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
Electrocatalytic carbon dioxide reduction is a crucial method for addressing energy issues and achieving carbon neutrality.Doping of Cu catalysts represents an effective approach to regulate electrocatalytic carbon di...Electrocatalytic carbon dioxide reduction is a crucial method for addressing energy issues and achieving carbon neutrality.Doping of Cu catalysts represents an effective approach to regulate electrocatalytic carbon dioxide reduction.This review article summarizes the research progress on improving the performance of Cu-based material electrocatalysts through doping regulation.The background,fundamental research,evaluation parameters,and methods for catalyst design,along with their influencing factors,are introduced.Emphasis is placed on the impact of doping with different elements(such as noble metals,transition metals,main-group metals,non-metals,etc.)on the performance of Cu-based catalysts,including the mechanisms for enhancing activity,selectivity,and stability.In-situ characterization techniques have revealed the structural evolution and catalytic mechanisms during the doping process.Mechanistic studies,leveraging the ever-advancing computational capabilities and high-throughput methods,have given rise to typical computational descriptors like volcano plots,free-energy diagrams,and machine-learning-based approaches.These descriptors have become key tools for screening high-efficiency catalysts in various application scenarios of the electrochemical carbon dioxide reduction reaction(CO_(2)RR).This article comprehensively summarizes the current research achievements and looks ahead to the future,indicating that strengthening the combination of theory and experiment and exploring industrial applications are the future research directions,aiming to provide a comprehensive reference for the development of highly efficient doped Cu-based electrocatalysts.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
Graphene/copper-based composite heat sinks demonstrate extensive application potential in military equipment thermal management,high-power electronic packaging,new energy vehicles,and 5G communication systems,due to t...Graphene/copper-based composite heat sinks demonstrate extensive application potential in military equipment thermal management,high-power electronic packaging,new energy vehicles,and 5G communication systems,due to their outstanding properties,including high thermal conductivity,tunable thermal expansion coefficients,excellent mechanical strength,and low density.However,the industrial-scale application of these composites faces critical challenges during the fabrication of components with complex structures,such as inhomogeneous dispersion of graphene within the copper matrix and poor interfacial bonding between the two phases,which substantially undermine the overall performance of graphene/copper-based composites.To address these issues,the preparation methods for graphene/copper-based composite heat sinks were reviewed.For each method,a rigorous analysis was presented to clarify its inherent advantages and unavoidable restrictions.Furthermore,the latest research progress in addressing three core scientific challenges was synthesized,including uniform dispersion of graphene,interfacial optimization mechanisms,and molecular dynamics simulations for elucidating the structure-property relationships.Finally,the future development directions of graphene/copper-based composite heat sinks in engineering applications were prospected.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
In this paper,the Ni/Al_(2)O_(3) monolithic catalyst with 15%Ni content was prepared using cordierite as a matrix,and the catalyst was modified with 10%NaOH to study the methanation performance of biomass gasification...In this paper,the Ni/Al_(2)O_(3) monolithic catalyst with 15%Ni content was prepared using cordierite as a matrix,and the catalyst was modified with 10%NaOH to study the methanation performance of biomass gasification simulated gas based on alkali-modified Ni/Al_(2)O_(3) monolithic catalyst.BET,TEM,H_(2)-TPR,XRD,CO_(2)-TPD and TG were used to characterize the physicochemical properties of the catalyst before and after modification.The results indicated that the CO conversion rate trends of unmodified and modified Ni/Al_(2)O_(3) monolithic catalysts over 2 h were fundamentally consistent.However,the Ni/Al_(2)O_(3) catalysts modified for 2 h demonstrated significantly enhanced performance compared to those modified for 1 h.Regarding CH4 selectivity,the modified Ni/Al_(2)O_(3) catalyst exhibited markedly better performance than the unmodified Ni/Al_(2)O_(3) catalyst,confirming the enhanced methane performance of the alkali-modified Ni/Al_(2)O_(3) monolithic catalyst.Under optimized conditions(H_(2)/CO volume ratio of 3∶1,space velocity of 10000 mL/(g·h),and temperature of 400℃),the methanation performance of the Ni/Al_(2)O_(3) monolithic catalyst modified for 2 h reached its peak,achieving a CO conversion rate of 97%with 100%CH4 selectivity.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
CuZnAl(CZA)is a classic industrial catalyst widely used for the synthesis of methanol from syngas,but its catalytic performance is not optimal for the hydrogenation of CO_(2) to methanol.Meanwhile,understanding the ca...CuZnAl(CZA)is a classic industrial catalyst widely used for the synthesis of methanol from syngas,but its catalytic performance is not optimal for the hydrogenation of CO_(2) to methanol.Meanwhile,understanding the catalytic mechanism of Cu species in the CZA catalyst remains a great challenge.In this study,we systematically investigated the valence state change of active Cu species in CZA catalyst and their influence on catalytic performance by modifying the catalysts with varying amounts of electron donor K,thus identifying the catalytic function of Cu species with different valence states.H2-TPR,XPS and HR-TEM characterizations reveal that the highly dispersed K species supported on CZA catalysts will inhibit the reduction of CuO,resulting in a small amount of Cu_(2)O active species being produced under reaction conditions thus causing a decrease in catalytic activity.Furthermore,XRD and Cu LMM spectra show that the proportion of Cu^(0) in K-modified CZA catalysts increases with K loading,but a higher proportion of Cu^(0) species on the surface obviously promotes the reverse water gas shift(RWGS)reaction.According to the results of in situ infrared spectroscopy,CZA catalyst follows the reaction pathway mediated by HCOO^(*)in the hydrogenation of CO_(2) to methanol.展开更多
Conventional treatments for non-small cell lung cancer(NSCLC)suffer from low remission rates,high drug resistance,and severe adverse effects.To leverage the therapeutic potential of reactive oxygen species(ROS),nanoca...Conventional treatments for non-small cell lung cancer(NSCLC)suffer from low remission rates,high drug resistance,and severe adverse effects.To leverage the therapeutic potential of reactive oxygen species(ROS),nanocatalytic medicine utilizes nanomaterials to generate ROS specifically within tumor sites,enabling efficient and targeted cancer treatment.In this study,hyaluronic acid(HA)-modified copper-N,N-dimethyl-Nphenylsulfonylbisamine(DMSA)-assembled nanoparticles(Cu-DMSA-HA NPs)are developed with tumor-targeting capability and efficiently catalyze ROS production via coordination chemistry.Targeted delivery is facilitated by HA surface modification through recognition of overexpressed cluster of differentiation 44 receptors on cancer cells,which enhances nanoparticle uptake.Once internalized,intracellular glutathione is depleted by the NPs,followed by a Fenton-like reaction that sustains ROS production.Both in vitro and in vivo studies demonstrate that this catalytic strategy effectively inhibits DNA replication,prevents cell cycle progression,downregulates glutathione peroxidase 4 expression,induces ferroptosis,and ultimately suppresses NSCLC progression.Overall,the readily prepared Cu-DMSA-HA NPs exhibit robust catalytic activity and tumor specificity,highlighting their strong potential for clinical translation in nanocatalytic cancer therapy.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
The oxygen evolution reaction(OER)suffers from sluggish kinetics,necessitating efficient electrocatalysts to reduce overpotentials in water splitting.Currently recognized OER mechanisms primarily include the adsorbate...The oxygen evolution reaction(OER)suffers from sluggish kinetics,necessitating efficient electrocatalysts to reduce overpotentials in water splitting.Currently recognized OER mechanisms primarily include the adsorbate evolution mechanism(AEM),lattice oxygen mechanism(LOM),and oxide path mechanism(OPM).Compared to AEM,limited by scaling relationships,and LOM,constrained by stability issues,the OPM offers a promising alternative by enabling direct O-O bond formation via dual active sites,thus bypassing^(*)OOH intermediates and lattice O involvement and achieving a balance between activity and durability.However,activating the OPM process requires precise control over the spatial and electronic structure of active sites,making the design of OPM-based catalysts challenging.While previous reviews have focused on homo/heteronuclear diatomic perspectives of OPM-based catalysts,it is urgent to systematically summarize design strategies to provide a rational reference for their development.Herein,a review of design strategies for OPM-based OER catalysts across three scales is comprehensively presented,including in-situ engineering,doping-enabled sites reconstruction,and introducing new sites for nanoparticles,direct synthesis or post-treatments for molecular catalysts,and doping or template strategies for atom pairs or arrays.The unique advantage of atom arrays is also highlighted,and their future research directions and possible strategies are discussed.This review provides a systematic summary and forward-looking perspectives for rationally designing high-performance OPM-based OER catalysts.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
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financially supported by the National Natural Science Foundation of China(52271200)Guangdong Basic and Applied Basic Research Foundation(2024A1515010393)USTB MatCom of Beijing Advanced Innovation Center for Materials Genome Engineering。
文摘Electrocatalytic carbon dioxide reduction is a crucial method for addressing energy issues and achieving carbon neutrality.Doping of Cu catalysts represents an effective approach to regulate electrocatalytic carbon dioxide reduction.This review article summarizes the research progress on improving the performance of Cu-based material electrocatalysts through doping regulation.The background,fundamental research,evaluation parameters,and methods for catalyst design,along with their influencing factors,are introduced.Emphasis is placed on the impact of doping with different elements(such as noble metals,transition metals,main-group metals,non-metals,etc.)on the performance of Cu-based catalysts,including the mechanisms for enhancing activity,selectivity,and stability.In-situ characterization techniques have revealed the structural evolution and catalytic mechanisms during the doping process.Mechanistic studies,leveraging the ever-advancing computational capabilities and high-throughput methods,have given rise to typical computational descriptors like volcano plots,free-energy diagrams,and machine-learning-based approaches.These descriptors have become key tools for screening high-efficiency catalysts in various application scenarios of the electrochemical carbon dioxide reduction reaction(CO_(2)RR).This article comprehensively summarizes the current research achievements and looks ahead to the future,indicating that strengthening the combination of theory and experiment and exploring industrial applications are the future research directions,aiming to provide a comprehensive reference for the development of highly efficient doped Cu-based electrocatalysts.
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Research Start-Up Fund Project of Anhui Polytechnic University(S022023017)University Research Project of Anhui Province(2023AH050937)+1 种基金Anhui Polytechnic University Research Foundation for Introducing Talents(2022YQQ003)Anhui Province Key Laboratory of Intelligent Vehicle Chassis by Wire。
文摘Graphene/copper-based composite heat sinks demonstrate extensive application potential in military equipment thermal management,high-power electronic packaging,new energy vehicles,and 5G communication systems,due to their outstanding properties,including high thermal conductivity,tunable thermal expansion coefficients,excellent mechanical strength,and low density.However,the industrial-scale application of these composites faces critical challenges during the fabrication of components with complex structures,such as inhomogeneous dispersion of graphene within the copper matrix and poor interfacial bonding between the two phases,which substantially undermine the overall performance of graphene/copper-based composites.To address these issues,the preparation methods for graphene/copper-based composite heat sinks were reviewed.For each method,a rigorous analysis was presented to clarify its inherent advantages and unavoidable restrictions.Furthermore,the latest research progress in addressing three core scientific challenges was synthesized,including uniform dispersion of graphene,interfacial optimization mechanisms,and molecular dynamics simulations for elucidating the structure-property relationships.Finally,the future development directions of graphene/copper-based composite heat sinks in engineering applications were prospected.
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 the National Natural Science Foundation of China(52506188,52476215)Natural Science Foundation of Liaoning Province(2024-MS-139,2024JH3/10200047)Scientific Research Program of Department of Education of Liaoning Province(310125042,LJ212410143033)。
文摘In this paper,the Ni/Al_(2)O_(3) monolithic catalyst with 15%Ni content was prepared using cordierite as a matrix,and the catalyst was modified with 10%NaOH to study the methanation performance of biomass gasification simulated gas based on alkali-modified Ni/Al_(2)O_(3) monolithic catalyst.BET,TEM,H_(2)-TPR,XRD,CO_(2)-TPD and TG were used to characterize the physicochemical properties of the catalyst before and after modification.The results indicated that the CO conversion rate trends of unmodified and modified Ni/Al_(2)O_(3) monolithic catalysts over 2 h were fundamentally consistent.However,the Ni/Al_(2)O_(3) catalysts modified for 2 h demonstrated significantly enhanced performance compared to those modified for 1 h.Regarding CH4 selectivity,the modified Ni/Al_(2)O_(3) catalyst exhibited markedly better performance than the unmodified Ni/Al_(2)O_(3) catalyst,confirming the enhanced methane performance of the alkali-modified Ni/Al_(2)O_(3) monolithic catalyst.Under optimized conditions(H_(2)/CO volume ratio of 3∶1,space velocity of 10000 mL/(g·h),and temperature of 400℃),the methanation performance of the Ni/Al_(2)O_(3) monolithic catalyst modified for 2 h reached its peak,achieving a CO conversion rate of 97%with 100%CH4 selectivity.
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Supported by the National Key Research and Development Program of China(2022YFB4101800)the National Natural Science Foundation of China(22172032,U22A20431)。
文摘CuZnAl(CZA)is a classic industrial catalyst widely used for the synthesis of methanol from syngas,but its catalytic performance is not optimal for the hydrogenation of CO_(2) to methanol.Meanwhile,understanding the catalytic mechanism of Cu species in the CZA catalyst remains a great challenge.In this study,we systematically investigated the valence state change of active Cu species in CZA catalyst and their influence on catalytic performance by modifying the catalysts with varying amounts of electron donor K,thus identifying the catalytic function of Cu species with different valence states.H2-TPR,XPS and HR-TEM characterizations reveal that the highly dispersed K species supported on CZA catalysts will inhibit the reduction of CuO,resulting in a small amount of Cu_(2)O active species being produced under reaction conditions thus causing a decrease in catalytic activity.Furthermore,XRD and Cu LMM spectra show that the proportion of Cu^(0) in K-modified CZA catalysts increases with K loading,but a higher proportion of Cu^(0) species on the surface obviously promotes the reverse water gas shift(RWGS)reaction.According to the results of in situ infrared spectroscopy,CZA catalyst follows the reaction pathway mediated by HCOO^(*)in the hydrogenation of CO_(2) to methanol.
基金supported by National Natural Science Foundation of China (82272943)Shanghai Municipal Science and Technology Commission (21Y11913400)+1 种基金Fundamental Research Funds for the Central UniversitiesNational Key Research and Development Program of China (2022YFC2407405)
文摘Conventional treatments for non-small cell lung cancer(NSCLC)suffer from low remission rates,high drug resistance,and severe adverse effects.To leverage the therapeutic potential of reactive oxygen species(ROS),nanocatalytic medicine utilizes nanomaterials to generate ROS specifically within tumor sites,enabling efficient and targeted cancer treatment.In this study,hyaluronic acid(HA)-modified copper-N,N-dimethyl-Nphenylsulfonylbisamine(DMSA)-assembled nanoparticles(Cu-DMSA-HA NPs)are developed with tumor-targeting capability and efficiently catalyze ROS production via coordination chemistry.Targeted delivery is facilitated by HA surface modification through recognition of overexpressed cluster of differentiation 44 receptors on cancer cells,which enhances nanoparticle uptake.Once internalized,intracellular glutathione is depleted by the NPs,followed by a Fenton-like reaction that sustains ROS production.Both in vitro and in vivo studies demonstrate that this catalytic strategy effectively inhibits DNA replication,prevents cell cycle progression,downregulates glutathione peroxidase 4 expression,induces ferroptosis,and ultimately suppresses NSCLC progression.Overall,the readily prepared Cu-DMSA-HA NPs exhibit robust catalytic activity and tumor specificity,highlighting their strong potential for clinical translation in nanocatalytic cancer therapy.
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funding from the National Natural Science Foundation of China(22378289)the Key Central Government Guides Local Funds for Science and Technology Development(YDZJSX2022A021)the special fund for Science and Technology Innovation Teams of Shanxi Province(202304051001026)。
文摘The oxygen evolution reaction(OER)suffers from sluggish kinetics,necessitating efficient electrocatalysts to reduce overpotentials in water splitting.Currently recognized OER mechanisms primarily include the adsorbate evolution mechanism(AEM),lattice oxygen mechanism(LOM),and oxide path mechanism(OPM).Compared to AEM,limited by scaling relationships,and LOM,constrained by stability issues,the OPM offers a promising alternative by enabling direct O-O bond formation via dual active sites,thus bypassing^(*)OOH intermediates and lattice O involvement and achieving a balance between activity and durability.However,activating the OPM process requires precise control over the spatial and electronic structure of active sites,making the design of OPM-based catalysts challenging.While previous reviews have focused on homo/heteronuclear diatomic perspectives of OPM-based catalysts,it is urgent to systematically summarize design strategies to provide a rational reference for their development.Herein,a review of design strategies for OPM-based OER catalysts across three scales is comprehensively presented,including in-situ engineering,doping-enabled sites reconstruction,and introducing new sites for nanoparticles,direct synthesis or post-treatments for molecular catalysts,and doping or template strategies for atom pairs or arrays.The unique advantage of atom arrays is also highlighted,and their future research directions and possible strategies are discussed.This review provides a systematic summary and forward-looking perspectives for rationally designing high-performance OPM-based OER catalysts.
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.
