution,oxygen evolution,and overall water splitting,highlighting their disorder-driven advantages over crystalline counterparts.Catalytic performance benchmarks are presented,and mechanistic insights are discussed,focusing on how multimetallic synergy,amorphization effect,and in‐situ reconstruction cooperatively regulate reaction pathways.These insights provide guidance for the rational design of next‐generation amorphous high‐entropy electrocatalysts with improved efficiency and durability.展开更多
Using photoelectrocatalytic CO_(2) reduction reaction(CO_(2)RR)to produce valuable fuels is a fascinating way to alleviate environmental issues and energy crises.Bismuth-based(Bi-based)catalysts have attracted widespr...Using photoelectrocatalytic CO_(2) reduction reaction(CO_(2)RR)to produce valuable fuels is a fascinating way to alleviate environmental issues and energy crises.Bismuth-based(Bi-based)catalysts have attracted widespread attention for CO_(2)RR due to their high catalytic activity,selectivity,excellent stability,and low cost.However,they still need to be further improved to meet the needs of industrial applications.This review article comprehensively summarizes the recent advances in regulation strategies of Bi-based catalysts and can be divided into six categories:(1)defect engineering,(2)atomic doping engineering,(3)organic framework engineering,(4)inorganic heterojunction engineering,(5)crystal face engineering,and(6)alloying and polarization engineering.Meanwhile,the corresponding catalytic mechanisms of each regulation strategy will also be discussed in detail,aiming to enable researchers to understand the structure-property relationship of the improved Bibased catalysts fundamentally.Finally,the challenges and future opportunities of the Bi-based catalysts in the photoelectrocatalytic CO_(2)RR application field will also be featured from the perspectives of the(1)combination or synergy of multiple regulatory strategies,(2)revealing formation mechanism and realizing controllable synthesis,and(3)in situ multiscale investigation of activation pathways and uncovering the catalytic mechanisms.On the one hand,through the comparative analysis and mechanism explanation of the six major regulatory strategies,a multidimensional knowledge framework of the structure-activity relationship of Bi-based catalysts can be constructed for researchers,which not only deepens the atomic-level understanding of catalytic active sites,charge transport paths,and the adsorption behavior of intermediate products,but also provides theoretical guiding principles for the controllable design of new catalysts;on the other hand,the promising collaborative regulation strategies,controllable synthetic paths,and the in situ multiscale characterization techniques presented in this work provides a paradigm reference for shortening the research and development cycle of high-performance catalysts,conducive to facilitating the transition of photoelectrocatalytic CO_(2)RR technology from the laboratory routes to industrial application.展开更多
In this work, we report a simple and inexpensive approach to synthesize effective multicomponent Cu-Cu2O-CuO catalysts for the Rochow process from industrial waste contact masses （WCMs）. WCMs from the organosilane i...In this work, we report a simple and inexpensive approach to synthesize effective multicomponent Cu-Cu2O-CuO catalysts for the Rochow process from industrial waste contact masses （WCMs）. WCMs from the organosilane industry were treated with acid followed by reduction with metallic iron powder. The obtained copper powder was then subjected to controlled oxidation in air at different temperatures, followed by ball milling. The orthogonal array approach was applied to optimize this process, and the stirring speed and pH were found to significantly affect the leaching ratio and copper yield, respectively. When used for the Rochow process, the optimized ternary Cu-Cu2O-CuO catalyst greatly enhanced the dimethyldichlorosilane selectivity and Si conversion compared with Cu-Cu2O-CuO catalysts prepared without ball milling, bare Cu catalysts, and Cu-Cu2O-CuO catalysts with different compositions. This could be attributed to their small particle size and the strong synergistic effect among the multiple components in the catalyst with the optimized composition.展开更多
Electrocatalytic carbon dioxide reduction reaction(CO_(2)RR)holds the promise of both overcoming the greenhouse effect and synthesizing a wealth of chemicals.Electrocatalytic CO_(2) reduction toward carbon-containing ...Electrocatalytic carbon dioxide reduction reaction(CO_(2)RR)holds the promise of both overcoming the greenhouse effect and synthesizing a wealth of chemicals.Electrocatalytic CO_(2) reduction toward carbon-containing products,including C1 products(carbon monoxide,formic acid,etc),C2 products(ethylene,ethanol,etc.)and multi-carbon products(e.g.,n-propanol),provides beneficial fuel and chemicals for industrial production.The complexity of the multi-proton transfer processes and difficulties of C-C coupling in electrochemical CO_(2) reduction toward multi-carbon(C2+)products have attracted increasing concerns on the design of catalysts in comparison with those of C1 products.In this paper,we review the main advances in the syntheses of multi-carbon products through electrocatalytic carbon dioxide reduction in recent years,introduce the basic principles of electrocatalytic CO_(2)RR,and detailly elucidate two widely accepted mechanisms of C-C coupling reactions.Among abundant nanomaterials,copper-based catalysts are outstanding catalysts for the preparation of multi-carbon chemicals in electrochemical CO_(2)RR attributing to effective C-C coupling reactions.Regarding the different selectivity of multi-carbon chemicals but extensively applied copper-based catalysts,we classify and summarize various Cu-based catalysts through separating diverse multi-carbon products,where the modification of spatial and electronic structures is beneficial to increase the coverage of CO or lower the activation energy barrier for forming C-C bond to form the key intermediates and increase the production of multi-carbon products.Challenges and prospects involving the fundamental and development of copper-based catalysts in electrochemical CO_(2) reduction reaction are also proposed.展开更多
CONSPECTUS:As one of the essential pathways to carbon neutrality or carbon negativity,the electrochemical reduction of CO_(2) offers tremendous prospects for platform chemicals and fuel production.Copper(Cu)is current...CONSPECTUS:As one of the essential pathways to carbon neutrality or carbon negativity,the electrochemical reduction of CO_(2) offers tremendous prospects for platform chemicals and fuel production.Copper(Cu)is currently the only metal material that is able to reduce CO_(2) to multicarbon(C2+)products.Despite the fact that copper-based materials have been investigated for decades,we still confront numerous challenges on the path to the fundamental understanding and large-scale deployment of copper-based electrocatalysts for CO_(2) reduction.For fundamental investigations,it remains a variety of open questions about the CO_(2) reduction mechanisms.The convoluted C−C coupling pathways and product bifurcation processes confuse the design of efficient catalysts.The active sites of copper-based catalysts remain ambiguous due to surface reconstruction.As for theoretical calculations,the construction of electrolyte−electrode models and the investigation of solvation effects are premature for obtaining confident conclusions.In addition,simple and easily scalable techniques for catalyst synthesis still need to be continuously developed.For practical applications,the CO_(2) electrolyzer with copper-based materials must be operated with high current densities,high Faradaic efficiencies,high energetic efficiencies,high single-pass conversion rates(high product concentration),and long stability.Nevertheless,due to the intricate nature of electrochemical systems,a high-performance copper-based electrocatalyst alone is not sufficient to meet all of the above commercialization requirements.Therefore,reactor design involving mass transfer enhancement calls for more research input.Based on the above background and the urgency of the net-zero goal,we initiated our research on CO_(2) electrolysis using copper-based materials with an emphasis on active site identification and mass transfer enhancement.This Account describes our contribution to the field of C_(2+)products formation.We first discuss the synthesis of copper-based materials with a controlled atomic arrangement and valence states based on neural network-accelerated computational simulations.Using the synthesized catalyst,the selectivity of the target product is improved and the energy consumption of CO_(2) electrolysis is reduced.Then,we describe the efforts to investigate the reaction mechanisms,such as using first-principles calculations at the atomic level,in situ surface-enhanced vibrational spectroscopies at the micrometer level,and electrochemical kinetics studies at the apparent performance level.We also overview our efforts in the field of reaction system engineering,consisting of a vapor-fed CO_(2) threecompartment flow cell and a large-scale CO_(2) membrane electrode assembly,which can increase the reaction rates and single-pass yield.Furthermore,we put forward the main technical obstacles that currently need to be surmounted and provide insights into the commercial application of CO_(2) electrolysis technology.展开更多
基金supported by the National Natural Science Foundation of China(No.52370113)Yunnan Fundamental Research Projects(No.202101BE070001-001)。
文摘Metal nanoparticle(NP_S)catalysts exhibit desirable activities in various catalytic reactions.However,the sintering of metal NPs at high-temperatures even in reducing atmospheres limits its practical application.In this work,we successfully synthesized TPA-ZSM-5 with pit-type defects by treating the ZSM-5 with tetrahydroxy ammonium hydroxide(TPAOH),which was then used as a support to prepare Ag-based and Cu-based catalysts.Stability testing results show that the Ag/TPA-ZSM-5 catalyst treated at 800℃with H_(2) could maintain the high performance in NH_(3)-SCO and the Cu/TPA-ZSM-5 catalyst treated at 900℃ with N_(2) could maintained its excellent activity in NH_(3)-SCR,however,the activities of Ag/ZSM-5 and Cu/ZSM-5 were drastically decreased or even deactivated after high-temperature treatment.In addition,a series of characterization analyses revealed that the excellent thermal stability is attribute to the presence of pit-type defects in the TPA-ZSM-5 as physical barriers to slow down or even inhibit the Ag NPs and Cu NPs sintering process.The strategy of using the pit-type defects to inhibit the sintering of metal NPs and improve the thermal stability can greatly enhance the practical application of catalysts.
基金supported by the National Natural Science Foundation of China(No.52270078)the Fundamental Research Funds for the Central Universities(No.xzy022023039).
文摘The CO_(2) reduction reaction(CO_(2)RR)is notable for itsmultiple advantages,such as mild reaction conditions,controllable product output,and ease of operation.The chemistry of CO_(2)RR to producemulticarbon products involvesmultiple electron-proton transfer steps,in which the adsorption of CO intermediates is usually the key rate-determining step of the reaction.Currently,Cu is the only metal catalyst known to efficiently reduce CO_(2) tomulticarbon products,mainly due to its appropriate adsorption energy for CO intermediates.However,single Cu catalysts often face challenges such as excessively high overpotentials and poor selectivity,which limit their potential application in CO_(2) reduction.In recent years,electrochemical CO_(2) reduction using copper-based tandem catalysts has become an effective strategy to enhance the overall performance of CO_(2)RR and a hot topic in the research field.Here we review recent research advances in the field of electrochemical CO_(2)RR where tandemmethods have been applied.Themajor points are the following:(1)the tandem process allows for more precise control of the electrochemical reduction pathway,thereby increasing the yield of the target product while reducing the generation of by-products;(2)Mass transportation of *CO intermediates and spatial management is important for the generation of multicarbon products;(3)a variety of tandem means for upgrading the product to a deeply reduced product are reviewed.
基金supported by the Joint Funds of the National Natural Science Foundation of China(U24B20201)National Natural Science Foundation of China(22372007 and 21972010).
文摘The need to secure environmentally sustainable sources of clean fuel has led to intensive research into the catalytic conversion of CO_(2)into valuable C_(2)+compounds.However,the intrinsically sluggish reduction kinetics and competing reaction pathways present challenges in achieving high product selectivity and efficiency.Herein,we focus on the transformation of CO_(2)into C_(2)+products,particularly emphasizing advances in non-copper-based catalytic systems,which have emerged as promising alternatives that present unique electronic structures and adsorption properties.Unlike conventional copper catalysts,these systems offer distinct advantages in selectivity and stability,particularly through the modulation of surface defect engineering.We systematically analyze the main reaction pathways leading to C_(2)+products,including ethylene formation and higher hydrocarbon(C_(2)-4)alcohols and oxygenates,while critically assessing the mechanistic insights that differentiate non-copper catalysts from their Cu-based counterparts.By summarizing recent developments,the key challenges,and optimization strategies,we provide a comprehensive overview of how non-copper catalysts can enable efficient and scalable CO_(2)reduction reactions,with an aim of assisting researchers in their design of novel catalysts that may reach industrial applications.
文摘The nano ZrO2-supported copper-based catalysts for methane combustion were investigated by means of N2 adsorption, TEM, XRD, H2-TPR techniques and the test of methane oxidation. Two kinds of ZrO2 were used as support, one （ZrO2-1） was obtained from the commercial ZrO2 and the other （ZrO2-2） was issued from the thermal decomposition of zirconium nitrate. It was found that the CuO/ZrO2-2 catalyst was more active than CuO/ZrO2-1. N2 adsorption, H2-TPR and XRD measurements showed that larger surface area, better reduction property, presence of tetragonal ZrO2 and higher dispersion of active component for CuO/ZrO2-2 than that of CuO/ZrO2-1. These factors could be the dominating reasons for its higher activity for methane combustion.
文摘Various Cu/ZnO/Al2O3 catalysts have been synthesized by different aluminum emulsions as aluminum sources and their pertormances tor methanol synthesis from syngas have been investigated. The influences of preparation methods of aluminum emulsions on physicochemical and catalytic properties of catalysts were studied by XRD, SEM, XPS,N2 adsorption-desorption techniques and methanol synthesis from syngas. The preparation methods of aluminum emulsions were found to influence the catalytic activity, CuO crystallite size, surface area and Cu0 surface area and reduction process. The results show that the catalyst CN using the aluminum source prepared by addition the ammonia into the aluminum nitrate （NP） exhibited the best catalytic performance for methanol synthesis from syngas.
基金supported by the National Natural Science Foundation of China(Nos.52172291,52122312 and 52473294)the“Shuguang Program”supported by Shanghai Education Development Foundation and Shanghai Municipal Education Commission(No.22SG31).
文摘Nitrogen is essential for life and ecosystems.The nitrogen cycle is fundamental to all life on earth and has been implicated in his-torical mass extinction events,where disruptions to its stability have played a critical role[1].Moreover,the nitrogen cycle's response to climate change could critically influence atmo-spheric CO_(2) levels and the trajectory of global warming[2].However,improper management of anthropogenic nitrogen-containing wastewater,including domestic sewage,agricultural runoff,and industrial effluents,has pushed the nitrogen cycle to the brink of imbalance[1].
基金supported by the“Pioneer”and“Leading Goose”R&D Programs of Zhejiang(2022C03146)National Natural Science Foundation of China(22225606 and 22176029)Central Government Guided Local Science and Technology Development Fund(2021ZY1022)。
文摘To date,copper-based catalysts are one of the most prominent catalysts that can electrochemically reduce CO_(2)towards highvalue fuels or chemicals,such as ethylene,ethanol,and acetic acid.However,the chemically active feature of Cu-based catalysts hinders the understanding of the intrinsic catalytic active sites during the initial and the operative processes of electrochemical CO_(2)reduction(CO_(2)RR).The identification and engineering of active sites during the dynamic evolution of catalysts are thereby vital to further improve the activity,selectivity,and durability of Cu-based catalysts for high-performance CO_(2)RR.In this regard,four triggers for the dynamic evolution of catalysts were introduced in detail.Afterward,three typical active-site theories during the dynamic reconstruction of catalysts were discussed.In addition,the strategies in catalyst design were summarized according to the latest reports of Cu-based catalysts for CO_(2)RR,including the tuning of electronic structure,controlling of the external potential,and regulation of local catalytic environment.Finally,the conclusions and perspectives were provided to inspire more investigations and studies on the intrinsic active sites during the dynamic evolution of catalysts,which could promote the optimization of the catalyst system to further improve the performance of CO_(2)RR.
基金Supported by National Key R&D Program of China(2022YFA1503400)。
文摘Aiming at the problems of insufficient activity and selectivity of Cu-based catalysts in CO_(2)hydrogenation to methanol,Al_(2)O_(3),ZrO_(2)and CeO_(2)modified Cu-ZnO catalysts by the co-precipitation method were prepared,and the influence mechanism of additives on the structure-performance relationship of the catalysts was systematically explored.Through a variety of characterization methods such as XRD,N2 physical adsorption-desorption,TEM,H_(2)-TPR,CO_(2)-TPD and XPS,combined with catalytic performance evaluation experiments,the correlation between the microstructure of catalysts and the reaction performance of CO_(2)hydrogenation to methanol was analyzed in depth.The results show that metal additives significantly improve the performance of catalysts.After the introduction of additives,the specific surface area and pore volume of the catalysts increase,the grain size of Cu decreases,and its dispersion improves.The Ce-modified CZC catalyst exhibited the best performance,with the grain size of CuO as small as 11.41 nm,and the surface oxygen vacancy concentration(OⅡ/OⅠ=3.15)was significantly higher than that of other samples.The reaction performance test shows that under the conditions of 2.8 MPa,8000 h−1 and 280℃,the CO_(2)conversion of the CZC catalyst reached 18.83%,the methanol selectivity was 68.40%,and the methanol yield was 12.88%,all of which are superior to other catalysts.Its excellent performance can be attributed to the fact that CeO_(2)enhances the metal-support interaction,increases the surface basicity,promotes the adsorption and activation of CO_(2),and simultaneously inhibits the reverse water-gas shift side reaction.This study clarifies the structure-activity regulation mechanism of additive modification on Cu-ZnO catalysts,providing a theoretical basis and technical reference for the development of efficient catalysts for CO_(2)hydrogenation to methanol.
基金Supported by Innovation Capability Support Program of Shaanxi(2024RS-CXTD-53,2024ZC-KJXX-096)the Key R&D Program of Shaanxi Province(2022QCY-LL-69)Xi’an Science and Technology Project(24GXFW0089)。
文摘Under the backdrop of“Carbon Peak and Carbon Neutrality”(dual carbon)goal in China,the methane-carbon dioxide reforming reaction has attracted considerable attention due to its environmental benefits of converting two greenhouse gases(methane and carbon dioxide)into syngas and its promising industrial applications.Nickel(Ni)-based catalysts,with high catalytic activity,low cost,and abundant resources,are considered ideal candidates for industrial applications.In this article,three reaction kinetic models were briefly introduced,namely the Power-Law(PL)model,the Eley-Rideal(ER)model,and the Langmuir-Hinshelwood-Hougen-Watson(LHHW)model.Based on the LHHW model,the reaction kinetics and mechanisms of different catalytic systems were systematically discussed,including the properties of supports,the doping of noble metals and transition metals,the role of promoters,and the influence of the geometric and electronic structures of Ni on the reaction mechanism.Furthermore,the kinetics of carbon deposition and elimination on various catalysts were analyzed.Based on the reaction rate expressions for carbon elimination,the reasons for the high activity of transition metal iron(Fe)-doped catalysts and core-shell structured catalysts in carbon elimination were explained.Based on the detailed collation and comparative analysis of the reaction mechanisms and kinetic characteristics across diverse Ni-based catalytic systems,a theoretical guidance for the designing of high-performance catalysts was provided in this work.
基金Supported by the National Natural Science Foundation of China(No.52273056)the Science and Technology Development Program of Jilin Province,China(No.YDZJ202501ZYTS305)。
文摘Electrochemical water splitting represents a sustainable technology for hydrogen(H_(2))production.However,its large-scale implementation is hindered by the high overpotentials required for both the cathodic hydrogen evolution reaction(HER)and the anodic oxygen evolution reaction(OER).Transition metal-based catalysts have garnered significant research interest as promising alternatives to noble-metal catalysts,owing to their low cost,tunable composition,and noble-metal-like catalytic activity.Nevertheless,systematic reviews on their application as bifunctional catalysts for overall water splitting(OWS)are still limited.This review comprehensively outlines the principal categories of bifunctional transition metal electrocatalysts derived from electrospun nanofibers(NFs),including metals,oxides,phosphides,sulfides,and carbides.Key strategies for enhancing their catalytic performance are systematically summarized,such as heterointerface engineering,heteroatom doping,metal-nonmetal-metal bridging architectures,and single-atom site design.Finally,current challenges and future research directions are discussed,aiming to provide insightful perspectives for the rational design of high-performance electrocatalysts for OWS.
文摘CO_(2)reduction technology can promote the resource utilization of carbon and help alleviate global warming and energy supply pressure.It is an effective way to achieve energy conversion and utilization.Covalent organic frameworks(COFs)are porous crystalline materials formed by connecting organic monomers through covalent bonds.They have the characteristics of functional diversity and rich chemical properties.Their advantages,such as high porosity,a wide range of visible light absorption,and excellent charge separation efficiency,give them good potential in CO_(2)capture,separation,and conversion.Currently,Cu is a key metal in the catalytic CO_(2)reduction reaction(CO_(2)RR)for the preparation of high-value-added chemicals.The preparation of highly stable and large-pore Cu-based COFs using COFs as an ideal sacrificial template for loading Cu can be used to develop high-performance electrocatalysts and photocatalysts.In this review,we discuss the latest advancements in this field,including the development of various Cu-based COFs and their applications as catalysts for CO_(2)RR.Here,we mainly introduce the synthesis strategies,some important characterization information,and the applications of electrocatalytic and photocatalytic CO_(2)conversion using these previously reported Cu-based COFs.
基金financial support from the National Natural Science Foundation of China(Nos.22401274,U23B6011)the Jilin Provincial Science and Technology Department Program(No.20250102070JC)。
文摘Catalysts are key for olefin polymerization reactions and are also ubiquitous in catalysis science.Multinuclear metal catalysts have witnessed enhanced performances in catalytic reactions relative to mononuclear catalysts,but which substantially involve multi-step,tedious,and difficult synthesis.Herein,this study reports an intriguing approach to construct multi-nuclear catalysts for the milestoneα-diimine nickel catalysts using an oligomeric strategy.A polymerizable norbornene unit is incorporated into theα-diimine ligand backbone,leading to the formation of the monomeric nickel catalyst Ni_(1)and its corresponding oligomeric nickel catalysts(Ni_(3)and Ni_(5))with varying degrees of polymerization(DP=3 and 5).Notably,the oligomeric catalyst Ni_(5)was facilely scaled up(50 g-level),showed enhanced thermal stability,exhibited 4.6 times higher activity,and yielded polyethylene elastomer with a 379%increased molecular weight in ethylene polymerization,compared to the monomeric catalyst Ni_(1).Catalytic performance enhancements of oligomeric catalysts were found to be DP-dependent.The kilogram-scale polyethylene,produced using Ni_(5)in a 20 L reactor,presented a highly branched all-hydrocarbon structure,which demonstrated typical elastic properties(tensile strength:4 MPa,elastic recovery:SR=72%)along with great processability(MFI=3.0 g/10 min),insulating characteristics(volume resistivity=2×10^(16)Ω/m),and hydrophobicity(water vapor permeability:0.03 g/m^(2)/day),suggesting potentially practical applications.
基金funded by the Innovative Research Group Project of the National Natural Science Foundation of China(52121004)the Research Development Fund(No.RDF-21-02-060)by Xi’an Jiaotong-Liverpool University+1 种基金support received from the Suzhou Industrial Park High Quality Innovation Platform of Functional Molecular Materials and Devices(YZCXPT2023105)the XJTLU Advanced Materials Research Center(AMRC).
文摘Seawater zinc-air batteries are promising energy storage devices due to their high energy density and utilization of seawater electrolytes.However,their efficiency is hindered by the sluggish oxygen reduction reaction(ORR)and chlorideinduced degradation over conventional catalysts.In this study,we proposed a universal synthetic strategy to construct heteroatom axially coordinated Fe–N_(4) single-atom seawater catalyst materials(Cl–Fe–N_(4) and S–Fe–N_(4)).X-ray absorption spectroscopy confirmed their five-coordinated square pyramidal structure.Systematic evaluation of catalytic activities revealed that compared with S–Fe–N_(4),Cl–Fe–N_(4) exhibits smaller electrochemical active surface area and specific surface area,yet demonstrates higher limiting current density(5.8 mA cm^(−2)).The assembled zinc-air batteries using Cl–Fe–N_(4) showed superior power density(187.7 mW cm^(−2) at 245.1 mA cm^(−2)),indicating that Cl axial coordination more effectively enhances the intrinsic ORR activity.Moreover,Cl–Fe–N_(4) demonstrates stronger Cl−poisoning resistance in seawater environments.Chronoamperometry tests and zinc-air battery cycling performance evaluations confirmed its enhanced stability.Density functional theory calculations revealed that the introduction of heteroatoms in the axial direction regulates the electron center of Fe single atom,leading to more active reaction intermediates and increased electron density of Fe single sites,thereby enhancing the reduction in adsorbed intermediates and hence the overall ORR catalytic activity.
基金supported by Guangxi Science and Technology Major Program(GuikeAA23062018)the Academic Newcomer Award Project of Guangxi University(2025GXUXSXR07)。
文摘In this paper,the research progress of Cu-based catalyst and the activity enhancement strategies in the hydrogenation of dimethyl oxalate(DMO)to ethylene glycol(EG)was reviewed.As a green and economical ethylene glycol production path,the core of DMO hydrogenation of EG lies in the rational design and optimization of catalysts.This paper first introduces the background of the DMO hydrogenation system EG significance and the important effect of Cu-based catalyst in the reaction,particularly emphasizing the coordination with the Cu^(+)-Cu^(0) species catalytic effect.Then,many factors affecting the activity of Cu-based catalysts were analyzed in detail,including the equilibrium effect between Cu^(0) and Cu+species,the surface dispersion of Cu species,the interaction between metal and support,and the morphology effect of the catalyst.Regarding strategies for improving catalyst performance,this paper summarized effective measures such as optimizing support structure,adding promoters and optimizing preparation methods,and demonstrated the practical application effects of these strategies through representative catalyst examples.In addition,this paper also discusses the complex relationship between the influencing factors and catalyst performance.It points out the key directions for future research,with in-depth exploration of the correlation between catalyst structure and performance,the development of new catalysts,and the application of machine learning and big data technology in the catalyst research and development.In summary,this paper provides comprehensive theoretical guidance and practical reference for the performance optimization of Cu-based catalysts for DMO hydrogenation to EG.
基金supported by the National Natural Science Foundation of China(No.52064035)the Key Research and Development Program of Gansu Province,China(No.25YFGA024)the Natural Science Foundation of Zhejiang Province,China(No.LGG22E020003).
文摘Lithium-sulfur(Li-S)batteries boast a theoretical energy density as high as 2600 Wh·kg^(−1),positioning them as a highly attractive option for future advanced energy storage systems.Challenges such as slow transformation kinetics and shuttle effects associated with lithium polysulfides(LiPSs)have seriously hindered their practical applications.In this paper,we present a new method for the synthesis of hollow carbon-sphere-supported Co monatomic catalysts(Co-N-C).This new synthesis method achieves pyrolytic coordination using a precursor rich in imide(-RC=N-)polymers.This synthesis method not only improves the adsorbability and catalytic activity of LiPS but also significantly weakens the shuttle effect and generates Co-N-C with superior conductivity,abundant hollow structures,and a high specific surface area,thus efficiently capturing and restricting the movement of LiPS intermediates.The dispersed Co monoatomic catalysts(Co SACs)were anchored to a highly conductive nitrogen-doped carbon framework and exhibited symmetric N-coordination active sites(Co-N_(4))to ensure fast redox kinetics of LiPS and Li_(2)S_(2)/Li_(2)S solid-state products.The lithium-sulfur battery with Co-N-C as the sulfur carrier showed excellent discharging capacity of 1146.6 mAh·g^(−1) at a discharge rate of 0.5 C and maintained excellent performance at a high discharge rate of 2 C.The capacity decay rate in 500 cycles was only 0.086%per cycle,reflecting excellent long-term cycle stability.This study highlights the key role of the synergistic effect between single-atom cobalt catalysts and hollow carbon spheres in enhancing the efficiency of lithium-sulfur(Li-S)batteries.It also provides valuable insights into the construction and fabrication of highly active monatomic catalysts.The catalytic conversion efficiency of lithium polysulfides is significantly enhanced when embedded in hollow carbon architectures,which serves as a critical strategy for optimizing the electrochemical behavior of next-generation Li-S batteries.
基金supported by the Australian Research Council(ARC)Projects(DP220101139,DP220101142,and LP240100542).
文摘High‐entropy amorphous catalysts(HEACs)integrate multielement synergy with structural disorder,making them promising candidates for water splitting.Their distinctive features—including flexible coordination environments,tunable electronic structures,abundant unsaturated active sites,and dynamic structural reassembly—collectively enhance electrochemical activity and durability under operating conditions.This review summarizes recent advances in HEACs for hydrogen evolution,oxygen evolution,and overall water splitting,highlighting their disorder-driven advantages over crystalline counterparts.Catalytic performance benchmarks are presented,and mechanistic insights are discussed,focusing on how multimetallic synergy,amorphization effect,and in‐situ reconstruction cooperatively regulate reaction pathways.These insights provide guidance for the rational design of next‐generation amorphous high‐entropy electrocatalysts with improved efficiency and durability.
基金supports from the National Natural Science Foundation of China(Grant Nos.12305372 and 22376217)the National Key Research&Development Program of China(Grant Nos.2022YFA1603802 and 2022YFB3504100)+1 种基金the projects of the key laboratory of advanced energy materials chemistry,ministry of education(Nankai University)key laboratory of Jiangxi Province for persistent pollutants prevention control and resource reuse(2023SSY02061)are gratefully acknowledged.
文摘Using photoelectrocatalytic CO_(2) reduction reaction(CO_(2)RR)to produce valuable fuels is a fascinating way to alleviate environmental issues and energy crises.Bismuth-based(Bi-based)catalysts have attracted widespread attention for CO_(2)RR due to their high catalytic activity,selectivity,excellent stability,and low cost.However,they still need to be further improved to meet the needs of industrial applications.This review article comprehensively summarizes the recent advances in regulation strategies of Bi-based catalysts and can be divided into six categories:(1)defect engineering,(2)atomic doping engineering,(3)organic framework engineering,(4)inorganic heterojunction engineering,(5)crystal face engineering,and(6)alloying and polarization engineering.Meanwhile,the corresponding catalytic mechanisms of each regulation strategy will also be discussed in detail,aiming to enable researchers to understand the structure-property relationship of the improved Bibased catalysts fundamentally.Finally,the challenges and future opportunities of the Bi-based catalysts in the photoelectrocatalytic CO_(2)RR application field will also be featured from the perspectives of the(1)combination or synergy of multiple regulatory strategies,(2)revealing formation mechanism and realizing controllable synthesis,and(3)in situ multiscale investigation of activation pathways and uncovering the catalytic mechanisms.On the one hand,through the comparative analysis and mechanism explanation of the six major regulatory strategies,a multidimensional knowledge framework of the structure-activity relationship of Bi-based catalysts can be constructed for researchers,which not only deepens the atomic-level understanding of catalytic active sites,charge transport paths,and the adsorption behavior of intermediate products,but also provides theoretical guiding principles for the controllable design of new catalysts;on the other hand,the promising collaborative regulation strategies,controllable synthetic paths,and the in situ multiscale characterization techniques presented in this work provides a paradigm reference for shortening the research and development cycle of high-performance catalysts,conducive to facilitating the transition of photoelectrocatalytic CO_(2)RR technology from the laboratory routes to industrial application.
基金The work was supported by the National Natural Science Foundation of China （grant number 21506224）. Z.Z. is grateful for support from the Institute of Chemical and Engineering Sciences.
文摘In this work, we report a simple and inexpensive approach to synthesize effective multicomponent Cu-Cu2O-CuO catalysts for the Rochow process from industrial waste contact masses （WCMs）. WCMs from the organosilane industry were treated with acid followed by reduction with metallic iron powder. The obtained copper powder was then subjected to controlled oxidation in air at different temperatures, followed by ball milling. The orthogonal array approach was applied to optimize this process, and the stirring speed and pH were found to significantly affect the leaching ratio and copper yield, respectively. When used for the Rochow process, the optimized ternary Cu-Cu2O-CuO catalyst greatly enhanced the dimethyldichlorosilane selectivity and Si conversion compared with Cu-Cu2O-CuO catalysts prepared without ball milling, bare Cu catalysts, and Cu-Cu2O-CuO catalysts with different compositions. This could be attributed to their small particle size and the strong synergistic effect among the multiple components in the catalyst with the optimized composition.
基金supported by the National Key R&D Program of China(2021YFA1500700)the National Nature Science Foundation of China(22102057)Shanghai Sailing Program(21YF1409400).
文摘Electrocatalytic carbon dioxide reduction reaction(CO_(2)RR)holds the promise of both overcoming the greenhouse effect and synthesizing a wealth of chemicals.Electrocatalytic CO_(2) reduction toward carbon-containing products,including C1 products(carbon monoxide,formic acid,etc),C2 products(ethylene,ethanol,etc.)and multi-carbon products(e.g.,n-propanol),provides beneficial fuel and chemicals for industrial production.The complexity of the multi-proton transfer processes and difficulties of C-C coupling in electrochemical CO_(2) reduction toward multi-carbon(C2+)products have attracted increasing concerns on the design of catalysts in comparison with those of C1 products.In this paper,we review the main advances in the syntheses of multi-carbon products through electrocatalytic carbon dioxide reduction in recent years,introduce the basic principles of electrocatalytic CO_(2)RR,and detailly elucidate two widely accepted mechanisms of C-C coupling reactions.Among abundant nanomaterials,copper-based catalysts are outstanding catalysts for the preparation of multi-carbon chemicals in electrochemical CO_(2)RR attributing to effective C-C coupling reactions.Regarding the different selectivity of multi-carbon chemicals but extensively applied copper-based catalysts,we classify and summarize various Cu-based catalysts through separating diverse multi-carbon products,where the modification of spatial and electronic structures is beneficial to increase the coverage of CO or lower the activation energy barrier for forming C-C bond to form the key intermediates and increase the production of multi-carbon products.Challenges and prospects involving the fundamental and development of copper-based catalysts in electrochemical CO_(2) reduction reaction are also proposed.
基金We acknowledge the National Key R&D Program of China(2021YFA1501503)the National Natural Science Foundation of China(22121004,22038009,and 51861125104)+2 种基金the Natural Science Foundation o f Tianjin City(18JCJQJC47500),Haihe Laboratory of Sustainable Chemical Transformations(CYZC202107)the Program of Introducing Talents of Discipline to Universities(no.BP0618007)the Xplorer Prize for financial support.
文摘CONSPECTUS:As one of the essential pathways to carbon neutrality or carbon negativity,the electrochemical reduction of CO_(2) offers tremendous prospects for platform chemicals and fuel production.Copper(Cu)is currently the only metal material that is able to reduce CO_(2) to multicarbon(C2+)products.Despite the fact that copper-based materials have been investigated for decades,we still confront numerous challenges on the path to the fundamental understanding and large-scale deployment of copper-based electrocatalysts for CO_(2) reduction.For fundamental investigations,it remains a variety of open questions about the CO_(2) reduction mechanisms.The convoluted C−C coupling pathways and product bifurcation processes confuse the design of efficient catalysts.The active sites of copper-based catalysts remain ambiguous due to surface reconstruction.As for theoretical calculations,the construction of electrolyte−electrode models and the investigation of solvation effects are premature for obtaining confident conclusions.In addition,simple and easily scalable techniques for catalyst synthesis still need to be continuously developed.For practical applications,the CO_(2) electrolyzer with copper-based materials must be operated with high current densities,high Faradaic efficiencies,high energetic efficiencies,high single-pass conversion rates(high product concentration),and long stability.Nevertheless,due to the intricate nature of electrochemical systems,a high-performance copper-based electrocatalyst alone is not sufficient to meet all of the above commercialization requirements.Therefore,reactor design involving mass transfer enhancement calls for more research input.Based on the above background and the urgency of the net-zero goal,we initiated our research on CO_(2) electrolysis using copper-based materials with an emphasis on active site identification and mass transfer enhancement.This Account describes our contribution to the field of C_(2+)products formation.We first discuss the synthesis of copper-based materials with a controlled atomic arrangement and valence states based on neural network-accelerated computational simulations.Using the synthesized catalyst,the selectivity of the target product is improved and the energy consumption of CO_(2) electrolysis is reduced.Then,we describe the efforts to investigate the reaction mechanisms,such as using first-principles calculations at the atomic level,in situ surface-enhanced vibrational spectroscopies at the micrometer level,and electrochemical kinetics studies at the apparent performance level.We also overview our efforts in the field of reaction system engineering,consisting of a vapor-fed CO_(2) threecompartment flow cell and a large-scale CO_(2) membrane electrode assembly,which can increase the reaction rates and single-pass yield.Furthermore,we put forward the main technical obstacles that currently need to be surmounted and provide insights into the commercial application of CO_(2) electrolysis technology.
