Despite their interesting applications,direct and diverse syntheses of aryl-fused 2-alkyl cyclic amines still remain challenging.Here,the concept of incorporating a C–C coupling process into the N-heteroaryl reductio...Despite their interesting applications,direct and diverse syntheses of aryl-fused 2-alkyl cyclic amines still remain challenging.Here,the concept of incorporating a C–C coupling process into the N-heteroaryl reduction was successfully applied to fulfill such a synthetic purpose.Due to our use of controllable electroreduction coupled with proton abstraction,we can report a room-temperature reductiveα-alkylation of the inert N-heteroarenes with abundantly available styrenes in an undivided Zn(+)/C(−)cell.This proceeds with good substrate compatibility and operational simplicity,utilizes cost-effective sacrificial Zn-anode,exhibits high selectivity,and does not need pressurized H2 gas and transition-metal catalysts.This current work offers a useful platform for direct construction of valuable aryl-fused 2-alkyl cyclic amines that are difficult to access with conventional methods.展开更多
Electroreduction of nitrate has been gaining wide attention in recent years owing to it's beneficial for converting nitrate into benign N_(2) from the perspective of electrocatalytic denitrification or into value-...Electroreduction of nitrate has been gaining wide attention in recent years owing to it's beneficial for converting nitrate into benign N_(2) from the perspective of electrocatalytic denitrification or into value-added ammonia from the perspective of electrocatalytic NH_(3) synthesis.By reason of the undesired formation of ammonia is dominant during electroreduction of nitrate-containing wastewater,chloride has been widely used to improve N_(2) selectivity.Nevertheless,selective electroreduction of nitrate to N2 gas in chloride-containing system poses several drawbacks.In this review,we focus on the key strategies for efficiently enhancing N_(2) selectivity of electroreduction of nitrate in chloride-free system,including optimal selection of elements,combining an active metal catalyst with another metal,manipulating the crystalline morphology and facet orientation,constructing core–shell structure catalysts,etc.Before summarizing the strategies,four possible reaction pathways of electro-reduction of nitrate to N_(2) are discussed.Overall,this review attempts to provide practical strategies for enhancing N2 selectivity without the aid of electrochlorination and highlight directions for future research for designing appropriate electrocatalyst for final electrocatalytic denitrifi-cation.展开更多
CO_(2) electrochemical reduction(CO_(2)ER)is an important research area for carbon neutralization.However,available catalysts for CO_(2) reduction are still characterized by limited stability and activity.Recently,met...CO_(2) electrochemical reduction(CO_(2)ER)is an important research area for carbon neutralization.However,available catalysts for CO_(2) reduction are still characterized by limited stability and activity.Recently,metallic bismuth(Bi)has emerged as a promising catalyst for CO_(2) ER.Herein,we report the solid cathode electroreduction of commercial micronized Bi2O3as a straightforward approach for the preparation of nanostructured Bi.At-1.1 V versus reversible hydrogen electrode in a KHCO3aqueous electrolyte,the resulting nanostructure Bi delivers a formate current density of~40 mA·cm^(-2) with a current efficiency of~86%,and the formate selectivity reaches97.6% at-0.78 V.Using nanosized Bi2O3as the precursor can further reduce the primary particle sizes of the resulting Bi,leading to a significantly increased formate selectivity at relatively low overpotentials.The high catalytic activity of nanostructured Bi is attributable to the ultrafine and interconnected Bi nanoparticles in the nanoporous structure,which exposes abundant active sites for CO_(2) electrocatalytic reduction.展开更多
The d-d orbital coupling induced by crystal-phase engineering can effectively adjust the electronic structure of electrocatalysts,thus showing significant catalytic performance,while it has been rarely explored in ele...The d-d orbital coupling induced by crystal-phase engineering can effectively adjust the electronic structure of electrocatalysts,thus showing significant catalytic performance,while it has been rarely explored in electrochemical acetonitrile reduction reaction(ARR)to date.Herein,we successfully realize the structural transformation of Pd Cu metallic aerogels(MAs)from face-centered cubic(FCC)to body-centered cubic(BCC)through annealing treatment.Specifically,the BCC Pd Cu MAs exhibit excellent ARR performance with high ethylamine selectivity of 90.91%,Faradaic efficiency of 88.60%,yield rate of 316.0 mmol h^(-1)g^(-1)_(Pd+Cu)and long-term stability for consecutive electrolysis within 20 h at-0.55 V vs.reversible hydrogen electrode,outperforming than those of FCC Pd Cu MAs.Under the membrane electrode assembly system,BCC Pd Cu MAs also demonstrate excellent ethylamine yield rate of 389.5 mmol h^(-1)g^(-1)_(Pd+Cu).Density functional theory calculation reveals that the d-d orbital coupling in BCC Pd Cu MAs results in an evident correlation effect for the interaction of Pd and Cu sites,which boosts up the Cu sites electronic activities to enhance ARR performance.Our work opens a new route to develop efficient ARR electrocatalysts from the perspective of crystalline structure transformation.展开更多
Electrocatalytic converting CO_(2) into chemical products has emerged as a promising approach to achieving carbon neutrality.Herein,we report a bismuth-based catalyst with high curvature terminal and amorphous layer w...Electrocatalytic converting CO_(2) into chemical products has emerged as a promising approach to achieving carbon neutrality.Herein,we report a bismuth-based catalyst with high curvature terminal and amorphous layer which fabricated via two-step electrodeposition achieves stable formate output in a wide voltage window of 600 mV.The Faraday efficiency(FE) of formate reached up to 99.4% at-0.8 V vs.RHE and it remained constant for more than 92 h at-15 mA cm^(-2).More intriguingly,FE formate of95.4% can be realized at a current density of industrial grade(-667.7 mA cm^(-2)) in flow cell.The special structure promoted CO_(2) adsorption and reduced its activation energy and enhanced the electric-thermal field and K^(+) enrichment which accelerated the reaction kinetics.In situ spectroscopy and theoretical calculation further confirmed that the introduction of amorphous structure is beneficial to adsorpting CO_(2)and stabling*OCHO intermediate.This work provides special insights to fabricate efficient electrocatalysts by means of structural and crystal engineering and makes efforts to realize the industrialization of bismuth-based catalysts.展开更多
Renewable energy driven N_(2) electroreduction with air as nitrogen source holds great promise for realizing scalable green ammonia production.However,relevant out-lab research is still in its infancy.Herein,a novel S...Renewable energy driven N_(2) electroreduction with air as nitrogen source holds great promise for realizing scalable green ammonia production.However,relevant out-lab research is still in its infancy.Herein,a novel Sn-based MXene/MAX hybrid with abundant Sn vacancies,Sn@Ti_(2)CTX/Ti_(2)SnC–V,was synthesized by controlled etching Sn@Ti_(2)SnC MAX phase and demonstrated as an efficient electrocatalyst for electrocatalytic N2 reduction.Due to the synergistic effect of MXene/MAX heterostructure,the existence of Sn vacancies and the highly dispersed Sn active sites,the obtained Sn@Ti2CTX/Ti_(2)SnC–V exhibits an optimal NH_(3) yield of 28.4μg h^(−1) mg_(cat)^(−1) with an excellent FE of 15.57% at−0.4 V versus reversible hydrogen electrode in 0.1 M Na_(2)SO_(4),as well as an ultra-long durability.Noticeably,this catalyst represents a satisfactory NH3 yield rate of 10.53μg h^(−1) mg^(−1) in the home-made simulation device,where commercial electrochemical photovoltaic cell was employed as power source,air and ultrapure water as feed stock.The as-proposed strategy represents great potential toward ammonia production in terms of financial cost according to the systematic technical economic analysis.This work is of significance for large-scale green ammonia production.展开更多
The global concerns of energy crisis and climate change,primarily caused by carbon dioxide(CO_(2)),are of utmost importance.Recently,the electrocatalytic CO_(2) reduction reaction(CO_(2)RR) to high value-added multi-c...The global concerns of energy crisis and climate change,primarily caused by carbon dioxide(CO_(2)),are of utmost importance.Recently,the electrocatalytic CO_(2) reduction reaction(CO_(2)RR) to high value-added multi-carbon(C_(2+)) products driven by renewable electricity has emerged as a highly promising solution to alleviate energy shortages and achieve carbon neutrality.Among these C_(2+) products,ethylene(C_(2)H_(4))holds particular importance in the petrochemical industry.Accordingly,this review aims to establish a connection between the fundamentals of electrocatalytic CO_(2) reduction reaction to ethylene(CO_(2)RRto-C_(2)H_(4)) in laboratory-scale research(lab) and its potential applications in industrial-level fabrication(fab).The review begins by summarizing the fundamental aspects,including the design strategies of high-performance Cu-based electrocatalysts and advanced electrolyzer devices.Subsequently,innovative and value-added techniques are presented to address the inherent challenges encountered during the implementations of CO_(2)RR-to-C_(2)H_(4) in industrial scenarios.Additionally,case studies of the technoeconomic analysis of the CO_(2)RR-to-C_(2)H_(4) process are discussed,taking into factors such as costeffectiveness,scalability,and market potential.The review concludes by outlining the perspectives and challenges associated with scaling up the CO_(2)RR-to-C_(2)H_(4) process.The insights presented in this review are expected to make a valuable contribution in advancing the CO_(2)RR-to-C_(2)H_(4) process from lab to fab.展开更多
Industrial CO_(2)electroreduction has received tremendous attentions for resolution of the current energy and environmental crisis,but its performance is greatly limited by mass transport at high current density.In th...Industrial CO_(2)electroreduction has received tremendous attentions for resolution of the current energy and environmental crisis,but its performance is greatly limited by mass transport at high current density.In this work,an ion‐polymer‐modified gas‐diffusion electrode is used to tackle this proton limit.It is found that gas diffusion electrode‐Nafion shows an impressive performance of 75.2%Faradaic efficiency in multicarbon products at an industrial current density of 1.16 A/cm^(2).Significantly,in‐depth electrochemical characterizations combined with in situ Raman have been used to determine the full workflow of protons,and it is found that HCO_(3)^(−)acts as a proton pool near the reaction environment,and HCO_(3)^(−)and H_(3)O^(+)are local proton donors that interact with the proton shuttle−SO_(3)^(−)from Nafion.With rich proton hopping sites that decrease the activation energy,a“Grotthuss”mechanism for proton transport in the above system has been identified rather than the“Vehicle”mechanism with a higher energy barrier.Therefore,this work could be very useful in terms of the achievement of industrial CO_(2)reduction fundamentally and practically.展开更多
Electrochemical CO_(2)reduction to formate is a potential approach to achieving global carbon neutrality.Here,Cu1Bi1bimetallic catalyst was prepared by a co-precipitation method.It has a ginger like composite structur...Electrochemical CO_(2)reduction to formate is a potential approach to achieving global carbon neutrality.Here,Cu1Bi1bimetallic catalyst was prepared by a co-precipitation method.It has a ginger like composite structure(CuO/CuBi_(2)O_(4))and exhibited a high formate faradaic efficiency of 98.07%at–0.98 V and a large current density of–56.12 mA.cm^(-2)at–1.28 V,which is twice as high as Bi2O3catalyst.Especially,high selectivity(FE^(–)_(HCOO)>85%)is maintained over a wide potential window of 500 mV.In-situ Raman measurements and structure characterization revealed that the reduced Cu1Bi1bimetallic catalyst possesses abundant Cu-Bi interfaces and residual Bi-O structures.The abundant Cu-Bi interface structures on the catalyst surface can provide abundant active sites for CO_(2)RR,while the Bi-O structures may stabilize the CO_(2)^(*–)intermediate.The synergistic effect of abundant Cu-Bi interfaces and Bi-O species promotes the efficient synthesis of formate by following the OCHO^(*)pathway.展开更多
Electrochemical CO_(2)reduction(CO_(2)RR)over molecular catalysts is a paramount approach for CO_(2)conversion to CO.Herein,we report a novel phthalocyanine-derived catalyst synthesized by a two-step method with a muc...Electrochemical CO_(2)reduction(CO_(2)RR)over molecular catalysts is a paramount approach for CO_(2)conversion to CO.Herein,we report a novel phthalocyanine-derived catalyst synthesized by a two-step method with a much improved electroconductivity.Furthermore,the catalyst contains both Ni-N4sites and highly dispersed metallic Ni nanoclusters,leading to an increased CO_(2)RR currents by two folds.Isotope labelling study and in situ spectroscopic analysis demonstrate that the existence of metallic Ni nanoclusters is the key factor for the activity enhancement and can shift the CO_(2)RR mechanism from being electron transfer(ET)-limited(forming*COO^(-))to concerted proton-electron transfer(CPET)-limited(forming CO).展开更多
Earth-abundant and nontoxic Sn-based materials have been regarded as promising catalysts for the electrochemical conversion of CO_(2)to C1 products,e.g.,CO and formate.However,it is still difficult for Snbased materia...Earth-abundant and nontoxic Sn-based materials have been regarded as promising catalysts for the electrochemical conversion of CO_(2)to C1 products,e.g.,CO and formate.However,it is still difficult for Snbased materials to obtain satisfactory performance at low-to-moderate overpotentials.Herein,a simple and facile electrospinning technique is utilized to prepare a composite of a bimetallic Sn-Co oxide/carbon matrix with a hollow nanotube structure(Sn Co-HNT).Sn Co-HNT can maintain>90%faradaic efficiencies for C1 products within a wide potential range from-0.6 VRHE to-1.2 VRHE,and a highest 94.1%selectivity towards CO in an H-type cell.Moreover,a 91.2%faradaic efficiency with a 241.3 m A cm^(-2)partial current density for C1 products could be achieved using a flow cell.According to theoretical calculations,the fusing of Sn/Co oxides on the carbon matrix accelerates electron transfer at the atomic level,causing electron deficiency of Sn centers and reversible variation between Co^(2+)and Co^(3+)centers.The synergistic effect of the Sn/Co composition improves the electron affinity of the catalyst surface,which is conducive to the adsorption and stabilization of key intermediates and eventually increases the catalytic activity in CO_(2)electroreduction.This study could provide a new strategy for the construction of oxide-derived catalysts for CO_(2)electroreduction.展开更多
Development of high-performance hydroxide-conductive membranes is a focus research subject owing to promising applications in electrochemical reduction of CO_(2)(eCO_(2)RR).However,few satisfactory membranes have been...Development of high-performance hydroxide-conductive membranes is a focus research subject owing to promising applications in electrochemical reduction of CO_(2)(eCO_(2)RR).However,few satisfactory membranes have been developed to maximize the performance of CO_(2) electrolyzers,despite its role as the core in regulating ion transport and preventing product crossover or fuel loss.Herein,we report the synthesis of alkaline anion-exchange membranes fabricated by poly(vinyl-alcohol)(PVA)and poly[(3-methyl-1-vinylimidazoliummethylsulfate)-co-(1-vinylpyrrolidone)](PQ44)for use in CO_(2) electrolysis.Owing to the unique imidazolium ring structure coupled with a three-dimensional semiinterpenetrating porous internal architecture,the PVA/PQ44-OH-membranes provide a high hydroxide conductivity(21.47 mS cm^(-1)),preferable mechanical property and thermal stability.In particular,the eCO_(2)RR used PVA/PQ44-OH^(-) as electrolyte membrane realized a charming Faradaic efficiency(88%)and partial current density(29 mA cm^(-2))at0.96 VRHE and,delivered the excellent durability over 20 h electrolysis in 0.5 mol L^(-1) KHCO_(3) electrolyte.Notably,it can even enable an ultrahigh current density beyond 100 mA cm^(-2) at^(-1).11 VRHE when the electrolyte was KOH instead,and produced the FEHCOOof 85%at a low potential of0.81 VRHE,superior to both commercial alkaline A201 and acidic Nafion117 membrane.展开更多
Regulating the selectivity toward a target hydrocarbon product is still the focus of CO_(2)electroreduction.Here,we discover that the original surface Cu species in Cu gas-diffusion electrodes plays a more important r...Regulating the selectivity toward a target hydrocarbon product is still the focus of CO_(2)electroreduction.Here,we discover that the original surface Cu species in Cu gas-diffusion electrodes plays a more important role than the surface roughness,local pH,and facet in governing the selectivity toward C_(1)or C_(2)hydrocarbons.The selectivity toward C_(2)H_(4) progressively increases,while CH_(4) decreases steadily upon lowering the Cu oxidation species fraction.At a relatively low electrodeposition voltage of 1.5 V,the Cu gas-diffusion electrode with the highest Cu^(δ+)/Cu^(0)ratio favors the pathways of∗CO hydrogenation to form CH_(4) with maximum Faradaic efficiency of 65.4%and partial current density of 228 mA cm^(−2)at−0.83 V vs RHE.At 2.0 V,the Cu gas-diffusion electrode with the lowest Cu^(δ+)/Cu^(0)ratio prefers C-C coupling to form C_(2)+products with Faradaic efficiency topping 80.1%at−0.75 V vs RHE,where the Faradaic efficiency of C_(2)H_(4) accounts for 46.4%and the partial current density of C_(2)H_(4) achieves 279 mA cm^(−2).This work demonstrates that the selectivity from CH_(4) to C_(2)H_(4) is switchable by tuning surface Cu species composition of Cu gas-diffusion electrodes.展开更多
Implant-associated infections caused by biomedical catheters severely threaten patients'health.The use of electrochemical control on NO release from benign nitrite equipped in the catheter can potentially resolve ...Implant-associated infections caused by biomedical catheters severely threaten patients'health.The use of electrochemical control on NO release from benign nitrite equipped in the catheter can potentially resolve this issue with excellent biocompatibility.Inspired by nitrite reductase,a Cu-BDC(BDC:benzene-1,4-dicarboxylic acid)catalyst with coordinated Cu(Ⅱ)sites was constructed as a heterogeneous electrocatalyst to control nitrite reduction to nitric oxide for catheter antibacteria.The combined results of in situ and ex situ tests unveil the key function of interconversion between Cu(Ⅱ)and Cu(Ⅰ)species in NO_(2)^(-)reduction to NO.After being incorporated into the actual catheter,the Cu-BDC catalyst exhibits high electrocatalytic activity toward NO_(2)^(-)reduction to NO and excellent antibacteria efficacy with a sterilizing rate of 99.9%,paving the way for the development of advanced metal-organic frameworks(MOFs)electrocatalysts for catheter antibacteria.展开更多
Simultaneously achieving high activity,selectivity and stability for electrochemical CO_(2)reduction reaction(CO_(2)RR)remains great challenges.Herein,a phosphorus-modified Sn/Sn Oxcore/shell(P-Sn/SnO_x)catalyst,deriv...Simultaneously achieving high activity,selectivity and stability for electrochemical CO_(2)reduction reaction(CO_(2)RR)remains great challenges.Herein,a phosphorus-modified Sn/Sn Oxcore/shell(P-Sn/SnO_x)catalyst,derived from in situ electrochemical reduction of an amorphous Sn(HPO_(4))_(2) pre-catalyst,exhibits high CO_(2)RR performance.The total Faradaic efficiency(FE)of C_(1) products is close to 100%in a broad potential range from-0.49 to-1.02 V vs.reversible hydrogen electrode,and a total current density of 315.0 m A cm^(-2)is achieved.Moreover,the P-Sn/SnO_(x) catalyst maintains a formate FE of~90%for 120 h.Density functional theory calculations suggest that the phosphorus-modified Sn/SnO_(x) core/shell structure effectively facilitates formate production by enhancing CO_(2)adsorption and improving free energy profile of formate formation.展开更多
Cu-based materials are ideal catalysts for CO_(2) electrocatalytic reduction reaction(CO_(2)RR) into multicarbon products.However,such reactions require stringent conditions on local environments of catalyst surfaces,...Cu-based materials are ideal catalysts for CO_(2) electrocatalytic reduction reaction(CO_(2)RR) into multicarbon products.However,such reactions require stringent conditions on local environments of catalyst surfaces,which currently are the global pressing challenges.Here,a stabilized activation of Cu^(0)/Cu^(+)-onAg interface by N_(2) cold plasma treatment was developed for improving Faradaic efficiency(FE) of CO_(2)RR into C2 products.The resultant Ag@Cu-CuN_x exhibits a C2 FE of 72% with a partial current density of-14.9 mA cm^(-2) at-1.0 V vs.RHE(reversible hydrogen electrode).Combining density functional theory(DFT) and experimental investigations,we unveiled that Cu^(0)/Cu^(+) species can be co ntrollably tu ned by the incorporation of nitrogen to form CuN_x on Ag surface,i.e.,Ag@Cu-CuN_x.This strategy enhances ^(*)CO intermediates generation and accelerates C-C coupling both thermodynamically and kinetically.The intermediates O^(*)C^(*)CO,^(*)COOH,and ^(*)CO were detected by in-situ attenuated total internal reflection surface enhanced infrared absorption spectroscopy(ATR-SEIRAS).The uncovered CO_(2)RR-into-C2 products were carried out along CO_(2)→^(*)COOH→^(*)CO→O^(*)C^(*)CO→^(*)C_(2)H_(3)O→^(*)C_(2)H_(4)O→ C_(2)H_(5)OH(or ^(*)C_(2)H_(3)O→^(*)O+C_(2)H_(4)) paths over Ag@Cu-CuN_x electrocatalyst.This work provides a new approach to design Cu-based electrocatalysts with high-efficiency,mild condition,and stable CO_(2)RR to C2 products.展开更多
Electrochemical CO reduction reaction(CORR) provides a promising approach for producing valuable multicarbon products(C_(2+)), while the low solubility of CO in aqueous solution and high energy barrier of C–C couplin...Electrochemical CO reduction reaction(CORR) provides a promising approach for producing valuable multicarbon products(C_(2+)), while the low solubility of CO in aqueous solution and high energy barrier of C–C coupling as well as the competing hydrogen evolution reaction(HER) largely limit the efficiency for C_(2+)production in CORR. Here we report an overturn on the Faradaic efficiency of CORR from being HER-dominant to C_(2+)formation-dominant over a wide potential window, accompanied by a significant activity enhancement over a Moss-like Cu catalyst via pressuring CO. With the CO pressure rising from 1 to 40 atm, the C_(2+)Faradaic efficiency and partial current density remarkably increase from 22.8%and 18.9 mA cm^(-2)to 89.7% and 116.7 mA cm^(-2), respectively. Experimental and theoretical investigations reveal that high pressure-induced high CO coverage on metallic Cu surface weakens the Cu–C bond via reducing electron transfer from Cu to adsorbed CO and restrains hydrogen adsorption, which significantly facilitates the C–C coupling while suppressing HER on the predominant Cu(111) surface, thereby boosting the CO electroreduction to C_(2+)activity.展开更多
The continued increase in population and the industrial revolution have led to an increase in atmospheric carbon dioxide(CO_(2)) concentration. Consequently, developing and implementing effective solutions to reduce C...The continued increase in population and the industrial revolution have led to an increase in atmospheric carbon dioxide(CO_(2)) concentration. Consequently, developing and implementing effective solutions to reduce CO_(2) emissions is a global priority. The electrochemical CO_(2) reduction reaction(CO_(2)RR) is strongly believed to be a promising alternative to fossil fuel-based technologies for the production of value-added chemicals. So far, the implementation of CO_(2)RR is hindered by associated electrochemical reactions, such as low selectivity, hydrogen evolution reaction(HER), and additional overpotential induced in some cases. As a result, it is necessary to conduct a timely evaluation of the state-of-the-art strategies in CO_(2)RR, with a focus on the engineering of the electrocatalytic systems. Catalyst morphology is one factor that plays a critical role in overcoming these drawbacks and significantly contributes to enhancing product selectivity and Faradaic efficiency(FE). This review article summarizes the recent advances in the rational design of electrocatalysts with various morphologies and the influence of these morphologies on CO_(2)RR. To compare literature findings in a meaningful way, the article focuses on results reported under a well-defined period and considers the first three rows of the d-block metal catalysts. The discussion typically covers the design of nanostructured catalysts and the molecular-level understanding of morphology-performance relationship in terms of activity, selectivity, and stability during CO_(2) electrolysis. Among others, it would be convenient to recommend a comprehensive discussion on the morphologies of single metals and heterostructures, with a detailed emphasis on their impact on CO_(2) conversion.展开更多
Ammonia plays an essential role in human production and life as a raw material for chemical fertilizers.The nitrate electroreduction to ammonia reaction(NO_(3)RR)has garnered attention due to its advantages over the H...Ammonia plays an essential role in human production and life as a raw material for chemical fertilizers.The nitrate electroreduction to ammonia reaction(NO_(3)RR)has garnered attention due to its advantages over the Haber-Bosch process and electrochemical nitrogen reduction reaction.Therefore,it represents a promising approach to safeguard the ecological environment by enabling the cycling of nitrogen species.This review begins by discussing the theoretical insights of the NO_(3)RR.It then summarizes recent advances in catalyst design and construction strategies,including alloying,structure engineering,surface engineering,and heterostructure engineering.Finally,the challenges and prospects in this field are presented.This review aims to guide for enhancing the efficiency of electrocatalysts in the NO_(3)RR,and offers insights for converting NO_(3)-to NH_(3).展开更多
Electroreduction of CO_(2)shows great potential for global CO_(2)utilization and uptake when collaborated with renewable electricity.Recent advances have been achieved in fundamental understanding and electrocatalyst ...Electroreduction of CO_(2)shows great potential for global CO_(2)utilization and uptake when collaborated with renewable electricity.Recent advances have been achieved in fundamental understanding and electrocatalyst development for CO_(2)electroreduction.We think this research area has progressed to the stage where significant efforts can focus on translating the obtained knowledge to the development of largescale electrolyzers,which have the potential to accelerate the transition of the current energy system into a sustainable and zero-carbon emission energy structure.In this perspective paper,we first critically evaluate the advancement of vapor-feed devices that use CO_(2)as reactants,from the point of view of industry applications.Then,by carefully comparing their performance to the state-of-the-art water electrolyzers which are well-established technology providing realistic performance targets,we looped back and discussed the remaining challenges including electrode catalysts,reaction conditions,mass transporting,membrane,device durability,operation mode,and so on.Finally,we provide perspectives on the challenges and suggest opportunities for generating fundamental knowledge and achieving technological progress toward the development of practical CO_(2)electrolyzers for the goal of building lowcarbon or/and net carbon-free economies.展开更多
基金support of the National Natural Science Foundation of China(grant no.21971071)the Natural Science Foundation of Guangdong Province(grant no.2021A1515010155).
文摘Despite their interesting applications,direct and diverse syntheses of aryl-fused 2-alkyl cyclic amines still remain challenging.Here,the concept of incorporating a C–C coupling process into the N-heteroaryl reduction was successfully applied to fulfill such a synthetic purpose.Due to our use of controllable electroreduction coupled with proton abstraction,we can report a room-temperature reductiveα-alkylation of the inert N-heteroarenes with abundantly available styrenes in an undivided Zn(+)/C(−)cell.This proceeds with good substrate compatibility and operational simplicity,utilizes cost-effective sacrificial Zn-anode,exhibits high selectivity,and does not need pressurized H2 gas and transition-metal catalysts.This current work offers a useful platform for direct construction of valuable aryl-fused 2-alkyl cyclic amines that are difficult to access with conventional methods.
基金supported by State Key Laboratory of Water Resource Protection and Utilization in Coal Mining(No.GJNY-18-73.17).
文摘Electroreduction of nitrate has been gaining wide attention in recent years owing to it's beneficial for converting nitrate into benign N_(2) from the perspective of electrocatalytic denitrification or into value-added ammonia from the perspective of electrocatalytic NH_(3) synthesis.By reason of the undesired formation of ammonia is dominant during electroreduction of nitrate-containing wastewater,chloride has been widely used to improve N_(2) selectivity.Nevertheless,selective electroreduction of nitrate to N2 gas in chloride-containing system poses several drawbacks.In this review,we focus on the key strategies for efficiently enhancing N_(2) selectivity of electroreduction of nitrate in chloride-free system,including optimal selection of elements,combining an active metal catalyst with another metal,manipulating the crystalline morphology and facet orientation,constructing core–shell structure catalysts,etc.Before summarizing the strategies,four possible reaction pathways of electro-reduction of nitrate to N_(2) are discussed.Overall,this review attempts to provide practical strategies for enhancing N2 selectivity without the aid of electrochlorination and highlight directions for future research for designing appropriate electrocatalyst for final electrocatalytic denitrifi-cation.
基金financially supported by the National Natural Science Foundation of China(Nos.22072110 and 21872107)the Key Research and Development Projects of Hubei Province,China(2022BAA083)。
文摘CO_(2) electrochemical reduction(CO_(2)ER)is an important research area for carbon neutralization.However,available catalysts for CO_(2) reduction are still characterized by limited stability and activity.Recently,metallic bismuth(Bi)has emerged as a promising catalyst for CO_(2) ER.Herein,we report the solid cathode electroreduction of commercial micronized Bi2O3as a straightforward approach for the preparation of nanostructured Bi.At-1.1 V versus reversible hydrogen electrode in a KHCO3aqueous electrolyte,the resulting nanostructure Bi delivers a formate current density of~40 mA·cm^(-2) with a current efficiency of~86%,and the formate selectivity reaches97.6% at-0.78 V.Using nanosized Bi2O3as the precursor can further reduce the primary particle sizes of the resulting Bi,leading to a significantly increased formate selectivity at relatively low overpotentials.The high catalytic activity of nanostructured Bi is attributable to the ultrafine and interconnected Bi nanoparticles in the nanoporous structure,which exposes abundant active sites for CO_(2) electrocatalytic reduction.
基金financially supported by the National Natural Science Foundation of China(Grant Nos.52161135302,22105087)the Postdoctoral Research Foundation of China(Grant No.2022M721360)the Natural Science Foundation of Jiangsu Province(Grant No.BK20210446)。
文摘The d-d orbital coupling induced by crystal-phase engineering can effectively adjust the electronic structure of electrocatalysts,thus showing significant catalytic performance,while it has been rarely explored in electrochemical acetonitrile reduction reaction(ARR)to date.Herein,we successfully realize the structural transformation of Pd Cu metallic aerogels(MAs)from face-centered cubic(FCC)to body-centered cubic(BCC)through annealing treatment.Specifically,the BCC Pd Cu MAs exhibit excellent ARR performance with high ethylamine selectivity of 90.91%,Faradaic efficiency of 88.60%,yield rate of 316.0 mmol h^(-1)g^(-1)_(Pd+Cu)and long-term stability for consecutive electrolysis within 20 h at-0.55 V vs.reversible hydrogen electrode,outperforming than those of FCC Pd Cu MAs.Under the membrane electrode assembly system,BCC Pd Cu MAs also demonstrate excellent ethylamine yield rate of 389.5 mmol h^(-1)g^(-1)_(Pd+Cu).Density functional theory calculation reveals that the d-d orbital coupling in BCC Pd Cu MAs results in an evident correlation effect for the interaction of Pd and Cu sites,which boosts up the Cu sites electronic activities to enhance ARR performance.Our work opens a new route to develop efficient ARR electrocatalysts from the perspective of crystalline structure transformation.
基金financial support from the Zhejiang Provincial Natural Science Foundation of China(LQ22B060007)the National Natural Science Foundation of China(22206042)+2 种基金the Scientific Research Start-up of Hangzhou Normal University(2021GDL014)the Hebei Natural Science Foundation(E2021203047)the Hebei Provincial Foundation for Returness(C20200369)。
文摘Electrocatalytic converting CO_(2) into chemical products has emerged as a promising approach to achieving carbon neutrality.Herein,we report a bismuth-based catalyst with high curvature terminal and amorphous layer which fabricated via two-step electrodeposition achieves stable formate output in a wide voltage window of 600 mV.The Faraday efficiency(FE) of formate reached up to 99.4% at-0.8 V vs.RHE and it remained constant for more than 92 h at-15 mA cm^(-2).More intriguingly,FE formate of95.4% can be realized at a current density of industrial grade(-667.7 mA cm^(-2)) in flow cell.The special structure promoted CO_(2) adsorption and reduced its activation energy and enhanced the electric-thermal field and K^(+) enrichment which accelerated the reaction kinetics.In situ spectroscopy and theoretical calculation further confirmed that the introduction of amorphous structure is beneficial to adsorpting CO_(2)and stabling*OCHO intermediate.This work provides special insights to fabricate efficient electrocatalysts by means of structural and crystal engineering and makes efforts to realize the industrialization of bismuth-based catalysts.
基金This work was supported by the National Natural Science Foundation of China(Nos.22308139,52071171,52202248)Natural Science Foundation of Liaoning Province(2023-MS-140)+11 种基金Liaoning BaiQianWan Talents Program(LNBQW2018B0048)Shenyang Science and Technology Project(21-108-9-04)Young Scientific and Technological Talents Project of the Department of Education of Liaoning Province(LQN202008)Key Research Project of Department of Education of Liaoning Province(LJKZZ20220015)Foundation of State Key Laboratory of Clean and Efficient Coal Utilization,Taiyuan University of Technology(MJNYSKL202301)Foundation of State Key Laboratory of High-efficiency Utilization of Coal and Green Chemical Engineering(KF2023006)Anhui Province Key Laboratory of Coal Clean Conversion and High Valued Utilization,Anhui University of Technology(CHV22-05)Australian Research Council(ARC)through Future Fellowship(FT210100298,FT210100806)Discovery Project(DP220100603)Linkage Project(LP210100467,LP210200504,LP210200345,LP220100088)Industrial Transformation Training Centre(IC180100005)schemesthe Australian Government through the Cooperative Research Centres Projects(CRCPXIII000077).
文摘Renewable energy driven N_(2) electroreduction with air as nitrogen source holds great promise for realizing scalable green ammonia production.However,relevant out-lab research is still in its infancy.Herein,a novel Sn-based MXene/MAX hybrid with abundant Sn vacancies,Sn@Ti_(2)CTX/Ti_(2)SnC–V,was synthesized by controlled etching Sn@Ti_(2)SnC MAX phase and demonstrated as an efficient electrocatalyst for electrocatalytic N2 reduction.Due to the synergistic effect of MXene/MAX heterostructure,the existence of Sn vacancies and the highly dispersed Sn active sites,the obtained Sn@Ti2CTX/Ti_(2)SnC–V exhibits an optimal NH_(3) yield of 28.4μg h^(−1) mg_(cat)^(−1) with an excellent FE of 15.57% at−0.4 V versus reversible hydrogen electrode in 0.1 M Na_(2)SO_(4),as well as an ultra-long durability.Noticeably,this catalyst represents a satisfactory NH3 yield rate of 10.53μg h^(−1) mg^(−1) in the home-made simulation device,where commercial electrochemical photovoltaic cell was employed as power source,air and ultrapure water as feed stock.The as-proposed strategy represents great potential toward ammonia production in terms of financial cost according to the systematic technical economic analysis.This work is of significance for large-scale green ammonia production.
基金supported by Zhejiang Provincial Department of Science and Technology under its Provincial Key Laboratory Program(2020E10018)the financial support from Fundamental Research Funds for the Central Universities(2022LHJH01-03,2022ZFJH04,2022QZJH14)+5 种基金Pioneer R&D Program of Zhejiang Province(2022C03040)the financial aid from National Natural Science Foundation of China(22005266)Zhejiang Provincial Natural Science Foundation(LR21E020003)Fundamental Research Funds for the Central Universities(2021FZZX001-09)supported by the Royal Academy of Engineering under the Chairs in Emerging Technologies scheme(CiET2021_17)University of Nottingham Ningbo China for providing a full PhD scholarship。
文摘The global concerns of energy crisis and climate change,primarily caused by carbon dioxide(CO_(2)),are of utmost importance.Recently,the electrocatalytic CO_(2) reduction reaction(CO_(2)RR) to high value-added multi-carbon(C_(2+)) products driven by renewable electricity has emerged as a highly promising solution to alleviate energy shortages and achieve carbon neutrality.Among these C_(2+) products,ethylene(C_(2)H_(4))holds particular importance in the petrochemical industry.Accordingly,this review aims to establish a connection between the fundamentals of electrocatalytic CO_(2) reduction reaction to ethylene(CO_(2)RRto-C_(2)H_(4)) in laboratory-scale research(lab) and its potential applications in industrial-level fabrication(fab).The review begins by summarizing the fundamental aspects,including the design strategies of high-performance Cu-based electrocatalysts and advanced electrolyzer devices.Subsequently,innovative and value-added techniques are presented to address the inherent challenges encountered during the implementations of CO_(2)RR-to-C_(2)H_(4) in industrial scenarios.Additionally,case studies of the technoeconomic analysis of the CO_(2)RR-to-C_(2)H_(4) process are discussed,taking into factors such as costeffectiveness,scalability,and market potential.The review concludes by outlining the perspectives and challenges associated with scaling up the CO_(2)RR-to-C_(2)H_(4) process.The insights presented in this review are expected to make a valuable contribution in advancing the CO_(2)RR-to-C_(2)H_(4) process from lab to fab.
基金National Key R&D Program of China,Grant/Award Number:2021YFF0500700Fundamental Research Funds for the Central Universities,Grant/Award Numbers:30921013103,30920041113+1 种基金Jiangsu Natural Science Foundation,Grant/Award Number:BK20190460National Natural Science Foundation of China,Grant/Award Numbers:51888103,52006105,92163124。
文摘Industrial CO_(2)electroreduction has received tremendous attentions for resolution of the current energy and environmental crisis,but its performance is greatly limited by mass transport at high current density.In this work,an ion‐polymer‐modified gas‐diffusion electrode is used to tackle this proton limit.It is found that gas diffusion electrode‐Nafion shows an impressive performance of 75.2%Faradaic efficiency in multicarbon products at an industrial current density of 1.16 A/cm^(2).Significantly,in‐depth electrochemical characterizations combined with in situ Raman have been used to determine the full workflow of protons,and it is found that HCO_(3)^(−)acts as a proton pool near the reaction environment,and HCO_(3)^(−)and H_(3)O^(+)are local proton donors that interact with the proton shuttle−SO_(3)^(−)from Nafion.With rich proton hopping sites that decrease the activation energy,a“Grotthuss”mechanism for proton transport in the above system has been identified rather than the“Vehicle”mechanism with a higher energy barrier.Therefore,this work could be very useful in terms of the achievement of industrial CO_(2)reduction fundamentally and practically.
基金financially supported by the National Natural Science Foundation of China(22172082,21978137,and 21878162)the Natural Science Foundation of Tianjin(20JCZDJC00770)+1 种基金the NCC Fund(NCC2020FH05)the Fundamental Research Funds for the Central Universities。
文摘Electrochemical CO_(2)reduction to formate is a potential approach to achieving global carbon neutrality.Here,Cu1Bi1bimetallic catalyst was prepared by a co-precipitation method.It has a ginger like composite structure(CuO/CuBi_(2)O_(4))and exhibited a high formate faradaic efficiency of 98.07%at–0.98 V and a large current density of–56.12 mA.cm^(-2)at–1.28 V,which is twice as high as Bi2O3catalyst.Especially,high selectivity(FE^(–)_(HCOO)>85%)is maintained over a wide potential window of 500 mV.In-situ Raman measurements and structure characterization revealed that the reduced Cu1Bi1bimetallic catalyst possesses abundant Cu-Bi interfaces and residual Bi-O structures.The abundant Cu-Bi interface structures on the catalyst surface can provide abundant active sites for CO_(2)RR,while the Bi-O structures may stabilize the CO_(2)^(*–)intermediate.The synergistic effect of abundant Cu-Bi interfaces and Bi-O species promotes the efficient synthesis of formate by following the OCHO^(*)pathway.
基金sponsored by the Program for Professor of Special Appointment(Eastern Scholar)at Shanghai Institutions of Higher Learning and Shanghai Sailing Program(19YF1410600)。
文摘Electrochemical CO_(2)reduction(CO_(2)RR)over molecular catalysts is a paramount approach for CO_(2)conversion to CO.Herein,we report a novel phthalocyanine-derived catalyst synthesized by a two-step method with a much improved electroconductivity.Furthermore,the catalyst contains both Ni-N4sites and highly dispersed metallic Ni nanoclusters,leading to an increased CO_(2)RR currents by two folds.Isotope labelling study and in situ spectroscopic analysis demonstrate that the existence of metallic Ni nanoclusters is the key factor for the activity enhancement and can shift the CO_(2)RR mechanism from being electron transfer(ET)-limited(forming*COO^(-))to concerted proton-electron transfer(CPET)-limited(forming CO).
基金supported by the National Natural Science Foundation of China(U21A20312,22172099,21975162,51902209)the Natural Science Foundation of Guangdong(2020A1515010840)the Shenzhen Science and Technology Program(SGDX20201103095802006,RCBS20200714114819161,JCYJ20190808111801674,JCYJ20200109105803806,RCYX20200714114535052)。
文摘Earth-abundant and nontoxic Sn-based materials have been regarded as promising catalysts for the electrochemical conversion of CO_(2)to C1 products,e.g.,CO and formate.However,it is still difficult for Snbased materials to obtain satisfactory performance at low-to-moderate overpotentials.Herein,a simple and facile electrospinning technique is utilized to prepare a composite of a bimetallic Sn-Co oxide/carbon matrix with a hollow nanotube structure(Sn Co-HNT).Sn Co-HNT can maintain>90%faradaic efficiencies for C1 products within a wide potential range from-0.6 VRHE to-1.2 VRHE,and a highest 94.1%selectivity towards CO in an H-type cell.Moreover,a 91.2%faradaic efficiency with a 241.3 m A cm^(-2)partial current density for C1 products could be achieved using a flow cell.According to theoretical calculations,the fusing of Sn/Co oxides on the carbon matrix accelerates electron transfer at the atomic level,causing electron deficiency of Sn centers and reversible variation between Co^(2+)and Co^(3+)centers.The synergistic effect of the Sn/Co composition improves the electron affinity of the catalyst surface,which is conducive to the adsorption and stabilization of key intermediates and eventually increases the catalytic activity in CO_(2)electroreduction.This study could provide a new strategy for the construction of oxide-derived catalysts for CO_(2)electroreduction.
基金support from the“Scientific and Technical Innovation Action Plan”Basic Research Field of Shanghai Science and Technology Committee (19JC1410500)the National Natural Science Foundation of China (21972017).
文摘Development of high-performance hydroxide-conductive membranes is a focus research subject owing to promising applications in electrochemical reduction of CO_(2)(eCO_(2)RR).However,few satisfactory membranes have been developed to maximize the performance of CO_(2) electrolyzers,despite its role as the core in regulating ion transport and preventing product crossover or fuel loss.Herein,we report the synthesis of alkaline anion-exchange membranes fabricated by poly(vinyl-alcohol)(PVA)and poly[(3-methyl-1-vinylimidazoliummethylsulfate)-co-(1-vinylpyrrolidone)](PQ44)for use in CO_(2) electrolysis.Owing to the unique imidazolium ring structure coupled with a three-dimensional semiinterpenetrating porous internal architecture,the PVA/PQ44-OH-membranes provide a high hydroxide conductivity(21.47 mS cm^(-1)),preferable mechanical property and thermal stability.In particular,the eCO_(2)RR used PVA/PQ44-OH^(-) as electrolyte membrane realized a charming Faradaic efficiency(88%)and partial current density(29 mA cm^(-2))at0.96 VRHE and,delivered the excellent durability over 20 h electrolysis in 0.5 mol L^(-1) KHCO_(3) electrolyte.Notably,it can even enable an ultrahigh current density beyond 100 mA cm^(-2) at^(-1).11 VRHE when the electrolyte was KOH instead,and produced the FEHCOOof 85%at a low potential of0.81 VRHE,superior to both commercial alkaline A201 and acidic Nafion117 membrane.
基金partially financially supported by NSF CBET-2033343.J.Z.thanks the support from National Natural Science Foundation of China(52172293,51772072,and 51672065)the Fundamental Research Funds for the Central Universities(JZ2021HGQB0282 and PA2021GDSK0088)+3 种基金financial support from the Key R&D Projects of Anhui Province(202104b11020016)the 111 Project(B18018)the National Synchrotron Light Source II,a U.S.Department of Energy(DOE)Office of Science User Facility operated for the DOE Office of Science by Brookhaven National Laboratory under Contract No.DE-SC0012704the use of facilities within the Eyring Materials Center at Arizona State University supported in part by NNCI-ECCS-1542160.
文摘Regulating the selectivity toward a target hydrocarbon product is still the focus of CO_(2)electroreduction.Here,we discover that the original surface Cu species in Cu gas-diffusion electrodes plays a more important role than the surface roughness,local pH,and facet in governing the selectivity toward C_(1)or C_(2)hydrocarbons.The selectivity toward C_(2)H_(4) progressively increases,while CH_(4) decreases steadily upon lowering the Cu oxidation species fraction.At a relatively low electrodeposition voltage of 1.5 V,the Cu gas-diffusion electrode with the highest Cu^(δ+)/Cu^(0)ratio favors the pathways of∗CO hydrogenation to form CH_(4) with maximum Faradaic efficiency of 65.4%and partial current density of 228 mA cm^(−2)at−0.83 V vs RHE.At 2.0 V,the Cu gas-diffusion electrode with the lowest Cu^(δ+)/Cu^(0)ratio prefers C-C coupling to form C_(2)+products with Faradaic efficiency topping 80.1%at−0.75 V vs RHE,where the Faradaic efficiency of C_(2)H_(4) accounts for 46.4%and the partial current density of C_(2)H_(4) achieves 279 mA cm^(−2).This work demonstrates that the selectivity from CH_(4) to C_(2)H_(4) is switchable by tuning surface Cu species composition of Cu gas-diffusion electrodes.
基金the financial support from National Postdoctoral Science Foundation of China(Nos.2021M702436 and BX2021211)Haihe Laboratory of Sustainable Chemical Transformations+1 种基金National Natural Science Foundation of China(Nos.22101202 and 22071173)Tianjin Science and Technology Programme(Nos.20JCJQJC00050 and 22ZYJDSS00060)。
文摘Implant-associated infections caused by biomedical catheters severely threaten patients'health.The use of electrochemical control on NO release from benign nitrite equipped in the catheter can potentially resolve this issue with excellent biocompatibility.Inspired by nitrite reductase,a Cu-BDC(BDC:benzene-1,4-dicarboxylic acid)catalyst with coordinated Cu(Ⅱ)sites was constructed as a heterogeneous electrocatalyst to control nitrite reduction to nitric oxide for catheter antibacteria.The combined results of in situ and ex situ tests unveil the key function of interconversion between Cu(Ⅱ)and Cu(Ⅰ)species in NO_(2)^(-)reduction to NO.After being incorporated into the actual catheter,the Cu-BDC catalyst exhibits high electrocatalytic activity toward NO_(2)^(-)reduction to NO and excellent antibacteria efficacy with a sterilizing rate of 99.9%,paving the way for the development of advanced metal-organic frameworks(MOFs)electrocatalysts for catheter antibacteria.
基金supported by the National Key R&D Program of China (2021YFA1501503)the National Natural Science Foundation of China (22125205,22002155,22002158,92045302)+5 种基金the“Transformational Technologies for Clean Energy and Demonstration”Strategic Priority Research Program of the Chinese Academy of Sciences (XDA21070613)the Fundamental Research Funds for the Central Universities (20720220008)the China Postdoctoral Science Foundation (2019M661142)the Natural Science Foundation of Liaoning Province (2021-MS-022)the High-Level Talents Innovation Project of Dalian City (2020RQ038)the support from the Photon Science Center for Carbon Neutrality。
文摘Simultaneously achieving high activity,selectivity and stability for electrochemical CO_(2)reduction reaction(CO_(2)RR)remains great challenges.Herein,a phosphorus-modified Sn/Sn Oxcore/shell(P-Sn/SnO_x)catalyst,derived from in situ electrochemical reduction of an amorphous Sn(HPO_(4))_(2) pre-catalyst,exhibits high CO_(2)RR performance.The total Faradaic efficiency(FE)of C_(1) products is close to 100%in a broad potential range from-0.49 to-1.02 V vs.reversible hydrogen electrode,and a total current density of 315.0 m A cm^(-2)is achieved.Moreover,the P-Sn/SnO_(x) catalyst maintains a formate FE of~90%for 120 h.Density functional theory calculations suggest that the phosphorus-modified Sn/SnO_(x) core/shell structure effectively facilitates formate production by enhancing CO_(2)adsorption and improving free energy profile of formate formation.
基金the National Natural Science Foundation of China (21902017)the Foundation of technological innovation and application development of Chongqing (cstc2021jscxmsxm X0308, CSTB2022BSXM-JCX0132)+1 种基金the Youth project of science and technology research program of Chongqing Education Commission of China (KJQN20211107)the Scientific Research Foundation of Chongqing University of Technology (2020ZDZ022, 2021PYZ13)。
文摘Cu-based materials are ideal catalysts for CO_(2) electrocatalytic reduction reaction(CO_(2)RR) into multicarbon products.However,such reactions require stringent conditions on local environments of catalyst surfaces,which currently are the global pressing challenges.Here,a stabilized activation of Cu^(0)/Cu^(+)-onAg interface by N_(2) cold plasma treatment was developed for improving Faradaic efficiency(FE) of CO_(2)RR into C2 products.The resultant Ag@Cu-CuN_x exhibits a C2 FE of 72% with a partial current density of-14.9 mA cm^(-2) at-1.0 V vs.RHE(reversible hydrogen electrode).Combining density functional theory(DFT) and experimental investigations,we unveiled that Cu^(0)/Cu^(+) species can be co ntrollably tu ned by the incorporation of nitrogen to form CuN_x on Ag surface,i.e.,Ag@Cu-CuN_x.This strategy enhances ^(*)CO intermediates generation and accelerates C-C coupling both thermodynamically and kinetically.The intermediates O^(*)C^(*)CO,^(*)COOH,and ^(*)CO were detected by in-situ attenuated total internal reflection surface enhanced infrared absorption spectroscopy(ATR-SEIRAS).The uncovered CO_(2)RR-into-C2 products were carried out along CO_(2)→^(*)COOH→^(*)CO→O^(*)C^(*)CO→^(*)C_(2)H_(3)O→^(*)C_(2)H_(4)O→ C_(2)H_(5)OH(or ^(*)C_(2)H_(3)O→^(*)O+C_(2)H_(4)) paths over Ag@Cu-CuN_x electrocatalyst.This work provides a new approach to design Cu-based electrocatalysts with high-efficiency,mild condition,and stable CO_(2)RR to C2 products.
基金financial support from the National Key R&D Program of China (Nos. 2022YFA1504500, 2022YFA1503100)the National Natural Science Foundation of China (Nos. 21988101, 21890753, 22225204, 92145301, 22002160 and 22272174)+4 种基金the Strategic Priority Research Program of the Chinese Academy of Sciences (No. XDB36030200)the CAS Project for Young Scientists in Basic Research (No. YSBR-028)the Fundamental Research Funds for the Central Universities (No. 20720220008)the Dalian National Lab for Clean Energy (DNL Cooperation Fund 202001)the Innovation Research Fund Project of DICP (No. DICP I202016)。
文摘Electrochemical CO reduction reaction(CORR) provides a promising approach for producing valuable multicarbon products(C_(2+)), while the low solubility of CO in aqueous solution and high energy barrier of C–C coupling as well as the competing hydrogen evolution reaction(HER) largely limit the efficiency for C_(2+)production in CORR. Here we report an overturn on the Faradaic efficiency of CORR from being HER-dominant to C_(2+)formation-dominant over a wide potential window, accompanied by a significant activity enhancement over a Moss-like Cu catalyst via pressuring CO. With the CO pressure rising from 1 to 40 atm, the C_(2+)Faradaic efficiency and partial current density remarkably increase from 22.8%and 18.9 mA cm^(-2)to 89.7% and 116.7 mA cm^(-2), respectively. Experimental and theoretical investigations reveal that high pressure-induced high CO coverage on metallic Cu surface weakens the Cu–C bond via reducing electron transfer from Cu to adsorbed CO and restrains hydrogen adsorption, which significantly facilitates the C–C coupling while suppressing HER on the predominant Cu(111) surface, thereby boosting the CO electroreduction to C_(2+)activity.
文摘The continued increase in population and the industrial revolution have led to an increase in atmospheric carbon dioxide(CO_(2)) concentration. Consequently, developing and implementing effective solutions to reduce CO_(2) emissions is a global priority. The electrochemical CO_(2) reduction reaction(CO_(2)RR) is strongly believed to be a promising alternative to fossil fuel-based technologies for the production of value-added chemicals. So far, the implementation of CO_(2)RR is hindered by associated electrochemical reactions, such as low selectivity, hydrogen evolution reaction(HER), and additional overpotential induced in some cases. As a result, it is necessary to conduct a timely evaluation of the state-of-the-art strategies in CO_(2)RR, with a focus on the engineering of the electrocatalytic systems. Catalyst morphology is one factor that plays a critical role in overcoming these drawbacks and significantly contributes to enhancing product selectivity and Faradaic efficiency(FE). This review article summarizes the recent advances in the rational design of electrocatalysts with various morphologies and the influence of these morphologies on CO_(2)RR. To compare literature findings in a meaningful way, the article focuses on results reported under a well-defined period and considers the first three rows of the d-block metal catalysts. The discussion typically covers the design of nanostructured catalysts and the molecular-level understanding of morphology-performance relationship in terms of activity, selectivity, and stability during CO_(2) electrolysis. Among others, it would be convenient to recommend a comprehensive discussion on the morphologies of single metals and heterostructures, with a detailed emphasis on their impact on CO_(2) conversion.
基金supported by the National Natural Science Foundation of China(22202151)Fundamental Research Program of Shanxi Province(202203021212243)。
文摘Ammonia plays an essential role in human production and life as a raw material for chemical fertilizers.The nitrate electroreduction to ammonia reaction(NO_(3)RR)has garnered attention due to its advantages over the Haber-Bosch process and electrochemical nitrogen reduction reaction.Therefore,it represents a promising approach to safeguard the ecological environment by enabling the cycling of nitrogen species.This review begins by discussing the theoretical insights of the NO_(3)RR.It then summarizes recent advances in catalyst design and construction strategies,including alloying,structure engineering,surface engineering,and heterostructure engineering.Finally,the challenges and prospects in this field are presented.This review aims to guide for enhancing the efficiency of electrocatalysts in the NO_(3)RR,and offers insights for converting NO_(3)-to NH_(3).
基金financially supported by the Zhejiang Energy Group Co.,Ltd.(ZNKJ-2021-111)Zhejiang Province key research and development program(2022C03040)。
文摘Electroreduction of CO_(2)shows great potential for global CO_(2)utilization and uptake when collaborated with renewable electricity.Recent advances have been achieved in fundamental understanding and electrocatalyst development for CO_(2)electroreduction.We think this research area has progressed to the stage where significant efforts can focus on translating the obtained knowledge to the development of largescale electrolyzers,which have the potential to accelerate the transition of the current energy system into a sustainable and zero-carbon emission energy structure.In this perspective paper,we first critically evaluate the advancement of vapor-feed devices that use CO_(2)as reactants,from the point of view of industry applications.Then,by carefully comparing their performance to the state-of-the-art water electrolyzers which are well-established technology providing realistic performance targets,we looped back and discussed the remaining challenges including electrode catalysts,reaction conditions,mass transporting,membrane,device durability,operation mode,and so on.Finally,we provide perspectives on the challenges and suggest opportunities for generating fundamental knowledge and achieving technological progress toward the development of practical CO_(2)electrolyzers for the goal of building lowcarbon or/and net carbon-free economies.