Electrochemical reduction of CO_(2)(CO_(2)RR)to form high-energy-density and high-value-added multicarbon products has attracted much attention.Selective reduction of CO_(2)to C^(2+)products face the problems of low r...Electrochemical reduction of CO_(2)(CO_(2)RR)to form high-energy-density and high-value-added multicarbon products has attracted much attention.Selective reduction of CO_(2)to C^(2+)products face the problems of low reaction rate,complex mechanism and low selectivity.Currently,except for a few examples,copper-based catalysts are the only option capable of achieving efficient generation of C^(2+)products.However,the continuous dynamic reconstruction of the catalyst causes great difficulty in understanding the structure-performance relationship of CO_(2)RR.In this review,we first discuss the mechanism of C^(2+)product generation.The structural factors promoting C^(2+)product generation are outlined,and the dynamic evolution of these structural factors is discussed.Furthermore,the effects of electrolyte and electrolysis conditions are reviewed in a vision of dynamic surface.Finally,further exploration of the reconstruction mechanism of Cu-based catalysts and the application of emerging robotic AI chemists are discussed.展开更多
Electrocatalytic carbon dioxide reduction(ECO_(2)RR)serves as a promising approach for converting CO_(2)into energy-dense fuels and high-value chemicals,garnering substantial interest across academic and industrial se...Electrocatalytic carbon dioxide reduction(ECO_(2)RR)serves as a promising approach for converting CO_(2)into energy-dense fuels and high-value chemicals,garnering substantial interest across academic and industrial sectors.Copper(Cu)-based electrocatalysts are widely acknowledged as highly effective for ECO_(2)RR,primarily due to their optimal adsorption energy for*CO.Nonetheless,significant challenges remain to be addressed in transitioning Cu-based catalysts from research settings to industrial applications,including the low stability and unavoidable side reactions.This article aims to i)systematically examine the deactivation mechanisms of Cu-based catalysts,including changes in valence states,surface poisoning,and restructuring(agglomeration,dissolution,Ostwald ripening);ii)provide a timely overview of cutting-edge strategies to enhance the stability of Cu-based catalysts,such as ligand effects,heteroatom doping,support optimization,size effect,and restructuring;iii)highlight critical areas and prospective development directions that warrant further exploration to expedite the industrial adoption of Cu-based catalysts in ECO_(2)RR.展开更多
Dual atomic catalysts(DAC),particularly copper(Cu_(2))-based nitrogen(N)doped graphene,show great potential to effectively convert CO_(2)and nitrate(NO_(3)-)into important industrial chemicals such as ethylene,glycol,...Dual atomic catalysts(DAC),particularly copper(Cu_(2))-based nitrogen(N)doped graphene,show great potential to effectively convert CO_(2)and nitrate(NO_(3)-)into important industrial chemicals such as ethylene,glycol,acetamide,and urea through an efficient catalytical process that involves C–C and C–N coupling.However,the origin of the coupling activity remained unclear,which substantially hinders the rational design of Cu-based catalysts for the N-integrated CO_(2)reduction reaction(CO_(2)RR).To address this challenge,this work performed advanced density functional theory calculations incorporating explicit solvation based on a Cu_(2)-based N-doped carbon(Cu_(2)N_(6)C_(10))catalyst for CO_(2)RR.These calculations are aimed to gain insight into the reaction mechanisms for the synthesis of ethylene,acetamide,and urea via coupling in the interfacial reaction micro-environment.Due to the sluggishness of CO_(2),the formation of a solvation electric layer by anions(F^(-),Cl^(-),Br^(-),and I^(-))and cations(Na+,Mg^(2+),K+,and Ca^(2+))leads to electron transfer towards the Cu surface.This process significantly accelerates the reduction of CO_(2).These results reveal that*CO intermediates play a pivotal role in N-integrated CO_(2)RR.Remarkably,the Cu_(2)-based N-doped carbon catalyst examined in this study has demonstrated the most potential for C–N coupling to date.Our findings reveal that through the process of a condensation reaction between*CO and NH_(2)OH for urea synthesis,*NO_(3)-is reduced to*NH_(3),and*CO_(2)to*CCO at dual Cu atom sites.This dual-site reduction facilitates the synthesis of acetamide through a nucleophilic reaction between NH_(3)and the ketene intermediate.Furthermore,we found that the I-and Mg^(2+)ions,influenced by pH,were highly effective for acetamide and ammonia synthesis,except when F-and Ca^(2+)were present.Furthermore,the mechanisms of C–N bond formation were investigated via ab-initio molecular dynamics simulations,and we found that adjusting the micro-environment can change the dominant side reaction,shifting from hydrogen production in acidic conditions to water reduction in alkaline ones.This study introduces a novel approach using ion-H_(2)O cages to significantly enhance the efficiency of C–N coupling reactions.展开更多
Global investment in ethylene(C_(2)H_(4))production via nonpetroleum pathways is rising,highlighting its growing importance in the energy and environmental sectors.The electroreduction of carbon dioxide(CO_(2))to C_(2...Global investment in ethylene(C_(2)H_(4))production via nonpetroleum pathways is rising,highlighting its growing importance in the energy and environmental sectors.The electroreduction of carbon dioxide(CO_(2))to C_(2)H_(4) inflow cells is emerging as a promising technology with broad practical applications.Direct delivery of gaseous CO_(2) to the cathode catalyst layer overcomes mass transfer limitations,enhancing reaction rates and enabling high current density.This review summarizes recent research progress in the electrocatalytic CO_(2) reduction reaction(eCO_(2)RR)for selective C_(2)H_(4) production inflow cells.It outlines the principles of eCO_(2)RR to C_(2)H_(4) and discusses the influence of copper-based catalyst morphology,crystal facet,oxidation state,surface modification strategy,and synergistic effects on catalytic performance.In addition,it highlights the compositional structure of theflow cell,and the selection and optimization of operating conditions,including gas diffusion electrodes,electrolytes,ion exchange membranes,and alternative anode reaction types beyond the oxygen evolution reaction.Finally,advances in machine learning are presented for accelerating catalyst screening and predicting dynamic changes in catalysts during reduction.This comprehensive review serves as a valuable reference for the development of efficient catalysts and the construction of electrolytic devices for the electrocatalytic reduction of CO_(2) to C_(2)H_(4).展开更多
Carbon dioxide conversion into valuable products using photocatalysis and electrocatalysis is an effective approach to mitigate global environmental issues and the energy shortages. Among the materials utilized for ca...Carbon dioxide conversion into valuable products using photocatalysis and electrocatalysis is an effective approach to mitigate global environmental issues and the energy shortages. Among the materials utilized for catalytic reduction of CO_(2), Cu-based materials are highly advantageous owing to their widespread availability, cost-effectiveness, and environmental sustainability. Furthermore, Cu-based materials demonstrate interesting abilities in the adsorption and activation of carbon dioxide, allowing the formation of C_(2+) compounds through C–C coupling process. Herein, the basic principles of photocatalytic CO_(2) reduction reactions(PCO_(2)RR) and electrocatalytic CO_(2) reduction reaction(ECO_(2)RR) and the pathways for the generation C_(2+) products are introduced. This review categorizes Cu-based materials into different groups including Cu metal, Cu oxides, Cu alloys, and Cu SACs, Cu heterojunctions based on their catalytic applications. The relationship between the Cu surfaces and their efficiency in both PCO_(2)RR and ECO_(2)RR is emphasized. Through a review of recent studies on PCO_(2)RR and ECO_(2)RR using Cu-based catalysts, the focus is on understanding the underlying reasons for the enhanced selectivity toward C_(2+) products. Finally, the opportunities and challenges associated with Cu-based materials in the CO_(2) catalytic reduction applications are presented, along with research directions that can guide for the design of highly active and selective Cu-based materials for CO_(2) reduction processes in the future.展开更多
Electrocatalytic CO_(2) reduction reaction(CO_(2)RR)technology,which enables carbon capture storage and resource utilization by reducing CO_(2) to valuable chemicals or fuels,has become a global research hotspot in re...Electrocatalytic CO_(2) reduction reaction(CO_(2)RR)technology,which enables carbon capture storage and resource utilization by reducing CO_(2) to valuable chemicals or fuels,has become a global research hotspot in recent decades.Among the many products of CO_(2)RR(carbon monoxide,acids,aldehydes and alcohols,olefins,etc.),alcohols(methanol,ethanol,propanol,etc.)have a higher market value and energy density,but it is also more difficult to produce.Copper is known to be effective in catalyzing CO_(2) to high valueadded alcohols,but with poor selectivity.The progress of Cu-based catalysts for the selective generation of alcohols,including copper oxides,bimetals,single atoms and composites is reviewed.Meanwhile,to improve Cu-based catalyst activity and modulate product selectivity,the modulation strategies are straighten out,including morphological regulation,crystalline surface,oxidation state,as well as elemental doping and defect engineering.Based on the research progress of electrocatalytic CO_(2) reduction for alcohol production on Cu-based materials,the reaction pathways and the key intermediates of the electrocatalytic CO_(2)RR to methanol,ethanol and propanol are summarized.Finally,the problems of traditional electrocatalytic CO_(2)RR are introduced,and the future applications of machine learning and theoretical calculations are prospected.An in-depth discussion and a comprehensive review of the reaction mechanism,catalyst types and regulation strategies were carried out with a view to promoting the development of electrocatalytic CO_(2)RR to alcohols.展开更多
Electrocatalytic reduction of CO_(2)is crucial for environmental sustainability and renewable energy storage,with Cu-based catalysts excelling in producing high-value C_(2+)products.However,a comprehensive analysis of...Electrocatalytic reduction of CO_(2)is crucial for environmental sustainability and renewable energy storage,with Cu-based catalysts excelling in producing high-value C_(2+)products.However,a comprehensive analysis of how specific electrolyte influences Cu-based catalysts is lacking.This review addresses this gap by focusing on how electrolytes impact surface reconstruction and the CO_(2) reduction process on Cu-based electrocatalysts,identifying specific electrolyte compositions that enhance the density and stability of active sites,and providing insights into how different electrolyte environments modulate the selectivity and efficiency of C_(2+)product formation.The review begins by exploring how electrolytes induce favorable surface reconstruction in Cu-based catalysts,affecting surface roughness through dissolution-redeposition of Cu species and interactions with halogens and molecular additives.It also covers changes in crystalline facets of Cu and Cu_(2)O,and oxidation states,highlighting transitions from Cu^(0) to Cu^(δ+)and the stabilization of Cu^(+).The role of electrolytes in the C–C coupling process is examined,emphasizing their effects in modulating mass and charge transfer,CO_(2) adsorption,intermediate evolution,and product desorption.Subsequently,the mechanisms by non-aqueous electrolytes,including organic solvents,ionic liquids,and mixed electrolytes,affecting CO_(2) reduction are analyzed,highlighting the unique advantages and challenges of each type.The review concludes by addressing current challenges,proposing solutions,and research directions,such as optimizing electrolyte composition by integrating diverse cations and anions and employing advanced in-situ characterization techniques.These insights can significantly enhance CO_(2)reduction performance on Cu-based electrocatalysts,advancing efficient and sustainable green energy technologies.展开更多
Bulk Cu50Zr40Ti10 amorphous alloy composites reinforced with carbon nanotube （CNT） were successfully fabricated by hot pressing technique. Their density, thermal conductivity, and mechanical properties were systemic...Bulk Cu50Zr40Ti10 amorphous alloy composites reinforced with carbon nanotube （CNT） were successfully fabricated by hot pressing technique. Their density, thermal conductivity, and mechanical properties were systemically investigated. The density and the compression strength of the compacts both decrease with increasing CNT content. The thermal conductivity of the compacts decreases when the CNT content is less than 0.10% or exceeds 0.60% （mass fraction）, while increases when the CNT content is in the range of 0.1%-0.6%. The strain limit and the modulus of the compacts are obviously improved when the CNT content is less than 1.0% and then decrease significantly when the CNT content exceeds 1.00%. The optimum CNT addition is less than 0.20% at the comprehensive properties point of view.展开更多
The glassy rods were successfully fabricated in the Cu-Zr-Ti-In alloy system by casting into a copper mold. The value of ATx reaches a maximum of 66 K for the BMG CusoZraTTi8In5 alloy. The reasons for enhancing glass ...The glassy rods were successfully fabricated in the Cu-Zr-Ti-In alloy system by casting into a copper mold. The value of ATx reaches a maximum of 66 K for the BMG CusoZraTTi8In5 alloy. The reasons for enhancing glass forming ability of Cu-based BMGs with the addition of indium were discussed from atomic size and thermodynamics. Alternatively, the BMG Cu52Zra7Ti8In3 exhibits the highest compressive strength （1981 MPa） and the best plasticity among glassy Cu55-xZra7TisInx （x_〈5）. The total plastic deformation of Cu52Zr37TisIn3 before fracture approaches 1.2%.展开更多
Cu50Zr40Ti10 bulk amorphous alloys were fabricated by hot pressing gas-atomized Cu50Zr40Ti10 amorphous powder under different consolidation conditions without vacuum and inert gas protection. The consolidation conditi...Cu50Zr40Ti10 bulk amorphous alloys were fabricated by hot pressing gas-atomized Cu50Zr40Ti10 amorphous powder under different consolidation conditions without vacuum and inert gas protection. The consolidation conditions of the Cu50Zr40Ti10 amorphous powder were investigated based on an L9（34） orthogonal design. The compression strength and strain limit of the Cu50Zr40Ti10 bulk amorphous alloys can reach up to 1090.4 MPa and 11.9 %, respectively. The consolidation pressure significantly influences the strain limit and compression strength of the compact. But the mechanical properties are not significantly influenced by the consolidation temperature. In addition, the preforming pressure significantly influences not the compression strength but the strain limit. The optimum consolidation condition for the Cu50Zr40Ti10 amorphous powder is first precompacted under the pressure of 150 MPa, and then consolidated under the pressure of 450 MPa and the temperature of 380 °C.展开更多
Room-temperature mechanical properties of Cu50Zr40Ti10-xNix（0≤x≤4,mole fraction,%） bulk metallic glasses （BMG） with aspect ratios in the range of 1：1-2.5：1 and loading rates in the range of1×10^-5-1×...Room-temperature mechanical properties of Cu50Zr40Ti10-xNix（0≤x≤4,mole fraction,%） bulk metallic glasses （BMG） with aspect ratios in the range of 1：1-2.5：1 and loading rates in the range of1×10^-5-1×10^-2s^-1were systematically investigated by room-temperatureuniaxialcompression test.In the condition of an aspect ratio of 1：1, the superplasticity can be clearly observed for Cu50Zr40Ti10BMG when the loading rate is1×10^-4s^-1, while for Cu50Zr40Ti10-xNix（x=1-3, mole fraction, %） BMGs when the loading rate is1×10^-2s^-1. The plastic strain （εp）, yielding strength （σy） and fracture strength （σf） of the studied Cu-based BMGs significantly depend on the aspect ratio and the loading rate. In addition, theσyof the studied Cu-based BMGs with an aspect ratio of 1：1 is close to the σfof those with the other aspect ratios when the loading rate is1×10^-2s^-1. The mechanism for the mechanical response to the loading rate and the aspect ratiowas also discussed.展开更多
To improve the sliding wear resistance of AZ91D magnesium alloy, Cu-based amorphous composite coatings made of CuaTTi34Zr11Nis and Cu47Ti34Zr11Ni8＋20 wt pct SiC powders were fabricated on AZ91D magnesium alloy by las...To improve the sliding wear resistance of AZ91D magnesium alloy, Cu-based amorphous composite coatings made of CuaTTi34Zr11Nis and Cu47Ti34Zr11Ni8＋20 wt pct SiC powders were fabricated on AZ91D magnesium alloy by laser cladding, respectively. SEM （scanning electron microscopy）, EDS （energy dispersive X-ray spectroscopy）, XRD （X-ray diffraction） and TEM （transmission electron microscopy） techniques were employed to study the phases of the coatings. The results show that the coatings mainly consist of amorphous phase and different intermetallic compounds. The reason of formation of amorphous phase and the function of SiC particles were explained in details.展开更多
CuSn powders and Till2 powders were milled using high energy mechanical milling to prepare Cu-based alloy powders for brazing diamond. And Ce was added to the milled Cu-based alloy powders to improve the wettability. ...CuSn powders and Till2 powders were milled using high energy mechanical milling to prepare Cu-based alloy powders for brazing diamond. And Ce was added to the milled Cu-based alloy powders to improve the wettability. It is found that the wetting angle reaches the minimum value 13.2° and the maximum spreading area 178 mm2 is achieved when the amount of Ce is 0.75 wt%. And Ce remarkably reduces the surface tension of liquid alloy, which improves the climbing height along the diamond and forms a massive support profile. And the results show that Ce can effectively improve the transverse rupture strength （TRS） due to high wettability. The wear characteristics of the diamonds brazed with Cu-based alloy containing 0.75 wt% Ce mainly consist of integrity, micro-fracture, fracture and rubdown, diamonds pull-out can not easily happen.展开更多
The effects of various structure factors on the properties(superelasticity mainly) of Cu-based shape memory alloys(SMAs) were systematically evaluated in this review article through literatures combining with our work...The effects of various structure factors on the properties(superelasticity mainly) of Cu-based shape memory alloys(SMAs) were systematically evaluated in this review article through literatures combining with our work. It is concluded that besides the decisive role of grain orientation, the grain boundary(GB) characteristics also play important roles in the superelasticity, which include GB area, GB type, GB morphology and GB direction in descending order of the effect significance. According to the above results, the prior principles of structure design are proposed for high-performance Cu-based SMAs from most to least important:(1) obtaining grain orientation with high phase transformation strain;(2) increasing grain size or reducing GB area;(3) obtaining straight low-energy GBs, especially low-angle GBs;(4) trying to make GB direction parallel to external stress. Consistent with the main or all principles, the bamboo-like-grained and columnar-grained(CG) Cu-based SMAs show excellent comprehensive properties.展开更多
Electrochemical reduction of CO_(2)(CO_(2)RR)to high value-added chemicals is an effective way to remove excess CO_(2) from the atmosphere.Due to the unique propensity of Cu for valuable hydrocarbons,Cu-based electroc...Electrochemical reduction of CO_(2)(CO_(2)RR)to high value-added chemicals is an effective way to remove excess CO_(2) from the atmosphere.Due to the unique propensity of Cu for valuable hydrocarbons,Cu-based electrocatalysts are the most potential catalysts that allow the conversion of CO_(2) into a variety of C_(2) products such as ethylene and ethanol.Rational design of Cu-based catalysts can improve their directional selectivity to C_(2) products.Hence,in this review,we summarize the recent progress in the mechanistic studies of Cu-based catalysts on reducing CO_(2) to C_(2) products.We focus on three key strategies for efficiently enhancing electrocatalytic performance of Cu-based catalysts,including tuning electronic structure,surface structure,and coordination environment.The correlation between the structural characteristics of Cu-based catalysts and their activity and selectivity to C_(2) products is discussed.Finally,we discuss the challenges in the field of CO_(2) electroreduction to C_(2) products and provide the perspectives to design efficient Cu-based catalysts in the future.展开更多
COconversion via photocatalysis is a potential solution to address global warming and energy shortage.Photocatalysis can directly utilize the inexhaustible sunlight as an energy source to catalyze the reduction of COt...COconversion via photocatalysis is a potential solution to address global warming and energy shortage.Photocatalysis can directly utilize the inexhaustible sunlight as an energy source to catalyze the reduction of COto useful solar fuels such as CO, CH, CHOH, and CHOH. Among studied formulations, Cubased photocatalysts are the most attractive for COconversion because the Cu-based photocatalysts are low-cost and abundance comparing noble metal-based catalysts. In this literature review, a comprehensive summary of recent progress on Cu-based photocatalysts for COconversion, which includes metallic copper, copper alloy nanoparticles（NPs）, copper oxides, and copper sulfides photocatalysts, can be found. This review also included a detailed discussion on the correlations of morphology, structure, and performance for each type of Cu-based catalysts. The reaction mechanisms and possible pathways for productions of various solar fuels were analyzed, which provide insight into the nature of potential active sites for the catalysts. Finally, the current challenges and perspective future research directions were outlined, holding promise to advance Cu-based photocatalysts for COconversion with much-enhanced energy conversion efficiency and production rates.展开更多
In this study, S-doped NbSea （NbSo.aSel.8） powders were fabricated, and the corresponding Cu-based composites （Cu/NbSo.eSe1.8） were obtained by powder metallurgy technique. The phase compositions, physical, and tr...In this study, S-doped NbSea （NbSo.aSel.8） powders were fabricated, and the corresponding Cu-based composites （Cu/NbSo.eSe1.8） were obtained by powder metallurgy technique. The phase compositions, physical, and tribological properties of Cu-based composites were investigated systematically. The results show that Cu matrix reacts with NbSo.2Sel.8 to produce Cu2Se and Cu0.38NbSo.2Se1.8 during sintering process, which influences the physical and tribological properties of Cu-based composites significantly. Specially, with NbS0.2Se1.8 content increasing, the density of Cu/ NbSo.2Se1.8 composites decreases, and the hardness increases firstly and then decreases, while the electric resistivity in- creases slightly. In addition, the incorporation of NbSo.2Se1.8 enhances the tribological properties of Cu greatly, which is attributed to the lubricating effect of Cuo,38NbSo.2Se1.8 and the reinforcement effect of Cu2Se. In particular, when the content of NbSo.2Sel.8 is 6 wt%, the Cu-based composite has the best tribological properties.展开更多
Various strategies,including controls of morphology,oxidation state,defect,and doping,have been developed to improve the performance of Cu-based catalysts for CO_(2) reduction reaction(CO_(2)RR),generating a large amo...Various strategies,including controls of morphology,oxidation state,defect,and doping,have been developed to improve the performance of Cu-based catalysts for CO_(2) reduction reaction(CO_(2)RR),generating a large amount of data.However,a unified understanding of underlying mechanism for further optimization is still lacking.In this work,combining first-principles calculations and machine learning(ML)techniques,we elucidate critical factors influencing the catalytic properties,taking Cu-based single atom alloys(SAAs)as examples.Our method relies on high-throughput calculations of 2669 CO adsorption configurations on 43 types of Cu-based SAAs with various surfaces.Extensive ML analyses reveal that low generalized coordination numbers and valence electron number are key features to determine catalytic performance.Applying our ML model with cross-group learning scheme,we demonstrate the model generalizes well between Cu-based SAAs with different alloying elements.Further,electronic structure calculations suggest surface negative center could enhance CO adsorption by back donating electrons to antibonding orbitals of CO.Finally,several SAAs,including PCu,AgCu,GaCu,ZnCu,SnCu,GeCu,InCu,and SiCu,are identified as promising CO_(2)RR catalysts.Our work provides a paradigm for the rational design and fast screening of SAAs for various electrocatalytic reactions.展开更多
The curved martensite structures have been observed in CuZnAI-based shape memory alloys by both transmission electron microscope and optical microscope. It was found that the curved martensite structures observed in a...The curved martensite structures have been observed in CuZnAI-based shape memory alloys by both transmission electron microscope and optical microscope. It was found that the curved martensite structures observed in as-solution treated, as-aged and as-trained alloys usually occurred around dislocation tangles or precipitate, at the plate boundary or grain boundary, and when the growing plates collided with each other or alternate mutually.展开更多
Cu and Nb powders were used as starting materials to produce Cu-Nb and Cu-NbC-WC composites by mechanical alloying. X-ray diffraction, scanning electron microscopy, transmission electron microscopy observations and mi...Cu and Nb powders were used as starting materials to produce Cu-Nb and Cu-NbC-WC composites by mechanical alloying. X-ray diffraction, scanning electron microscopy, transmission electron microscopy observations and microhardness measurements have been used to study the effects of milling tools on the phase, microstructure and property of the composites. The results revealed that a single-phase nanocrystalline solid solution was obtained using stainless steel vials and balls （Alloy 1）. Nevertheless, Cu-7 wt% Nb powders milled by tungsten carbon vials and balls exhibited an amorphous phase （Alloy 2）. The as-milled powders were then vacuum hot-pressing sintered. The microstructure of sintered Alloy 1 consisted of Nb nanoparticles and Cu nanograins. Instead, Alloy 2 showed a microstructure with NbC nanoparticles and WC submicron-sized particles dispersed throughout the Cu matrix. Furthermore, Alloy 2 （～ 322 HV） had a higher microhardness than Alloy 1 （～ 302 HV）.展开更多
文摘Electrochemical reduction of CO_(2)(CO_(2)RR)to form high-energy-density and high-value-added multicarbon products has attracted much attention.Selective reduction of CO_(2)to C^(2+)products face the problems of low reaction rate,complex mechanism and low selectivity.Currently,except for a few examples,copper-based catalysts are the only option capable of achieving efficient generation of C^(2+)products.However,the continuous dynamic reconstruction of the catalyst causes great difficulty in understanding the structure-performance relationship of CO_(2)RR.In this review,we first discuss the mechanism of C^(2+)product generation.The structural factors promoting C^(2+)product generation are outlined,and the dynamic evolution of these structural factors is discussed.Furthermore,the effects of electrolyte and electrolysis conditions are reviewed in a vision of dynamic surface.Finally,further exploration of the reconstruction mechanism of Cu-based catalysts and the application of emerging robotic AI chemists are discussed.
基金support from the Technology Project of the State Grid Zhejiang Electric Power Company,Ltd.(No.B311DS230005).
文摘Electrocatalytic carbon dioxide reduction(ECO_(2)RR)serves as a promising approach for converting CO_(2)into energy-dense fuels and high-value chemicals,garnering substantial interest across academic and industrial sectors.Copper(Cu)-based electrocatalysts are widely acknowledged as highly effective for ECO_(2)RR,primarily due to their optimal adsorption energy for*CO.Nonetheless,significant challenges remain to be addressed in transitioning Cu-based catalysts from research settings to industrial applications,including the low stability and unavoidable side reactions.This article aims to i)systematically examine the deactivation mechanisms of Cu-based catalysts,including changes in valence states,surface poisoning,and restructuring(agglomeration,dissolution,Ostwald ripening);ii)provide a timely overview of cutting-edge strategies to enhance the stability of Cu-based catalysts,such as ligand effects,heteroatom doping,support optimization,size effect,and restructuring;iii)highlight critical areas and prospective development directions that warrant further exploration to expedite the industrial adoption of Cu-based catalysts in ECO_(2)RR.
基金National Natural Science Foundation of China(U22B20149,22308376)Outstanding Young Scholars Foundation of China University of Petroleum(Beijing)(2462023BJRC015)Foundation of United Institute for Carbon Neutrality(CNIF20230209)。
文摘Dual atomic catalysts(DAC),particularly copper(Cu_(2))-based nitrogen(N)doped graphene,show great potential to effectively convert CO_(2)and nitrate(NO_(3)-)into important industrial chemicals such as ethylene,glycol,acetamide,and urea through an efficient catalytical process that involves C–C and C–N coupling.However,the origin of the coupling activity remained unclear,which substantially hinders the rational design of Cu-based catalysts for the N-integrated CO_(2)reduction reaction(CO_(2)RR).To address this challenge,this work performed advanced density functional theory calculations incorporating explicit solvation based on a Cu_(2)-based N-doped carbon(Cu_(2)N_(6)C_(10))catalyst for CO_(2)RR.These calculations are aimed to gain insight into the reaction mechanisms for the synthesis of ethylene,acetamide,and urea via coupling in the interfacial reaction micro-environment.Due to the sluggishness of CO_(2),the formation of a solvation electric layer by anions(F^(-),Cl^(-),Br^(-),and I^(-))and cations(Na+,Mg^(2+),K+,and Ca^(2+))leads to electron transfer towards the Cu surface.This process significantly accelerates the reduction of CO_(2).These results reveal that*CO intermediates play a pivotal role in N-integrated CO_(2)RR.Remarkably,the Cu_(2)-based N-doped carbon catalyst examined in this study has demonstrated the most potential for C–N coupling to date.Our findings reveal that through the process of a condensation reaction between*CO and NH_(2)OH for urea synthesis,*NO_(3)-is reduced to*NH_(3),and*CO_(2)to*CCO at dual Cu atom sites.This dual-site reduction facilitates the synthesis of acetamide through a nucleophilic reaction between NH_(3)and the ketene intermediate.Furthermore,we found that the I-and Mg^(2+)ions,influenced by pH,were highly effective for acetamide and ammonia synthesis,except when F-and Ca^(2+)were present.Furthermore,the mechanisms of C–N bond formation were investigated via ab-initio molecular dynamics simulations,and we found that adjusting the micro-environment can change the dominant side reaction,shifting from hydrogen production in acidic conditions to water reduction in alkaline ones.This study introduces a novel approach using ion-H_(2)O cages to significantly enhance the efficiency of C–N coupling reactions.
基金supported by the National Natural Science Foundation of China(22272081 and 51802160)the Startup Foundation for Introducing Talent of NUIST(S8113082001).
文摘Global investment in ethylene(C_(2)H_(4))production via nonpetroleum pathways is rising,highlighting its growing importance in the energy and environmental sectors.The electroreduction of carbon dioxide(CO_(2))to C_(2)H_(4) inflow cells is emerging as a promising technology with broad practical applications.Direct delivery of gaseous CO_(2) to the cathode catalyst layer overcomes mass transfer limitations,enhancing reaction rates and enabling high current density.This review summarizes recent research progress in the electrocatalytic CO_(2) reduction reaction(eCO_(2)RR)for selective C_(2)H_(4) production inflow cells.It outlines the principles of eCO_(2)RR to C_(2)H_(4) and discusses the influence of copper-based catalyst morphology,crystal facet,oxidation state,surface modification strategy,and synergistic effects on catalytic performance.In addition,it highlights the compositional structure of theflow cell,and the selection and optimization of operating conditions,including gas diffusion electrodes,electrolytes,ion exchange membranes,and alternative anode reaction types beyond the oxygen evolution reaction.Finally,advances in machine learning are presented for accelerating catalyst screening and predicting dynamic changes in catalysts during reduction.This comprehensive review serves as a valuable reference for the development of efficient catalysts and the construction of electrolytic devices for the electrocatalytic reduction of CO_(2) to C_(2)H_(4).
基金supported by the National Natural Science Foundation of China (22178149)Jiangsu Distinguished Professor Program+4 种基金Natural Science Foundation of Jiangsu Province for Outstanding Youth Scientists (BK20211599)Key R and D Project of Zhenjiang City (CQ2022001)Scientific Research Startup Foundation of Jiangsu University (Nos. 202096 and 22JDG020)Open Project Program of the State Key Laboratory of Photocatalysis on Energy and Environment of Fuzhou University (SKLPEE-KF202310)the Opening Project of Structural Optimization and Application of Functional Molecules Key Laboratory of Sichuan Province (2023GNFZ-01)。
文摘Carbon dioxide conversion into valuable products using photocatalysis and electrocatalysis is an effective approach to mitigate global environmental issues and the energy shortages. Among the materials utilized for catalytic reduction of CO_(2), Cu-based materials are highly advantageous owing to their widespread availability, cost-effectiveness, and environmental sustainability. Furthermore, Cu-based materials demonstrate interesting abilities in the adsorption and activation of carbon dioxide, allowing the formation of C_(2+) compounds through C–C coupling process. Herein, the basic principles of photocatalytic CO_(2) reduction reactions(PCO_(2)RR) and electrocatalytic CO_(2) reduction reaction(ECO_(2)RR) and the pathways for the generation C_(2+) products are introduced. This review categorizes Cu-based materials into different groups including Cu metal, Cu oxides, Cu alloys, and Cu SACs, Cu heterojunctions based on their catalytic applications. The relationship between the Cu surfaces and their efficiency in both PCO_(2)RR and ECO_(2)RR is emphasized. Through a review of recent studies on PCO_(2)RR and ECO_(2)RR using Cu-based catalysts, the focus is on understanding the underlying reasons for the enhanced selectivity toward C_(2+) products. Finally, the opportunities and challenges associated with Cu-based materials in the CO_(2) catalytic reduction applications are presented, along with research directions that can guide for the design of highly active and selective Cu-based materials for CO_(2) reduction processes in the future.
基金supported by the Fundamental Research Funds for the Central Universities (FRF-EYIT-23-07)。
文摘Electrocatalytic CO_(2) reduction reaction(CO_(2)RR)technology,which enables carbon capture storage and resource utilization by reducing CO_(2) to valuable chemicals or fuels,has become a global research hotspot in recent decades.Among the many products of CO_(2)RR(carbon monoxide,acids,aldehydes and alcohols,olefins,etc.),alcohols(methanol,ethanol,propanol,etc.)have a higher market value and energy density,but it is also more difficult to produce.Copper is known to be effective in catalyzing CO_(2) to high valueadded alcohols,but with poor selectivity.The progress of Cu-based catalysts for the selective generation of alcohols,including copper oxides,bimetals,single atoms and composites is reviewed.Meanwhile,to improve Cu-based catalyst activity and modulate product selectivity,the modulation strategies are straighten out,including morphological regulation,crystalline surface,oxidation state,as well as elemental doping and defect engineering.Based on the research progress of electrocatalytic CO_(2) reduction for alcohol production on Cu-based materials,the reaction pathways and the key intermediates of the electrocatalytic CO_(2)RR to methanol,ethanol and propanol are summarized.Finally,the problems of traditional electrocatalytic CO_(2)RR are introduced,and the future applications of machine learning and theoretical calculations are prospected.An in-depth discussion and a comprehensive review of the reaction mechanism,catalyst types and regulation strategies were carried out with a view to promoting the development of electrocatalytic CO_(2)RR to alcohols.
基金supported by the Hubei Provincial Natural Science Foundation of China (2023AFB0049)the Scientific Research Fund Project of Wuhan Institute of Technology (No.K2024006)the Graduate Education Innovation Fund of Wuhan Institute of Technology (No. CX2023091)。
文摘Electrocatalytic reduction of CO_(2)is crucial for environmental sustainability and renewable energy storage,with Cu-based catalysts excelling in producing high-value C_(2+)products.However,a comprehensive analysis of how specific electrolyte influences Cu-based catalysts is lacking.This review addresses this gap by focusing on how electrolytes impact surface reconstruction and the CO_(2) reduction process on Cu-based electrocatalysts,identifying specific electrolyte compositions that enhance the density and stability of active sites,and providing insights into how different electrolyte environments modulate the selectivity and efficiency of C_(2+)product formation.The review begins by exploring how electrolytes induce favorable surface reconstruction in Cu-based catalysts,affecting surface roughness through dissolution-redeposition of Cu species and interactions with halogens and molecular additives.It also covers changes in crystalline facets of Cu and Cu_(2)O,and oxidation states,highlighting transitions from Cu^(0) to Cu^(δ+)and the stabilization of Cu^(+).The role of electrolytes in the C–C coupling process is examined,emphasizing their effects in modulating mass and charge transfer,CO_(2) adsorption,intermediate evolution,and product desorption.Subsequently,the mechanisms by non-aqueous electrolytes,including organic solvents,ionic liquids,and mixed electrolytes,affecting CO_(2) reduction are analyzed,highlighting the unique advantages and challenges of each type.The review concludes by addressing current challenges,proposing solutions,and research directions,such as optimizing electrolyte composition by integrating diverse cations and anions and employing advanced in-situ characterization techniques.These insights can significantly enhance CO_(2)reduction performance on Cu-based electrocatalysts,advancing efficient and sustainable green energy technologies.
基金Project (50874045) supported by the National Natural Science Foundation of ChinaProjects (200902472, 20080431021) supported by the China Postdoctoral Science FoundationProject (10A044) supported by the Research Foundation of Education Bureau of Hunan Province of China
文摘Bulk Cu50Zr40Ti10 amorphous alloy composites reinforced with carbon nanotube （CNT） were successfully fabricated by hot pressing technique. Their density, thermal conductivity, and mechanical properties were systemically investigated. The density and the compression strength of the compacts both decrease with increasing CNT content. The thermal conductivity of the compacts decreases when the CNT content is less than 0.10% or exceeds 0.60% （mass fraction）, while increases when the CNT content is in the range of 0.1%-0.6%. The strain limit and the modulus of the compacts are obviously improved when the CNT content is less than 1.0% and then decrease significantly when the CNT content exceeds 1.00%. The optimum CNT addition is less than 0.20% at the comprehensive properties point of view.
基金Project(50971041)support by the National Natural Science Foundation of China
文摘The glassy rods were successfully fabricated in the Cu-Zr-Ti-In alloy system by casting into a copper mold. The value of ATx reaches a maximum of 66 K for the BMG CusoZraTTi8In5 alloy. The reasons for enhancing glass forming ability of Cu-based BMGs with the addition of indium were discussed from atomic size and thermodynamics. Alternatively, the BMG Cu52Zra7Ti8In3 exhibits the highest compressive strength （1981 MPa） and the best plasticity among glassy Cu55-xZra7TisInx （x_〈5）. The total plastic deformation of Cu52Zr37TisIn3 before fracture approaches 1.2%.
基金Project (50874045) supported by the National Natural Science Foundation of ChinaProjects (200902472, 20080431021) supported by the China Postdoctoral Science FoundationProject (10A044) supported by the Research Foundation of Education Bureau of Hunan Province of China
文摘Cu50Zr40Ti10 bulk amorphous alloys were fabricated by hot pressing gas-atomized Cu50Zr40Ti10 amorphous powder under different consolidation conditions without vacuum and inert gas protection. The consolidation conditions of the Cu50Zr40Ti10 amorphous powder were investigated based on an L9（34） orthogonal design. The compression strength and strain limit of the Cu50Zr40Ti10 bulk amorphous alloys can reach up to 1090.4 MPa and 11.9 %, respectively. The consolidation pressure significantly influences the strain limit and compression strength of the compact. But the mechanical properties are not significantly influenced by the consolidation temperature. In addition, the preforming pressure significantly influences not the compression strength but the strain limit. The optimum consolidation condition for the Cu50Zr40Ti10 amorphous powder is first precompacted under the pressure of 150 MPa, and then consolidated under the pressure of 450 MPa and the temperature of 380 °C.
基金Projects(50874045,51301194)supported by the National Natural Science Foundation of ChinaProject(2144057)supported by the Beijing Natural Science Foundation,China
文摘Room-temperature mechanical properties of Cu50Zr40Ti10-xNix（0≤x≤4,mole fraction,%） bulk metallic glasses （BMG） with aspect ratios in the range of 1：1-2.5：1 and loading rates in the range of1×10^-5-1×10^-2s^-1were systematically investigated by room-temperatureuniaxialcompression test.In the condition of an aspect ratio of 1：1, the superplasticity can be clearly observed for Cu50Zr40Ti10BMG when the loading rate is1×10^-4s^-1, while for Cu50Zr40Ti10-xNix（x=1-3, mole fraction, %） BMGs when the loading rate is1×10^-2s^-1. The plastic strain （εp）, yielding strength （σy） and fracture strength （σf） of the studied Cu-based BMGs significantly depend on the aspect ratio and the loading rate. In addition, theσyof the studied Cu-based BMGs with an aspect ratio of 1：1 is close to the σfof those with the other aspect ratios when the loading rate is1×10^-2s^-1. The mechanism for the mechanical response to the loading rate and the aspect ratiowas also discussed.
基金supported by the Open Fund of the State Key Laboratory of Advanced Welding Production Technology in Harbin Institute of Technology,Chinathe Open Fund of the State Key Laboratory of Materials Processing and Die&Mould Technology in Huazhong University of Science and Technology,China
文摘To improve the sliding wear resistance of AZ91D magnesium alloy, Cu-based amorphous composite coatings made of CuaTTi34Zr11Nis and Cu47Ti34Zr11Ni8＋20 wt pct SiC powders were fabricated on AZ91D magnesium alloy by laser cladding, respectively. SEM （scanning electron microscopy）, EDS （energy dispersive X-ray spectroscopy）, XRD （X-ray diffraction） and TEM （transmission electron microscopy） techniques were employed to study the phases of the coatings. The results show that the coatings mainly consist of amorphous phase and different intermetallic compounds. The reason of formation of amorphous phase and the function of SiC particles were explained in details.
基金Project supported by National Natural Science Foundation of China(51575179,51205126)Natural Science Foundation of Hunan Province(2017JJ3073,12JJB006)
文摘CuSn powders and Till2 powders were milled using high energy mechanical milling to prepare Cu-based alloy powders for brazing diamond. And Ce was added to the milled Cu-based alloy powders to improve the wettability. It is found that the wetting angle reaches the minimum value 13.2° and the maximum spreading area 178 mm2 is achieved when the amount of Ce is 0.75 wt%. And Ce remarkably reduces the surface tension of liquid alloy, which improves the climbing height along the diamond and forms a massive support profile. And the results show that Ce can effectively improve the transverse rupture strength （TRS） due to high wettability. The wear characteristics of the diamonds brazed with Cu-based alloy containing 0.75 wt% Ce mainly consist of integrity, micro-fracture, fracture and rubdown, diamonds pull-out can not easily happen.
基金financially supported by the National Basic Research Program of China (No. 2011CB606300)the National Natural Science Foundation of China (No. 51104015)the Fundamental Research Funds for the Central Universities (No. FRF-TP-14-089A2)
文摘The effects of various structure factors on the properties(superelasticity mainly) of Cu-based shape memory alloys(SMAs) were systematically evaluated in this review article through literatures combining with our work. It is concluded that besides the decisive role of grain orientation, the grain boundary(GB) characteristics also play important roles in the superelasticity, which include GB area, GB type, GB morphology and GB direction in descending order of the effect significance. According to the above results, the prior principles of structure design are proposed for high-performance Cu-based SMAs from most to least important:(1) obtaining grain orientation with high phase transformation strain;(2) increasing grain size or reducing GB area;(3) obtaining straight low-energy GBs, especially low-angle GBs;(4) trying to make GB direction parallel to external stress. Consistent with the main or all principles, the bamboo-like-grained and columnar-grained(CG) Cu-based SMAs show excellent comprehensive properties.
基金the supports sponsored by the National Natural Science Foundation of China(22005215,22090031)the Hebei Province Innovation Ability Promotion Project(20544401D,20312201D)。
文摘Electrochemical reduction of CO_(2)(CO_(2)RR)to high value-added chemicals is an effective way to remove excess CO_(2) from the atmosphere.Due to the unique propensity of Cu for valuable hydrocarbons,Cu-based electrocatalysts are the most potential catalysts that allow the conversion of CO_(2) into a variety of C_(2) products such as ethylene and ethanol.Rational design of Cu-based catalysts can improve their directional selectivity to C_(2) products.Hence,in this review,we summarize the recent progress in the mechanistic studies of Cu-based catalysts on reducing CO_(2) to C_(2) products.We focus on three key strategies for efficiently enhancing electrocatalytic performance of Cu-based catalysts,including tuning electronic structure,surface structure,and coordination environment.The correlation between the structural characteristics of Cu-based catalysts and their activity and selectivity to C_(2) products is discussed.Finally,we discuss the challenges in the field of CO_(2) electroreduction to C_(2) products and provide the perspectives to design efficient Cu-based catalysts in the future.
基金financial supports from the National 1000 Young Talents Program of Chinathe National Nature Science Foundation of China (21603078)+1 种基金the National Materials Genome Project (2016YFB0700600)financial support from Research and Education in eNergy, Environment and Water (RENEW)Institute at the University at Buffalo, SUNY
文摘COconversion via photocatalysis is a potential solution to address global warming and energy shortage.Photocatalysis can directly utilize the inexhaustible sunlight as an energy source to catalyze the reduction of COto useful solar fuels such as CO, CH, CHOH, and CHOH. Among studied formulations, Cubased photocatalysts are the most attractive for COconversion because the Cu-based photocatalysts are low-cost and abundance comparing noble metal-based catalysts. In this literature review, a comprehensive summary of recent progress on Cu-based photocatalysts for COconversion, which includes metallic copper, copper alloy nanoparticles（NPs）, copper oxides, and copper sulfides photocatalysts, can be found. This review also included a detailed discussion on the correlations of morphology, structure, and performance for each type of Cu-based catalysts. The reaction mechanisms and possible pathways for productions of various solar fuels were analyzed, which provide insight into the nature of potential active sites for the catalysts. Finally, the current challenges and perspective future research directions were outlined, holding promise to advance Cu-based photocatalysts for COconversion with much-enhanced energy conversion efficiency and production rates.
基金financially supported by the National Nature Science Foundation of China(Nos.51405199 and21301075)the Natural Science Foundation of Jiangsu Province(Nos.BK20140551 and BK20140562)+4 种基金the Postdoctoral Science Foundation of China(No.2014M561579)the Postdoctoral Science Foundation of Jiangsu Province(No.1401106C)the Opening Foundation of Jiangsu Province Material Tribology Key Laboratory(No.Kjsmcx201304)the Senior Intellectuals Fund of Jiangsu University(No.13JDG099)the Industry-Academy-Research Union Foundation of Jiangsu Province(No.BY2013065-05)
文摘In this study, S-doped NbSea （NbSo.aSel.8） powders were fabricated, and the corresponding Cu-based composites （Cu/NbSo.eSe1.8） were obtained by powder metallurgy technique. The phase compositions, physical, and tribological properties of Cu-based composites were investigated systematically. The results show that Cu matrix reacts with NbSo.2Sel.8 to produce Cu2Se and Cu0.38NbSo.2Se1.8 during sintering process, which influences the physical and tribological properties of Cu-based composites significantly. Specially, with NbS0.2Se1.8 content increasing, the density of Cu/ NbSo.2Se1.8 composites decreases, and the hardness increases firstly and then decreases, while the electric resistivity in- creases slightly. In addition, the incorporation of NbSo.2Se1.8 enhances the tribological properties of Cu greatly, which is attributed to the lubricating effect of Cuo,38NbSo.2Se1.8 and the reinforcement effect of Cu2Se. In particular, when the content of NbSo.2Sel.8 is 6 wt%, the Cu-based composite has the best tribological properties.
基金supported by the National Natural Science Foundation of China (Grant Nos.62006219 and 62001266)Guangdong Innovative and Entrepre-neurial Research Team Program (grant No.2017ZT07C341)+2 种基金the Bureau of Industry and Information Technology of Shenzhen for the 2017 Graphene Manufacturing Innovation Center Project (No.201901171523)the China Postdoctoral Science Foundation (No.2020M680506)Guangdong Basic and Applied Basic Research Foundation (No.2020A1515110338).
文摘Various strategies,including controls of morphology,oxidation state,defect,and doping,have been developed to improve the performance of Cu-based catalysts for CO_(2) reduction reaction(CO_(2)RR),generating a large amount of data.However,a unified understanding of underlying mechanism for further optimization is still lacking.In this work,combining first-principles calculations and machine learning(ML)techniques,we elucidate critical factors influencing the catalytic properties,taking Cu-based single atom alloys(SAAs)as examples.Our method relies on high-throughput calculations of 2669 CO adsorption configurations on 43 types of Cu-based SAAs with various surfaces.Extensive ML analyses reveal that low generalized coordination numbers and valence electron number are key features to determine catalytic performance.Applying our ML model with cross-group learning scheme,we demonstrate the model generalizes well between Cu-based SAAs with different alloying elements.Further,electronic structure calculations suggest surface negative center could enhance CO adsorption by back donating electrons to antibonding orbitals of CO.Finally,several SAAs,including PCu,AgCu,GaCu,ZnCu,SnCu,GeCu,InCu,and SiCu,are identified as promising CO_(2)RR catalysts.Our work provides a paradigm for the rational design and fast screening of SAAs for various electrocatalytic reactions.
基金Science Council of Shandong Province!under Grant No.89F0274
文摘The curved martensite structures have been observed in CuZnAI-based shape memory alloys by both transmission electron microscope and optical microscope. It was found that the curved martensite structures observed in as-solution treated, as-aged and as-trained alloys usually occurred around dislocation tangles or precipitate, at the plate boundary or grain boundary, and when the growing plates collided with each other or alternate mutually.
基金financially supported by the National Natural Science Foundation of China (No.51401197)
文摘Cu and Nb powders were used as starting materials to produce Cu-Nb and Cu-NbC-WC composites by mechanical alloying. X-ray diffraction, scanning electron microscopy, transmission electron microscopy observations and microhardness measurements have been used to study the effects of milling tools on the phase, microstructure and property of the composites. The results revealed that a single-phase nanocrystalline solid solution was obtained using stainless steel vials and balls （Alloy 1）. Nevertheless, Cu-7 wt% Nb powders milled by tungsten carbon vials and balls exhibited an amorphous phase （Alloy 2）. The as-milled powders were then vacuum hot-pressing sintered. The microstructure of sintered Alloy 1 consisted of Nb nanoparticles and Cu nanograins. Instead, Alloy 2 showed a microstructure with NbC nanoparticles and WC submicron-sized particles dispersed throughout the Cu matrix. Furthermore, Alloy 2 （～ 322 HV） had a higher microhardness than Alloy 1 （～ 302 HV）.
