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
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
The ultrafine particles of a new style Fe-Cu-based catalysts for CO hydrogenation were prepared by impregnating the organic sol of Fe（OH）3 and Cu（OH）2 onto the activated Al2O3, in which the organic sol of Fe（OH）...The ultrafine particles of a new style Fe-Cu-based catalysts for CO hydrogenation were prepared by impregnating the organic sol of Fe（OH）3 and Cu（OH）2 onto the activated Al2O3, in which the organic sol of Fe（OH）3 and Cu（OH）2 were prepared in the microemulsion of dodecylbenzenesulfonic acid sodium（S）/n-butanol（A）/toluene（O）/water with V（A）/V（O） = 0.25 and W（A）/W（S） = 1.50. This catalyst was characterized by particle size analysis, XRD and TG. The results of particle size analysis showed that Fe（OH）3 particles with a mean size of 17.1 nm and Cu（OH）2 particles with an average size of 6.65 um were obtained. TG analysis and XRD patterns suggested that 673 K is the optimal calcination temperature. CO hydrogenation produced C＋OH with a high selectivity above 58 wt% by using the ultrafine particles as catalyst, and the total alcohol yield of 0.250 g·ml^-1 ·h^-1 was obtained when the contents of Al2O3 and K were 88.61 wt% and 1.60 wt%, respectively.展开更多
A novel strategy to synthesize copper-based nanoparticles supported on carbon nitride(C3 N4) was developed by popping of mixture containing C3 N4 and cupric nitrate. Characterizations such as X-ray photoelectron spect...A novel strategy to synthesize copper-based nanoparticles supported on carbon nitride(C3 N4) was developed by popping of mixture containing C3 N4 and cupric nitrate. Characterizations such as X-ray photoelectron spectroscopy(XPS) and X-ray diffraction(XRD) indicate that the structure of g-C3 N4 maintained although a popping process occurred. High resolution transmission electronic microscopy(HRTEM) characterization illustrated that copper-based nanoparticles with diameter of < 1 nm were well distributed on g-C3 N4. This kind of copper catalyst exhibits high catalytic activity and selectivity in arylation of pyrazole, a simple and effect strategy to construct C-N bond in organic chemistry.According to the results of control experiments and characterizations, cuprous oxide should be the catalytic active phase in the supported coperbased catalyst.展开更多
Dimethyl oxalate(DMO) hydrogenation is a crucial step in the coal to ethylene glycol(CTEG) process.Herein, Cu catalyst supported on fibrous mesoporous silica(Cu/FMS) was synthesized via liquid phase deposition techniq...Dimethyl oxalate(DMO) hydrogenation is a crucial step in the coal to ethylene glycol(CTEG) process.Herein, Cu catalyst supported on fibrous mesoporous silica(Cu/FMS) was synthesized via liquid phase deposition technique and applied for the DMO hydrogenation to EG. The catalyst exhibited a remarkable EG selectivity of 96.95% and maintained its activity without deactivation for 1000 h. Fibers of FMS support and liquid phase deposition technology cooperated to give high dispersion of Cu species in the Cu/FMS catalyst, resulting in a high Cu surface area. The formation of Si—O—Cu during catalyst preparation process increased the Cu^(+)/(Cu^(0)+ Cu^(+)) ratio and enhanced the thermal and valence stability of Cu species.The high Cu^(+) surface area and Cu stability(thermal and valence stability) of the Cu/FMS catalyst were key factors for achieving superior EG selectivity and ultra-high stability.展开更多
The Chemistry and Chemical Engineering School of Xiamen University has successfully developed the multi-walled nanotube catalyst with small and uniform diameter and has mastered the corresponding technology for manufa...The Chemistry and Chemical Engineering School of Xiamen University has successfully developed the multi-walled nanotube catalyst with small and uniform diameter and has mastered the corresponding technology for manufacture of carbon nanotube. It is learned that this technology has been for the first time developed inside ;and has reached the internationally advanced level with some indicators commanding a globally leading position.展开更多
Driven by the goal of global carbon neutrality,electrocatalytic carbon dioxide reduction reaction(eCO_(2)RR)technology has become a research hotspot due to its potential to efficiently convert CO_(2)into high value-ad...Driven by the goal of global carbon neutrality,electrocatalytic carbon dioxide reduction reaction(eCO_(2)RR)technology has become a research hotspot due to its potential to efficiently convert CO_(2)into high value-added products,such as ethylene and ethanol.Cu-based catalysts become the core material under their unique electronic structure and C–C coupling ability.It is precisely designed by single atomic sites(SACs)and diatomic site catalysts(DASCs).Combined with the stabilizing effect of composite carriers(such as metal–organic framework(MOF)materials)on the Cu active site,the product selectivity and reaction kinetics were significantly improved.In situ characterization and computational simulation revealed the dynamic reconfiguration of Cu sites and the adsorption mechanism of*CO intermediates.This result confirms that low-coordination Cu sites promote C–C coupling through the Eley–Rideal(ER)pathway,and high-pressure/high-temperature conditions can regulate the reaction path.Despite outstanding laboratory performance,industrial applications still face low stability at high current densities,high-scale preparation costs,and system integration challenges.In the future,it is necessary to focus on the analysis of atomic-level reaction mechanisms,the development of intelligent response materials,and the coupling technology of photoelectric and electrocatalysis,combined with green power matching and carbon tax policy coordination,to promote the leapfrog development of copper-based catalysts from basic research to industrial carbon cycle technology.展开更多
The electrochemical CO_(2)reduction reaction(CO_(2)RR)is a promising approach for converting CO_(2)into valuable chemicals and promoting carbon cycling.Among the products of CO_(2)RR,ethylene(C_(2)H_(4)),as a crucial ...The electrochemical CO_(2)reduction reaction(CO_(2)RR)is a promising approach for converting CO_(2)into valuable chemicals and promoting carbon cycling.Among the products of CO_(2)RR,ethylene(C_(2)H_(4)),as a crucial chemical feedstock,holds significant market demand and economic value.The design of an electrolyte-free cathode in membrane electrode assemblies(MEAs)can effectively mitigate mass transfer limitations,reduce ohmic losses,and enhance interfacial efficiency,thereby significantly improving current density and product selectivity.The integration of copper-based catalysts into MEAs is considered a promising strategy for the industrial-scale production of C_(2)H_(4) via CO_(2)RR.However,comprehensive reviews on the application of copper-based catalysts in MEAs for CO_(2)RR to C_(2)H_(4)remain limited,particularly regarding systematic analyses of catalyst design strategies,optimization of MEA components and operating conditions,and MEA device configurations.This review systematically summarizes the latest research progress on copper-based catalysts in MEAs for CO_(2)RR to C_(2)H_(4).Firstly,the reaction mechanism of CO_(2)RR to C_(2)H_(4) was summarized and the role of intermediate adsorption regulation was highlighted in MEA systems.Secondly,strategies applied to optimize ethylene production using copper-based catalysts in MEAs were also summarized accordingly.Next,the influence of components,operational conditions,and device design for MEA was discussed.Finally,the opportunities and challenges of using copper-based catalysts in MEAs for C_(2)H_(4)production were outlined.This review aims to provide insights and inspire further research efforts toward optimizing the performance of CO_(2)RR to C_(2)H_(4)in MEAs.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
Electrocatalytic CO_(2) reduction(ECR)is a promising approach for achieving carbon neutrality due to its ability to convert CO_(2) to valuable chemicals.Recent advances have significantly enhanced the ECR performance ...Electrocatalytic CO_(2) reduction(ECR)is a promising approach for achieving carbon neutrality due to its ability to convert CO_(2) to valuable chemicals.Recent advances have significantly enhanced the ECR performance of various catalysts by tuning their oxidation states,particularly for Cu-based catalysts that can reduce CO_(2) to multiple products.However,the oxidation state of copper(OSCu),especially Cu+,changes during the reaction process,posing significant challenges for both catalyst characterization and performance.In this review,the current understanding of the effect of oxidation states on product selectivity was first discussed.A comprehensive overview of in situ/operando characterization techniques,used to monitor the dynamic evolution of oxidation states during ECR,was then provided.Various strategies for stabilizing oxidation states through modification of catalysts and manipulation of external conditions were discussed.This review aimed to deepen the understanding of oxidation states in ECR and enlighten the development of more efficient electrocatalysts.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
Atomically dispersed Cu-based single-metal-site catalysts(Cu-N-C)have emerged as a frontier for electrocatalytic oxygen reduction reactions(ORR)because they can effectively optimize the D-band center of the Cu active ...Atomically dispersed Cu-based single-metal-site catalysts(Cu-N-C)have emerged as a frontier for electrocatalytic oxygen reduction reactions(ORR)because they can effectively optimize the D-band center of the Cu active site and provide appropriate adsorption/desorption energy for oxygen-containing intermediates.Metal-organic frameworks(MOFs)show excellent prospects in many fields because of their structural regularity and designability,but their direct use for electrocatalysis has been rarely reported due to the low intrinsic conductivity.Here,a MOF material(Cu-TCNQ)with highly regular single-atom copper active centers was successfully prepared using a solution chemical reaction method.Subsequently,Cu-TCNQ and graphene oxide(GO)were directly self-assembled to form a Cu-TCNQ/GO composite,which improved the conductivity of the catalyst while maintained the atomically precise controllability.The resistivity of the Cu-TCNQ/GO decreased by three orders of magnitude(1663.6-2.7 W/cm)compared with pure Cu-TCNQ.The half-wave potential was as high as 0.92 V in 0.1 mol/L KOH,even better than that of commercial 20%Pt/C.In alkaline polymer electrolyte fuel cells(APEFCs),the open-circuit voltage and power density of Cu-TCNQ/GO electrode reached 0.95 V and 320 m W/cm^(2),respectively,which suggests that Cu-TCNQ/GO has a good potential for application as a cathode ORR catalyst.展开更多
Copper-based catalysts have garnered wide attention in the field of electrocatalytic nitrate reduction for ammonia production due to their low hydrogen precipitation activity and high ammonia selectivity.However,they ...Copper-based catalysts have garnered wide attention in the field of electrocatalytic nitrate reduction for ammonia production due to their low hydrogen precipitation activity and high ammonia selectivity.However,they still face challenges pertaining of poor stability and low activity,which hinder their further application.Herein,we present a Cu_(2)O/Cu heterojunction catalyst supported on nitrogen-doped porous carbon for nitrate reduction.High resolution transmission electron microscopy(HRTEM)and X-ray Diffraction(XRD)results confirm the presence of Cu_(2)O/Cu heterojunctions,which serve as an active phase in catalysis.The nitrogen-doped porous carbon as a carrier not only enhances the catalyst’s stability,but also facilitates the exposure and dispersion of active sites.At-1.29 V(vs.RHE),the maximum production rate of ammonia reaches 8.8 mg/(mg·h)with a Faradaic efficiency of 92.8%.This study also elucidates the effect of Cu_(2)O-to-Cu ratio in the heterojunction on catalytic performance,thereby providing valuable insights for designing efficient nitrate reduction catalysts for ammonia production.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
To address the ever-increasing CO_(2)concentration problem in the atmospheric air arisen by massive consumption of fossil fuels,electrocatalytic technologies that reduce CO_(2)to generate high value-added products hav...To address the ever-increasing CO_(2)concentration problem in the atmospheric air arisen by massive consumption of fossil fuels,electrocatalytic technologies that reduce CO_(2)to generate high value-added products have been gaining increasing interest.Cu-based CO_(2)reduction catalysts have attracted widespread attention owing to their capability of generating C1 and C_(2+)products.However,Cu-based catalysts are highly challenged by their low product selectivity.Recently,Cu-based bimetallic catalysts have been found the unique catalytical activity and selectivity in CO_(2)reduction reactions(CO_(2)RR).The incorporation of other metals can change the electronic circumstance of Cu-based catalysts,promoting the adsorption ability of the intermediate products and consequently leading to high selectivity.In this minireview,we intend to summarize recent advances of Cu-based bimetallic catalysts in producing C1 and C_(2+)products,involving designing heterostructure,alloy,defects and surface modification engineering.We pay special attention to the regulation of electronic structure of the composite catalysts,as well as insights into the relationship between electronic property and catalytical performance for Cu-based bimetallic catalysts.展开更多
In the conversion process of syngas-to-C_(2)species,the OH species are inevitably produced accompanying the production of key intermediates CH_(x)(x=1-3),traditionally,the function of surface OH species is generally a...In the conversion process of syngas-to-C_(2)species,the OH species are inevitably produced accompanying the production of key intermediates CH_(x)(x=1-3),traditionally,the function of surface OH species is generally accepted as the hydrogenating reactive species.This work for the first time proposed and confirmed the assisted catalytic mechanism of surface OH species that performed as the promoter for syngas-to-C_(2)species on Cu-based catalysts.DFT and microkinetic modeling results reveal that the produced OH species accompanying the intermediates CH_(x)production on the MCu(M=Co,Fe,Rh)catalysts can stably exist to form OH/MCu catalysts,on which the presence of surface OH species as the promoter not only presented better activity and selectivity toward CH_(x)(x=1-3)compared to MCu catalysts,but also significantly suppressed CH_(3)OH production,providing enough CH_(x)sources to favor the production of C_(2)hydrocarbons and oxygenates.Correspondingly,the electronic properties analysis revealed the essential relationship between the electronic feature of OH/MCu catalysts and catalytic performance,attributing to the unique electronic micro-environment of the catalysts under the interaction of surface OH species.This new mechanism is called as OH-assisted catalytic mechanism,which may be applied in the reaction systems related to the generation of OH species.展开更多
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
High-performance and low-cost anode materials are critical for superior sodium-ion batteries(SIBs).Herein,high-yield porous carbon nanofiber(CNF)anode materials(named CNFs@Cu–Ni)are prepared by chemical vapor deposit...High-performance and low-cost anode materials are critical for superior sodium-ion batteries(SIBs).Herein,high-yield porous carbon nanofiber(CNF)anode materials(named CNFs@Cu–Ni)are prepared by chemical vapor deposition using a specialized nanoporous Cu–Ni alloy catalyst.Density functional theory calculations indicate that Ni incorporation results in a shift of the d-band center of the catalyst from−2.34157 to−1.93682 eV.This phenomenon elucidates the remarkable adsorption capacity of the Cu–Ni catalyst toward C2H2,thereby facilitating the catalytic growth of high-performance CNFs.With this approach,a superior yield of 258.6%for deposited carbon is reached after growth for 1 h.The CNFs@Cu–Ni anode presents an outstanding discharge capacity of 193.6 mAh·g^(−1) at 1.0 A·g^(−1)over 1000 cycles and an exceptional rate capability by maintaining a capacity of 158.9 mAh·g^(−1)even at 5.0 A·g^(−1)in an ether-based electrolyte.It also exhibits excellent performance in the CNFs@Cu–Ni//NVP full battery attributed to the presence of abundant Na+adsorption sites on its surface.This study presents a new concept for the advancement of high-performance carbonaceous electrodes for SIBs.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).
文摘The ultrafine particles of a new style Fe-Cu-based catalysts for CO hydrogenation were prepared by impregnating the organic sol of Fe（OH）3 and Cu（OH）2 onto the activated Al2O3, in which the organic sol of Fe（OH）3 and Cu（OH）2 were prepared in the microemulsion of dodecylbenzenesulfonic acid sodium（S）/n-butanol（A）/toluene（O）/water with V（A）/V（O） = 0.25 and W（A）/W（S） = 1.50. This catalyst was characterized by particle size analysis, XRD and TG. The results of particle size analysis showed that Fe（OH）3 particles with a mean size of 17.1 nm and Cu（OH）2 particles with an average size of 6.65 um were obtained. TG analysis and XRD patterns suggested that 673 K is the optimal calcination temperature. CO hydrogenation produced C＋OH with a high selectivity above 58 wt% by using the ultrafine particles as catalyst, and the total alcohol yield of 0.250 g·ml^-1 ·h^-1 was obtained when the contents of Al2O3 and K were 88.61 wt% and 1.60 wt%, respectively.
基金supported the following funders: One Hundred Talent Project of Hebei Province (Grant No. E2016100015)National Natural Science Foundation of China (No. 21773053)+2 种基金Hebei provincial Natural Science Foundation (No. B2017201084)Hebei Provincial Technology Foundation for High-level talents (No. CL201601)the science technology research and development guidance program project of Baoding City (No. 16ZF027)
文摘A novel strategy to synthesize copper-based nanoparticles supported on carbon nitride(C3 N4) was developed by popping of mixture containing C3 N4 and cupric nitrate. Characterizations such as X-ray photoelectron spectroscopy(XPS) and X-ray diffraction(XRD) indicate that the structure of g-C3 N4 maintained although a popping process occurred. High resolution transmission electronic microscopy(HRTEM) characterization illustrated that copper-based nanoparticles with diameter of < 1 nm were well distributed on g-C3 N4. This kind of copper catalyst exhibits high catalytic activity and selectivity in arylation of pyrazole, a simple and effect strategy to construct C-N bond in organic chemistry.According to the results of control experiments and characterizations, cuprous oxide should be the catalytic active phase in the supported coperbased catalyst.
基金financially supported by National Natural Science Foundation of China (22008166)Natural Science Foundation of Shanxi (201901D211047)Scientific and Technological Innovation Programs of Higher Education Institutions in Shanxi (2019L0185)。
文摘Dimethyl oxalate(DMO) hydrogenation is a crucial step in the coal to ethylene glycol(CTEG) process.Herein, Cu catalyst supported on fibrous mesoporous silica(Cu/FMS) was synthesized via liquid phase deposition technique and applied for the DMO hydrogenation to EG. The catalyst exhibited a remarkable EG selectivity of 96.95% and maintained its activity without deactivation for 1000 h. Fibers of FMS support and liquid phase deposition technology cooperated to give high dispersion of Cu species in the Cu/FMS catalyst, resulting in a high Cu surface area. The formation of Si—O—Cu during catalyst preparation process increased the Cu^(+)/(Cu^(0)+ Cu^(+)) ratio and enhanced the thermal and valence stability of Cu species.The high Cu^(+) surface area and Cu stability(thermal and valence stability) of the Cu/FMS catalyst were key factors for achieving superior EG selectivity and ultra-high stability.
文摘The Chemistry and Chemical Engineering School of Xiamen University has successfully developed the multi-walled nanotube catalyst with small and uniform diameter and has mastered the corresponding technology for manufacture of carbon nanotube. It is learned that this technology has been for the first time developed inside ;and has reached the internationally advanced level with some indicators commanding a globally leading position.
基金supported by the Science and Technology Major Project of Henan Province,Henan,China(No.CX0001F01800).
文摘Driven by the goal of global carbon neutrality,electrocatalytic carbon dioxide reduction reaction(eCO_(2)RR)technology has become a research hotspot due to its potential to efficiently convert CO_(2)into high value-added products,such as ethylene and ethanol.Cu-based catalysts become the core material under their unique electronic structure and C–C coupling ability.It is precisely designed by single atomic sites(SACs)and diatomic site catalysts(DASCs).Combined with the stabilizing effect of composite carriers(such as metal–organic framework(MOF)materials)on the Cu active site,the product selectivity and reaction kinetics were significantly improved.In situ characterization and computational simulation revealed the dynamic reconfiguration of Cu sites and the adsorption mechanism of*CO intermediates.This result confirms that low-coordination Cu sites promote C–C coupling through the Eley–Rideal(ER)pathway,and high-pressure/high-temperature conditions can regulate the reaction path.Despite outstanding laboratory performance,industrial applications still face low stability at high current densities,high-scale preparation costs,and system integration challenges.In the future,it is necessary to focus on the analysis of atomic-level reaction mechanisms,the development of intelligent response materials,and the coupling technology of photoelectric and electrocatalysis,combined with green power matching and carbon tax policy coordination,to promote the leapfrog development of copper-based catalysts from basic research to industrial carbon cycle technology.
基金supported by the Taishan Scholars Program(Nos.tsqn202306309,tstp20221151)Natural Science Foundation of Shandong Province(Nos.ZR2023YQ012,ZR2024QB295)the National Natural Science Foundation of China(Nos.52261145700,22261132517).
文摘The electrochemical CO_(2)reduction reaction(CO_(2)RR)is a promising approach for converting CO_(2)into valuable chemicals and promoting carbon cycling.Among the products of CO_(2)RR,ethylene(C_(2)H_(4)),as a crucial chemical feedstock,holds significant market demand and economic value.The design of an electrolyte-free cathode in membrane electrode assemblies(MEAs)can effectively mitigate mass transfer limitations,reduce ohmic losses,and enhance interfacial efficiency,thereby significantly improving current density and product selectivity.The integration of copper-based catalysts into MEAs is considered a promising strategy for the industrial-scale production of C_(2)H_(4) via CO_(2)RR.However,comprehensive reviews on the application of copper-based catalysts in MEAs for CO_(2)RR to C_(2)H_(4)remain limited,particularly regarding systematic analyses of catalyst design strategies,optimization of MEA components and operating conditions,and MEA device configurations.This review systematically summarizes the latest research progress on copper-based catalysts in MEAs for CO_(2)RR to C_(2)H_(4).Firstly,the reaction mechanism of CO_(2)RR to C_(2)H_(4) was summarized and the role of intermediate adsorption regulation was highlighted in MEA systems.Secondly,strategies applied to optimize ethylene production using copper-based catalysts in MEAs were also summarized accordingly.Next,the influence of components,operational conditions,and device design for MEA was discussed.Finally,the opportunities and challenges of using copper-based catalysts in MEAs for C_(2)H_(4)production were outlined.This review aims to provide insights and inspire further research efforts toward optimizing the performance of CO_(2)RR to C_(2)H_(4)in MEAs.
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(No.52221004)the Shenzhen Science and Technology Program(No.RCJC20221008092758099)+1 种基金the Shenzhen Pengrui Young Faculty Program of Shenzhen Pengrui Foundation(No.SZPR2023004)the Guangdong Higher Education Institutions Innovative Research Team of Urban Water Cycle and Ecological Safety(No.2023KCXTD053).
文摘Electrocatalytic CO_(2) reduction(ECR)is a promising approach for achieving carbon neutrality due to its ability to convert CO_(2) to valuable chemicals.Recent advances have significantly enhanced the ECR performance of various catalysts by tuning their oxidation states,particularly for Cu-based catalysts that can reduce CO_(2) to multiple products.However,the oxidation state of copper(OSCu),especially Cu+,changes during the reaction process,posing significant challenges for both catalyst characterization and performance.In this review,the current understanding of the effect of oxidation states on product selectivity was first discussed.A comprehensive overview of in situ/operando characterization techniques,used to monitor the dynamic evolution of oxidation states during ECR,was then provided.Various strategies for stabilizing oxidation states through modification of catalysts and manipulation of external conditions were discussed.This review aimed to deepen the understanding of oxidation states in ECR and enlighten the development of more efficient electrocatalysts.
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supported by the National Key Research and Development Program of China(No.2022YFB3807500)the National Natural Science Foundation of China(No.22220102003)+1 种基金the Beijing Natural Science Foundation(No.JL23003)“Double-First-Class”construction projects(Nos.XK180301 and XK1804-02)。
文摘Atomically dispersed Cu-based single-metal-site catalysts(Cu-N-C)have emerged as a frontier for electrocatalytic oxygen reduction reactions(ORR)because they can effectively optimize the D-band center of the Cu active site and provide appropriate adsorption/desorption energy for oxygen-containing intermediates.Metal-organic frameworks(MOFs)show excellent prospects in many fields because of their structural regularity and designability,but their direct use for electrocatalysis has been rarely reported due to the low intrinsic conductivity.Here,a MOF material(Cu-TCNQ)with highly regular single-atom copper active centers was successfully prepared using a solution chemical reaction method.Subsequently,Cu-TCNQ and graphene oxide(GO)were directly self-assembled to form a Cu-TCNQ/GO composite,which improved the conductivity of the catalyst while maintained the atomically precise controllability.The resistivity of the Cu-TCNQ/GO decreased by three orders of magnitude(1663.6-2.7 W/cm)compared with pure Cu-TCNQ.The half-wave potential was as high as 0.92 V in 0.1 mol/L KOH,even better than that of commercial 20%Pt/C.In alkaline polymer electrolyte fuel cells(APEFCs),the open-circuit voltage and power density of Cu-TCNQ/GO electrode reached 0.95 V and 320 m W/cm^(2),respectively,which suggests that Cu-TCNQ/GO has a good potential for application as a cathode ORR catalyst.
基金supported by the Fundamental Research Funds for the Central Universities(DUT22LAB601)the Technology Development Contract of Sinopec(123038).
文摘Copper-based catalysts have garnered wide attention in the field of electrocatalytic nitrate reduction for ammonia production due to their low hydrogen precipitation activity and high ammonia selectivity.However,they still face challenges pertaining of poor stability and low activity,which hinder their further application.Herein,we present a Cu_(2)O/Cu heterojunction catalyst supported on nitrogen-doped porous carbon for nitrate reduction.High resolution transmission electron microscopy(HRTEM)and X-ray Diffraction(XRD)results confirm the presence of Cu_(2)O/Cu heterojunctions,which serve as an active phase in catalysis.The nitrogen-doped porous carbon as a carrier not only enhances the catalyst’s stability,but also facilitates the exposure and dispersion of active sites.At-1.29 V(vs.RHE),the maximum production rate of ammonia reaches 8.8 mg/(mg·h)with a Faradaic efficiency of 92.8%.This study also elucidates the effect of Cu_(2)O-to-Cu ratio in the heterojunction on catalytic performance,thereby providing valuable insights for designing efficient nitrate reduction catalysts for ammonia production.
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supported by Hunan Provincial Key Laboratory of Micro&Nano Materials Interface Science,China,the National Natural Science Foundation of China(Nos.21773311,21972169)the Hunan Provincial Science and Technology Plan Project,China(No.2019TP1001)the Open Sharing Fund for the Large-scale Instruments and Equipments of Central South University,China.
文摘To address the ever-increasing CO_(2)concentration problem in the atmospheric air arisen by massive consumption of fossil fuels,electrocatalytic technologies that reduce CO_(2)to generate high value-added products have been gaining increasing interest.Cu-based CO_(2)reduction catalysts have attracted widespread attention owing to their capability of generating C1 and C_(2+)products.However,Cu-based catalysts are highly challenged by their low product selectivity.Recently,Cu-based bimetallic catalysts have been found the unique catalytical activity and selectivity in CO_(2)reduction reactions(CO_(2)RR).The incorporation of other metals can change the electronic circumstance of Cu-based catalysts,promoting the adsorption ability of the intermediate products and consequently leading to high selectivity.In this minireview,we intend to summarize recent advances of Cu-based bimetallic catalysts in producing C1 and C_(2+)products,involving designing heterostructure,alloy,defects and surface modification engineering.We pay special attention to the regulation of electronic structure of the composite catalysts,as well as insights into the relationship between electronic property and catalytical performance for Cu-based bimetallic catalysts.
基金financially supported by Key Projects of National Natural Science Foundation of China(No.21736007)National Natural Science Foundation of China(Nos.22078221,21776193,21476155)Top Young Innovative Talents of Shanxi。
文摘In the conversion process of syngas-to-C_(2)species,the OH species are inevitably produced accompanying the production of key intermediates CH_(x)(x=1-3),traditionally,the function of surface OH species is generally accepted as the hydrogenating reactive species.This work for the first time proposed and confirmed the assisted catalytic mechanism of surface OH species that performed as the promoter for syngas-to-C_(2)species on Cu-based catalysts.DFT and microkinetic modeling results reveal that the produced OH species accompanying the intermediates CH_(x)production on the MCu(M=Co,Fe,Rh)catalysts can stably exist to form OH/MCu catalysts,on which the presence of surface OH species as the promoter not only presented better activity and selectivity toward CH_(x)(x=1-3)compared to MCu catalysts,but also significantly suppressed CH_(3)OH production,providing enough CH_(x)sources to favor the production of C_(2)hydrocarbons and oxygenates.Correspondingly,the electronic properties analysis revealed the essential relationship between the electronic feature of OH/MCu catalysts and catalytic performance,attributing to the unique electronic micro-environment of the catalysts under the interaction of surface OH species.This new mechanism is called as OH-assisted catalytic mechanism,which may be applied in the reaction systems related to the generation of OH species.
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financially supported by the National Natural Science Foundation of China(Nos.52271011 and 52102291)the Structure Design and Mass Preparation of High Stability and Low Cost PEM Hydroelectrolysis Non-Iridium Catalyst,China(No.KC22453)
文摘High-performance and low-cost anode materials are critical for superior sodium-ion batteries(SIBs).Herein,high-yield porous carbon nanofiber(CNF)anode materials(named CNFs@Cu–Ni)are prepared by chemical vapor deposition using a specialized nanoporous Cu–Ni alloy catalyst.Density functional theory calculations indicate that Ni incorporation results in a shift of the d-band center of the catalyst from−2.34157 to−1.93682 eV.This phenomenon elucidates the remarkable adsorption capacity of the Cu–Ni catalyst toward C2H2,thereby facilitating the catalytic growth of high-performance CNFs.With this approach,a superior yield of 258.6%for deposited carbon is reached after growth for 1 h.The CNFs@Cu–Ni anode presents an outstanding discharge capacity of 193.6 mAh·g^(−1) at 1.0 A·g^(−1)over 1000 cycles and an exceptional rate capability by maintaining a capacity of 158.9 mAh·g^(−1)even at 5.0 A·g^(−1)in an ether-based electrolyte.It also exhibits excellent performance in the CNFs@Cu–Ni//NVP full battery attributed to the presence of abundant Na+adsorption sites on its surface.This study presents a new concept for the advancement of high-performance carbonaceous electrodes for SIBs.
