Atomically dispersed metal-nitrogen sites-anchored carbon materials have been developed as effective catalysts for CO2 electroreduction(CO2 ER),but they still suffer from the imprecisely control of type and coordinati...Atomically dispersed metal-nitrogen sites-anchored carbon materials have been developed as effective catalysts for CO2 electroreduction(CO2 ER),but they still suffer from the imprecisely control of type and coordination number of N atoms bonded with central metal.Herein,we develop a family of single metal atom bonded by N atoms anchored on carbons(SAs-M-N-C,M=Fe,Co,Ni,Cu)for CO2 ER,which composed of accurate pyrrole-type M-N4 structures with isolated metal atom coordinated by four pyrrolic N atoms.Benefitting from atomically coordinated environment and specific selectivity of M-N4 centers,SAs-Ni-N-C exhibits superior CO2 ER performance with onset potential of-0.3 V,CO Faradaic efficiency(F.E.) of 98.5%at-0.7 V,along with low Tafel slope of 115 mV dec-1 and superior stability of 50 h,exceeding all the previously reported M-N-C electrocatalysts for CO2-to-CO conversion.Experimental results manifest that the different intrinsic activities of M-N4 structures in SAs-M-N-C result in the corresponding sequence of Ni> Fe> Cu> Co for CO2 ER performance.An integrated Zn-CO2 battery with Zn foil and SAs-Ni-N-C is constructed to simultaneously achieve CO2-to-CO conversion and electric energy output,which delivers a peak power density of 1.4 mW cm-2 and maximum CO F.E.of 93.3%.展开更多
Electrochemical CO_(2) reduction reaction(CO_(2)RR) into valuable formate provides a strategy for carbon neutrality.Bismuth(Bi) catalysts,attributed to their appropriate energy barrier of OCHO*intermediate,have demons...Electrochemical CO_(2) reduction reaction(CO_(2)RR) into valuable formate provides a strategy for carbon neutrality.Bismuth(Bi) catalysts,attributed to their appropriate energy barrier of OCHO*intermediate,have demonstrated substantial potential for the advancement of electrocatalytic CO_(2) reduction to formate.However,due to the weak bonding of protons(H^(*)) of Bi,the available protonate of CO_(2) on Bi is insufficient,which limits the formation of OCHO^(*).Prediction by theoretical calculation,chlorine doping can effectively promote the dissociation of H_(2)O and thus achieve effective proton supply.We prepare chlorine-doped Bi(Cl-Bi) via an electrochemical conversion strategy for electroreduction of CO_(2) .An obvious improvement of faradaic efficiency(FE) of formate(96.7% at-0.95 V vs.RHE) can be achieved on Cl-Bi,higher than that of Bi(89.4%).Meanwhile,Cl-Bi has the highest formate production rate of 275 μmol h^(-1)cm^(-2)at-0.95 V vs.RHE,which is 1.2 times higher than that of Bi(224 μmol h^(-1)cm^(-2)).In situ characterizations and kinetic analysis reveal that chlorine doping promotes the activation of H_(2)O and supply sufficient protons to promote the protonation of CO_(2) to OCHO^(*),which is consistent with theoretical calculation.The study presents an effective strategy for rational design of highly efficient electrocatalysts to promote green chemical production.展开更多
Rationally regulating the adsorption strength of reaction intermediates on the surface of copper-based electrocatalysts would influence the product selectivity in the electrochemical CO_(2)reduction reaction(eCO_(2)RR...Rationally regulating the adsorption strength of reaction intermediates on the surface of copper-based electrocatalysts would influence the product selectivity in the electrochemical CO_(2)reduction reaction(eCO_(2)RR).Herein,theoretical screening results reveal that among the twelve metals,Mg,Al,Cr,Mn,Fe,Co,Ni,Zn,Sn,Bi,Mo and Ce,the introduction of the metals Bi,Ce,Mg and Mn into CuOOH nanosheets not only modulates the Cu active center,but also leads to a certain degree of conformational distortion,resulting in an increased occupation of electrons in the antibonding state and accelerating the formation of the ratedetermining step ^(*)HCOO.In situ spectroscopies combined with theoretical calculations confirm that Bi atoms modulate the electronic structure of Cu and enhance CO_(2)activation,while Cu sites promote the adsorption of ^(*)HCOO intermediate,significantly increasing the formation of HCOOH with Faradaic efficiency exceeding 90%on the CuBiOOH.Moreover,the introduction of Mn into CuOOH nanosheets can induce the formation of key intermediates(^(*)CHO and ^(*)CO),leading to enhanced asymmetric C–C coupling to generate ethanol.Our work provides deep insights into the structural regulation strategy of Cu sites at the atomic scale for converting CO_(2)to liquid chemical products.展开更多
Acidic electrochemical CO_(2) reduction(CO_(2) RR)mitigates CO_(2) loss and energy inefficiencies but suffers from limited selectivity.Insufficient understanding of the interfacial microenvironment and cation specific...Acidic electrochemical CO_(2) reduction(CO_(2) RR)mitigates CO_(2) loss and energy inefficiencies but suffers from limited selectivity.Insufficient understanding of the interfacial microenvironment and cation specificity hinders the development of efficient interfacial design methods.Here,we integrate ab initio-derived reaction kinetics with mass transfer modeling into a multiscale framework that reproduces the bell-shaped Faradaic efficiency profile inaccessible to the Butler-Volmer equations.Our results emphasize the role of hydrogen bonding in CO_(2) activation and reveal a potential-dependent shift in the rate-determining steps.We also demonstrate that cations inhibit competing hydrogen evolution by strengthening the interfacial electric field and disrupting the hydrogen-bond network.However,their accumulation near the outer Helmholtz plane induces strong steric effects,impeding CO_(2) supply.Furthermore,the parametric analysis highlights the critical role of strategies such as pressurization and pore-confined electrolyte control in overcoming interfacial CO_(2) transport limitations,enhancing selectivity,and broadening the operating potential window.This work advances a multiscale perspective on interfacial mass transfer and cation effects,establishing a unified framework for reaction interface design in acidic CO_(2) RR.展开更多
Electrocatalytic reduction of carbon dioxide(CO_(2))to carbon monoxide(CO)is an effective strategy to achieve carbon neutrality.High selective and low-cost catalysts for the electrocatalytic reduction of CO_(2)have re...Electrocatalytic reduction of carbon dioxide(CO_(2))to carbon monoxide(CO)is an effective strategy to achieve carbon neutrality.High selective and low-cost catalysts for the electrocatalytic reduction of CO_(2)have received increasing attention.In contrast to the conventional tube furnace method,the high-temperature shock(HTS)method enables ultra-fast thermal processing,superior atomic efficiency,and a streamlined synthesis protocol,offering a simplified method for the preparation of high-performance single-atom catalysts(SACs).The reports have shown that nickel-based SACs can be synthesized quickly and conveniently using the HTS method,making their application in CO_(2)reduction reactions(CO_(2)RR)a viable and promising avenue for further exploration.In this study,the effect of heating temperature,metal loading and different nitrogen(N)sources on the catalyst morphology,coordination environment and electrocatalytic performance were investigated.Under optimal conditions,0.05Ni-DCD-C-1050 showed excellent performance in reducing CO_(2)to CO,with CO selectivity close to 100%(−0.7 to−1.0 V vs RHE)and current density as high as 130 mA/cm^(2)(−1.1 V vs RHE)in a flow cell under alkaline environment.展开更多
Electrochemical reduction of carbon dioxide(CO_(2)RR)is a promising approach to complete the carbon cycle and potentially convert CO_(2)into valuable chemicals and fuels.Cu is unique among transition metals in its abi...Electrochemical reduction of carbon dioxide(CO_(2)RR)is a promising approach to complete the carbon cycle and potentially convert CO_(2)into valuable chemicals and fuels.Cu is unique among transition metals in its ability to catalyze the CO_(2)RR and produce multi-carbon products.However,achieving high selectivity for C2+products is challenging for copper-based catalysts,as C–C coupling reactions proceed slowly.Herein,a surface modification strategy involving grafting long alkyl chains onto copper nanowires(Cu NWs)has been proposed to regulate the electronic structure of Cu surface,which facilitates*CO-*CO coupling in the CO_(2)RR.The hydrophobicity of the catalysts increases greatly after the introduction of long alkyl chains,therefore the hydrogen evolution reaction(HER)has been inhibited effectively.Such surface modification approach proves to be highly efficient and universal,with the Faradaic efficiency(FE)of C_(2)H_(4) up to 53%for the optimized Cu–SH catalyst,representing a significant enhancement compared to the pristine Cu NWs(30%).In-situ characterizations and theoretical calculations demonstrate that the different terminal groups of the grafted octadecyl chains can effectively regulate the charge density of Cu NWs interface and change the adsorption configuration of*CO intermediate.The top-adsorbed*CO intermediates(*COtop)on Cu–SH catalytic interface endow Cu–SH with the highest charge density,which effectively lowers the reaction energy barrier for*CO-*CO coupling,promoting the formation of the*OCCO intermediate,thereby enhancing the selectivity towards C_(2)H_(4).This study provides a promising method for designing efficient Cu-based catalysts with high catalytic activity and selectivity towards C2H4.展开更多
The generation of economically valuable chemicals through electrocatalytic CO_(2)reduction reaction(CO_(2)RR)is a highly attractive strategy for achieving the carbon cycle.Bismuth(Bi)is a prospective element due to th...The generation of economically valuable chemicals through electrocatalytic CO_(2)reduction reaction(CO_(2)RR)is a highly attractive strategy for achieving the carbon cycle.Bismuth(Bi)is a prospective element due to the high selectivity for formate.Researches demonstrate the Bi–O bonds have a significant effect on the key*OCHO intermediate.Herein,we report a F-doped catalyst that displays remarkable performance in generating formate in pH-universal electrolytes.Specifically,the as-prepared F-Bi/BOC@GO achieves formate Faradaic efficiencies(FEformate)around 95%in a wide range of pH from 1 to 13.6.Furthermore,at an industrial level,current density of 200 mA cm^(-2),the F-Bi/BOC@GO catalyst shows a much more stable FE_(formate)than the catalyst without introducing F.In situ Raman reveals that the doped F can greatly improve the stability of Bi–O bonds during the electroreduction process.DFT calculations further demonstrate that fluorine doping raises the energy barrier for oxygen desorption from Bi–O motifs,thus enhancing the stability of active sites.Combined with X-ray photoelectron spectroscopy(XPS),the doped F acts as an electron trapping,which may direct electrons towards Bi–Bi bonds,thus protecting the key Bi–O motif.This work reveals the critical role of fluorine in stabilizing Bi–O active centers across a wide pH range,maintaining high formate Faradaic efficiency for a longer time than the catalyst without fluorine introduction.展开更多
The atomic-level exploration of structure-property correlations poses significant challenges in establishing precise design principles for electrocatalysts targeting efficient CO_(2)conversion.This study demonstrates ...The atomic-level exploration of structure-property correlations poses significant challenges in establishing precise design principles for electrocatalysts targeting efficient CO_(2)conversion.This study demonstrates how controlled exposure of metal sites governs CO_(2)electroreduction performance through two octanuclear bismuth-oxo clusters with distinct architectures.The Bi_(8)-DMF cluster,constructed using tert–butylthiacalix[4]arene(TC4A)as the sole ligand,features two surface-exposed Bi active sites,while the dual-ligand Bi_(8)-Fc(with TC4A/ferrocene carboxylate)forms a fully encapsulated structure.Electrocatalytic tests reveal Bi_(8)-DMF achieves exceptional formate selectivity(>90%Faradaic efficiency)across a broad potential window(-0.9 V to-1.6 V vs.RHE)with 20 h stability,outperforming Bi_(8)-Fc(60%efficiency at-1.5 V).Theoretical calculations attribute Bi_(8)-DMF's superiority to exposed Bi sites that stabilize the critical*OCHO intermediate via optimized orbital interactions.This work provides crucial guidance for polynuclear catalyst design:moderate exposure of metal active sites significantly enhances CO_(2)reduction performance.展开更多
The large current density of electrochemical CO_(2)reduction towards industrial application is challenging.Herein,without strong acid and reductant,the synthesized BiVO_(4)with abundant oxygen vacancies(Ovs)exhibited ...The large current density of electrochemical CO_(2)reduction towards industrial application is challenging.Herein,without strong acid and reductant,the synthesized BiVO_(4)with abundant oxygen vacancies(Ovs)exhibited a high formate Faradaic efficiency(FE)of 97.45%(-0.9 V)and a large partial current density of-45.82 mA/cm^(2)(-1.2 V).The good performance benefits from the reconstruction of BiVO_(4)to generate active metal Bi sites,which results in the electron redistribution to boost the OCHO∗formation.In flow cells,near industrial current density of 183.94 mA/cm^(2)was achieved,with the FE of formate above 95%from 20mA/cm^(2)to 180mA/cm^(2).Our work provides a facily synthesized BiVO_(4)precatalyst for CO_(2)electroreduction.展开更多
Leveraging the interplay between the metal component and the supporting material represents a cornerstone strategy for augmenting electrocatalytic efficiency,e.g.,electrocatalytic CO_(2)reduction reaction(CO_(2)RR).He...Leveraging the interplay between the metal component and the supporting material represents a cornerstone strategy for augmenting electrocatalytic efficiency,e.g.,electrocatalytic CO_(2)reduction reaction(CO_(2)RR).Herein,we employ freestanding porous carbon fibers(PCNF)as an efficacious and stable support for the uniformly distributed SnO_(2)nanoparticles(SnO_(2)PCNF),thereby capitalizing on the synergistic support effect that arises from their strong interaction.On one hand,the interaction between the SnO_(2)nanoparticles and the carbon support optimizes the electronic configuration of the active centers.This interaction leads to a noteworthy shift of the d-band center toward stronger intermediate adsorption energy,consequently lowering the energy barrier associated with CO_(2)reduction.As a result,the Sn O_(2)PCNF realizes a remarkable CO_(2)RR performance with excellent selectivity towards formate(98.1%).On the other hand,the porous carbon fibers enable the uniform and stable dispersion of SnO_(2)nanoparticles,and this superior porous structure of carbon supports can also facilitate the exposure of the SnO_(2)nanoparticles on the reaction interface to a great extent.Consequently,adequate contact between active sites,reactants,and electrolytes can significantly increase the metal utilization,eventually bringing forth a remarkable7.09 A/mg mass activity.This work might provide a useful idea for improving the utilization rate of metals in numerous electrocatalytic reactions.展开更多
Although the potential of microenvironment modulation to enhance electricity-driven CO_(2)reduction has been recognized,substantial challenges remain,particularly in effectively integrating multiple favorable microenv...Although the potential of microenvironment modulation to enhance electricity-driven CO_(2)reduction has been recognized,substantial challenges remain,particularly in effectively integrating multiple favorable microenvironments.Herein,we synthesize CeO_(2)with abundant oxygen vacancies to effectively disperse and anchor small-sized Ag_(2)O nanoparticles(Ag_(2)O/Vo-CeO_(2)).Vo-CeO_(2)acts as a multifunctional modulator,regulating both the reaction microenvironment and the electronic structure of Ag sites,thereby boosting CO_(2)reduction(CO_(2)RR)efficiency.Its strong CO_(2)adsorption and H_(2)O dissociation capabilities facilitate the supply of CO_(2)and active^(*)H species to Ag sites.The electron-withdrawing effect of VoCeO_(2)induces polarization at interfacial Ag sites,generating Agd+species that enhance CO_(2)affinity and activation.Moreover,the electronic coupling between Vo-CeO_(2)and Ag upshifts the d-band center of Ag,optimizing COOH binding and lowering the thermodynamic barrier of the potential-determining step.Ag_(2)O/Vo-CeO_(2)delivers a consistently high Faraday efficiency(FE)of over 99% for CO production even at industrially current density(up to 365 mA cm^(-2)herein),and the operational potential window spans an astonishing 1700 m V(FE>95%).The unprecedented activity,which overcomes the trade-off between the selectivity and current density for CO_(2)RR,outperforms state-of-the-art Ag-based catalysts reported to date.These findings offer a promising pathway to develop robust CO_(2)RR catalysts and present an engineering strategy for constructing the optimal microenvironment of active sites via the synergistic effects of multifunctional modulation.展开更多
Pulsed electrolysis for CO_(2)reduction reaction has emerged as an effective method to enhance catalyst efficiency and optimize product selectivity.However,challenges remain in understanding the mechanisms of surface ...Pulsed electrolysis for CO_(2)reduction reaction has emerged as an effective method to enhance catalyst efficiency and optimize product selectivity.However,challenges remain in understanding the mechanisms of surface transformation under pulsed conditions.In this study,using in-situ time-resolved surface-enhanced Raman spectroscopy and differential electrochemical mass spectroscopy,we found local pH at the surface and Cu–O–C species that was generated during the anodic pulse played a key role in pulsed electrolysis.During the pulsed oxidation,an oxidation layer first formed,depleting OH–and lowering the local pH.When the pH was below 8.4,HCO_(3)–transformed the oxidation layer to a nanometer-thick Cu–O–C species,which is a highly reactive catalyst.In the reduction pulse,about 7.4%of the surface Cu–O–C was transformed into CO and CuOx species,enhancing CO_(2)reduction activity.Even in Ar-saturated 0.1 M KHCO_(3),through a Cu–O–C intermediate,a Faradaic efficiency of 0.17%for bicarbonate reduction to CO was observed.Our findings highlight the crucial role of the anodic pulse process in improving CO_(2)reduction activity.展开更多
The Ni single-atom catalyst dispersed on nitrogen doped graphene support has attracted much interest due to the high selectivity in electro-catalyzing CO_(2)reduction to CO,yet the chemical inertness of the metal cent...The Ni single-atom catalyst dispersed on nitrogen doped graphene support has attracted much interest due to the high selectivity in electro-catalyzing CO_(2)reduction to CO,yet the chemical inertness of the metal center renders it to exhibit electrochemical activity only under high overpotentials.Herein,we report P-and S-doped Ni single-atom catalysts,i.e.symmetric Ni_(1)/PN_(4)and asymmetric Ni1/SN_(3)C can exhibit high catalytic activity of CO_(2)reduction with stable potential windows.It is revealed that the key intermediate*COOH in CO_(2)electroreduction is stabilized by heteroatom doping,which stems from the upward shift of the axial d_(z2)orbital of the active metal Ni atom.Furthermore,we investigate the potential-dependent free energetics and dynamic properties at the electrochemical interface on the Ni1/SN3C catalyst using ab initio molecular dynamics simulations with a full explicit solvent model.Based on the potential-dependent microkinetic model,we predict that S-atom doped Ni SAC shifts the onset potential of CO_(2)electroreduction from–0.88 to–0.80 V vs.RHE,exhibiting better activity.Overall,this work provides an in-depth understanding of structure-activity relationships and atomic-level electrochemical interfaces of catalytic systems,and offers insights into the rational design of heteroatom-doped catalysts for targeted catalysis.展开更多
CO_(2)electroreduction(CO_(2)RR)represents a promising negative-carbon technology,which is in urgent need for efficient and high-selectivity catalysts.Here,a support control strategy is employed for precise surface en...CO_(2)electroreduction(CO_(2)RR)represents a promising negative-carbon technology,which is in urgent need for efficient and high-selectivity catalysts.Here,a support control strategy is employed for precise surface engineering of charge-asymmetry nanocluster catalyst(CuZnSCN),in which zinc and copper atoms together form a metal cluster loaded on sulfur and nitrogen co-etched carbon matrix.The synergistic promotion mechanism of CO_(2)RR by Cu–Zn atom interactions and sulfur–nitrogen atom doping was investigated.A CO partial current density of 74.1 mA cm^(-2)was achieved in an alkaline electrolyte,as well as a considerable CO Faraday efficiency of 97.7%.In situ XAS(X-ray absorption spectroscopy)showed that the stabilization of Cu^(+)and Zn^(2+)species in the nanoclusters and doped sulfur atoms during the CO_(2)RR process contributes to the sustained adsorption of protons and the generation and conversion of the CO.This work verifies the possibility of metal-support and intermetallic interactions to synergistically enhance electrochemical catalytic performance and provides ideas for further bimetallic cluster catalyst development.展开更多
By manipulating the distribution of surface electrons,defect engineering enables effective control over the adsorption energy between adsorbates and active sites in the CO_(2)reduction reaction(CO_(2)RR).Herein,we rep...By manipulating the distribution of surface electrons,defect engineering enables effective control over the adsorption energy between adsorbates and active sites in the CO_(2)reduction reaction(CO_(2)RR).Herein,we report a hollow indium oxide nanotube containing both oxygen vacancy and sulfur doping(V_o-Sx-In_(2)O_(3))for improved CO_(2)-to-HCOOH electroreduction and Zn-CO_(2)battery.The componential synergy significantly reduces the*OCHO formation barrier to expedite protonation process and creates a favorable electronic micro-environment for*HCOOH desorption.As a result,the CO_(2)RR performance of Vo-Sx-In_(2)O_(3)outperforms Pure-In_(2)O_(3)and V_o-In_(2)O_(3),where V_o-S53-In_(2)O_(3)exhibits a maximal HCOOH Faradaic efficiency of 92.4%at-1,2 V vs.reversible hydrogen electrode(RHE)in H-cell and above 92%over a wide window potential with high current density(119.1 mA cm^(-2)at-1.1 V vs.RHE)in flow cell.Furthermore,the rechargeable Zn-CO_(2)battery utilizing V_o-S53-In_(2)O_(3)as cathode shows a high power density of 2.29 mW cm^(-2)and a long-term stability during charge-discharge cycles.This work provides a valuable perspective to elucidate co-defective catalysts in regulating the intermediates for efficient CO_(2)RR.展开更多
Electrochemical carbon dioxide reduction reaction(CO_(2)RR)converts CO_(2) into valuable chemicals by consuming renewable electricity at mild conditions,making it a promising approach to achieving carbon neutrality.Ho...Electrochemical carbon dioxide reduction reaction(CO_(2)RR)converts CO_(2) into valuable chemicals by consuming renewable electricity at mild conditions,making it a promising approach to achieving carbon neutrality.However,the reaction of CO_(2) with hydroxide ions to form carbonates leads to low carbon utilization and energy efficiency in near-neutral or alkaline CO_(2)RR.The high concentration of protons in acidic media can effectively mitigate carbonate formation and deposition,thereby significantly minimizing carbon loss and energy consumption.Unfortunately,hydrogen evolution reaction(HER)is more kinetically favorable than CO_(2)RR in acidic media.Herein,we comprehensively overview recent progress in acidic CO_(2)RR and propose two strategies derived from the competing reaction pathways of HER and CO_(2)RR:one focuses on regulating the H+mass transport,while the other aims to modulate the intrinsic kinetic activity of CO_(2)RR.The two strategies are designed to compete for the limited active sites on the catalyst surface,inhibit side reactions,and enhance the activity and selectivity of CO_(2)RR.The representative approaches include modulating the interface electric field,constructing a local alkaline environment,and regulating competing adsorption sites.Finally,we also review the technical challenges and future perspectives of acidic CO_(2)RR coupled with membrane electrode assemblies(MEAs).展开更多
The p-block metal(In,Sn,Bi,etc.)-based electrocatalysts have exhibited excellent activity in the electrocatalytic CO_(2)reduction(ECR)to formate.However,the rapid decrease in catalytic activity caused by catalyst reco...The p-block metal(In,Sn,Bi,etc.)-based electrocatalysts have exhibited excellent activity in the electrocatalytic CO_(2)reduction(ECR)to formate.However,the rapid decrease in catalytic activity caused by catalyst reconstruction and agglomeration under ECR conditions significantly restricts their practical applications.Herein,we developed a sulfur anchoring strategy to stabilize the high-density sub-3 nm In_(2)S_(3)nanoparticles on sulfur-doped porous carbon substrates(i-In_(2)S_(3)/S-C)for formate production.Systematic characterizations evidenced that the as-prepared catalyst exhibited a strong metal sulfide-support interaction(MSSI),which effectively regulated the electronic states of In_(2)S_(3),achieving a high formate Faradaic efficiency of 91%at−0.95 V vs.RHE.More importantly,the sulfur anchoring effectively immobilized the sub-3 nm In_(2)S_(3)nanoparticles to prevent them from agglomeration.It enabled the catalysts to exhibit much higher durability than the In_(2)S_(3)samples without sulfur anchoring,demonstrating that the strong MSSI and fast charge transfer on the catalytic interface could significantly promote the structural stability of In_(2)S_(3)catalysts.These results provide a viable approach for developing efficient and stable electrocatalysts for CO_(2)reduction.展开更多
基金financial support from Zhejiang Province Basic Public Welfare Research Project(LGF19B070006)financial supports from National Natural Science Foundation of China(21922811,21878270,51702284,21961160742)+2 种基金Zhejiang Provincial Natural Science Foundation of China(LR19B060002)supported by the Fundamental Research Funds for the Central Universitiesthe Startup Foundation for Hundred-Talent Program of Zhejiang University.
文摘Atomically dispersed metal-nitrogen sites-anchored carbon materials have been developed as effective catalysts for CO2 electroreduction(CO2 ER),but they still suffer from the imprecisely control of type and coordination number of N atoms bonded with central metal.Herein,we develop a family of single metal atom bonded by N atoms anchored on carbons(SAs-M-N-C,M=Fe,Co,Ni,Cu)for CO2 ER,which composed of accurate pyrrole-type M-N4 structures with isolated metal atom coordinated by four pyrrolic N atoms.Benefitting from atomically coordinated environment and specific selectivity of M-N4 centers,SAs-Ni-N-C exhibits superior CO2 ER performance with onset potential of-0.3 V,CO Faradaic efficiency(F.E.) of 98.5%at-0.7 V,along with low Tafel slope of 115 mV dec-1 and superior stability of 50 h,exceeding all the previously reported M-N-C electrocatalysts for CO2-to-CO conversion.Experimental results manifest that the different intrinsic activities of M-N4 structures in SAs-M-N-C result in the corresponding sequence of Ni> Fe> Cu> Co for CO2 ER performance.An integrated Zn-CO2 battery with Zn foil and SAs-Ni-N-C is constructed to simultaneously achieve CO2-to-CO conversion and electric energy output,which delivers a peak power density of 1.4 mW cm-2 and maximum CO F.E.of 93.3%.
基金financially supported by the Natural Science Foundation of Shandong Province (No.ZR2022QE076)the National Natural Science Foundation of China (No.52202092)the Science and Technology Support Plan for Youth Innovation of Colleges and Universities of Shandong Province of China (No.2023KJ104)。
文摘Electrochemical CO_(2) reduction reaction(CO_(2)RR) into valuable formate provides a strategy for carbon neutrality.Bismuth(Bi) catalysts,attributed to their appropriate energy barrier of OCHO*intermediate,have demonstrated substantial potential for the advancement of electrocatalytic CO_(2) reduction to formate.However,due to the weak bonding of protons(H^(*)) of Bi,the available protonate of CO_(2) on Bi is insufficient,which limits the formation of OCHO^(*).Prediction by theoretical calculation,chlorine doping can effectively promote the dissociation of H_(2)O and thus achieve effective proton supply.We prepare chlorine-doped Bi(Cl-Bi) via an electrochemical conversion strategy for electroreduction of CO_(2) .An obvious improvement of faradaic efficiency(FE) of formate(96.7% at-0.95 V vs.RHE) can be achieved on Cl-Bi,higher than that of Bi(89.4%).Meanwhile,Cl-Bi has the highest formate production rate of 275 μmol h^(-1)cm^(-2)at-0.95 V vs.RHE,which is 1.2 times higher than that of Bi(224 μmol h^(-1)cm^(-2)).In situ characterizations and kinetic analysis reveal that chlorine doping promotes the activation of H_(2)O and supply sufficient protons to promote the protonation of CO_(2) to OCHO^(*),which is consistent with theoretical calculation.The study presents an effective strategy for rational design of highly efficient electrocatalysts to promote green chemical production.
基金supported by the Natural Science Foundation of Jilin Province(20220101051JC)the National Natural Science Foundation of China(22075099)。
文摘Rationally regulating the adsorption strength of reaction intermediates on the surface of copper-based electrocatalysts would influence the product selectivity in the electrochemical CO_(2)reduction reaction(eCO_(2)RR).Herein,theoretical screening results reveal that among the twelve metals,Mg,Al,Cr,Mn,Fe,Co,Ni,Zn,Sn,Bi,Mo and Ce,the introduction of the metals Bi,Ce,Mg and Mn into CuOOH nanosheets not only modulates the Cu active center,but also leads to a certain degree of conformational distortion,resulting in an increased occupation of electrons in the antibonding state and accelerating the formation of the ratedetermining step ^(*)HCOO.In situ spectroscopies combined with theoretical calculations confirm that Bi atoms modulate the electronic structure of Cu and enhance CO_(2)activation,while Cu sites promote the adsorption of ^(*)HCOO intermediate,significantly increasing the formation of HCOOH with Faradaic efficiency exceeding 90%on the CuBiOOH.Moreover,the introduction of Mn into CuOOH nanosheets can induce the formation of key intermediates(^(*)CHO and ^(*)CO),leading to enhanced asymmetric C–C coupling to generate ethanol.Our work provides deep insights into the structural regulation strategy of Cu sites at the atomic scale for converting CO_(2)to liquid chemical products.
基金supported by the National Natural Science Foundation of China(52394202 and 52476056)key project of the Joint Fund for Innovation and Development of Chongqing Natural Science Foundation(CSTB2022NSCQ-LZX0013)+1 种基金the Innovative Research Group Project of the National Natural Science Foundation of China(52021004)the Natural Science Foundation of Chongqing,China(CSTB2024NSCQ-MSX0915).
文摘Acidic electrochemical CO_(2) reduction(CO_(2) RR)mitigates CO_(2) loss and energy inefficiencies but suffers from limited selectivity.Insufficient understanding of the interfacial microenvironment and cation specificity hinders the development of efficient interfacial design methods.Here,we integrate ab initio-derived reaction kinetics with mass transfer modeling into a multiscale framework that reproduces the bell-shaped Faradaic efficiency profile inaccessible to the Butler-Volmer equations.Our results emphasize the role of hydrogen bonding in CO_(2) activation and reveal a potential-dependent shift in the rate-determining steps.We also demonstrate that cations inhibit competing hydrogen evolution by strengthening the interfacial electric field and disrupting the hydrogen-bond network.However,their accumulation near the outer Helmholtz plane induces strong steric effects,impeding CO_(2) supply.Furthermore,the parametric analysis highlights the critical role of strategies such as pressurization and pore-confined electrolyte control in overcoming interfacial CO_(2) transport limitations,enhancing selectivity,and broadening the operating potential window.This work advances a multiscale perspective on interfacial mass transfer and cation effects,establishing a unified framework for reaction interface design in acidic CO_(2) RR.
基金supported by the National Key R&D Program of China(2024YFB4106400)National Natural Science Foundation of China(22209200,52302331)。
文摘Electrocatalytic reduction of carbon dioxide(CO_(2))to carbon monoxide(CO)is an effective strategy to achieve carbon neutrality.High selective and low-cost catalysts for the electrocatalytic reduction of CO_(2)have received increasing attention.In contrast to the conventional tube furnace method,the high-temperature shock(HTS)method enables ultra-fast thermal processing,superior atomic efficiency,and a streamlined synthesis protocol,offering a simplified method for the preparation of high-performance single-atom catalysts(SACs).The reports have shown that nickel-based SACs can be synthesized quickly and conveniently using the HTS method,making their application in CO_(2)reduction reactions(CO_(2)RR)a viable and promising avenue for further exploration.In this study,the effect of heating temperature,metal loading and different nitrogen(N)sources on the catalyst morphology,coordination environment and electrocatalytic performance were investigated.Under optimal conditions,0.05Ni-DCD-C-1050 showed excellent performance in reducing CO_(2)to CO,with CO selectivity close to 100%(−0.7 to−1.0 V vs RHE)and current density as high as 130 mA/cm^(2)(−1.1 V vs RHE)in a flow cell under alkaline environment.
文摘Electrochemical reduction of carbon dioxide(CO_(2)RR)is a promising approach to complete the carbon cycle and potentially convert CO_(2)into valuable chemicals and fuels.Cu is unique among transition metals in its ability to catalyze the CO_(2)RR and produce multi-carbon products.However,achieving high selectivity for C2+products is challenging for copper-based catalysts,as C–C coupling reactions proceed slowly.Herein,a surface modification strategy involving grafting long alkyl chains onto copper nanowires(Cu NWs)has been proposed to regulate the electronic structure of Cu surface,which facilitates*CO-*CO coupling in the CO_(2)RR.The hydrophobicity of the catalysts increases greatly after the introduction of long alkyl chains,therefore the hydrogen evolution reaction(HER)has been inhibited effectively.Such surface modification approach proves to be highly efficient and universal,with the Faradaic efficiency(FE)of C_(2)H_(4) up to 53%for the optimized Cu–SH catalyst,representing a significant enhancement compared to the pristine Cu NWs(30%).In-situ characterizations and theoretical calculations demonstrate that the different terminal groups of the grafted octadecyl chains can effectively regulate the charge density of Cu NWs interface and change the adsorption configuration of*CO intermediate.The top-adsorbed*CO intermediates(*COtop)on Cu–SH catalytic interface endow Cu–SH with the highest charge density,which effectively lowers the reaction energy barrier for*CO-*CO coupling,promoting the formation of the*OCCO intermediate,thereby enhancing the selectivity towards C_(2)H_(4).This study provides a promising method for designing efficient Cu-based catalysts with high catalytic activity and selectivity towards C2H4.
基金supported by the National Natural Science Foundation of China(22322805,22178104,U22B20143,U24A20546)Shanghai Municipal Science and Technology Major Project+1 种基金the Shanghai Scientific and Technological Innovation Project(22dz1205900)the Fundamental Research Funds for the Central Universities,and Shanghai Rising-Star Program(23QA1402200)。
文摘The generation of economically valuable chemicals through electrocatalytic CO_(2)reduction reaction(CO_(2)RR)is a highly attractive strategy for achieving the carbon cycle.Bismuth(Bi)is a prospective element due to the high selectivity for formate.Researches demonstrate the Bi–O bonds have a significant effect on the key*OCHO intermediate.Herein,we report a F-doped catalyst that displays remarkable performance in generating formate in pH-universal electrolytes.Specifically,the as-prepared F-Bi/BOC@GO achieves formate Faradaic efficiencies(FEformate)around 95%in a wide range of pH from 1 to 13.6.Furthermore,at an industrial level,current density of 200 mA cm^(-2),the F-Bi/BOC@GO catalyst shows a much more stable FE_(formate)than the catalyst without introducing F.In situ Raman reveals that the doped F can greatly improve the stability of Bi–O bonds during the electroreduction process.DFT calculations further demonstrate that fluorine doping raises the energy barrier for oxygen desorption from Bi–O motifs,thus enhancing the stability of active sites.Combined with X-ray photoelectron spectroscopy(XPS),the doped F acts as an electron trapping,which may direct electrons towards Bi–Bi bonds,thus protecting the key Bi–O motif.This work reveals the critical role of fluorine in stabilizing Bi–O active centers across a wide pH range,maintaining high formate Faradaic efficiency for a longer time than the catalyst without fluorine introduction.
基金supported by the Natural Science Foundation of Hunan Province(No.2023JJ30650)the Central South University Innovation-Driven Research Programme(No.2023CXQD061)。
文摘The atomic-level exploration of structure-property correlations poses significant challenges in establishing precise design principles for electrocatalysts targeting efficient CO_(2)conversion.This study demonstrates how controlled exposure of metal sites governs CO_(2)electroreduction performance through two octanuclear bismuth-oxo clusters with distinct architectures.The Bi_(8)-DMF cluster,constructed using tert–butylthiacalix[4]arene(TC4A)as the sole ligand,features two surface-exposed Bi active sites,while the dual-ligand Bi_(8)-Fc(with TC4A/ferrocene carboxylate)forms a fully encapsulated structure.Electrocatalytic tests reveal Bi_(8)-DMF achieves exceptional formate selectivity(>90%Faradaic efficiency)across a broad potential window(-0.9 V to-1.6 V vs.RHE)with 20 h stability,outperforming Bi_(8)-Fc(60%efficiency at-1.5 V).Theoretical calculations attribute Bi_(8)-DMF's superiority to exposed Bi sites that stabilize the critical*OCHO intermediate via optimized orbital interactions.This work provides crucial guidance for polynuclear catalyst design:moderate exposure of metal active sites significantly enhances CO_(2)reduction performance.
基金financially supported by the Fundamental Research Funds for the Central Universities of Central South University(No.2022ZZTS0579).
文摘The large current density of electrochemical CO_(2)reduction towards industrial application is challenging.Herein,without strong acid and reductant,the synthesized BiVO_(4)with abundant oxygen vacancies(Ovs)exhibited a high formate Faradaic efficiency(FE)of 97.45%(-0.9 V)and a large partial current density of-45.82 mA/cm^(2)(-1.2 V).The good performance benefits from the reconstruction of BiVO_(4)to generate active metal Bi sites,which results in the electron redistribution to boost the OCHO∗formation.In flow cells,near industrial current density of 183.94 mA/cm^(2)was achieved,with the FE of formate above 95%from 20mA/cm^(2)to 180mA/cm^(2).Our work provides a facily synthesized BiVO_(4)precatalyst for CO_(2)electroreduction.
基金supported by the National Natural Science Foundation of China(Nos.22172099,U21A20312)Guangdong Basic and Applied Basic Research Foundation(Nos.2023A1515012776,2022B1515120084)the Shenzhen Science and Technology Program(No.RCYX20200714114535052)。
文摘Leveraging the interplay between the metal component and the supporting material represents a cornerstone strategy for augmenting electrocatalytic efficiency,e.g.,electrocatalytic CO_(2)reduction reaction(CO_(2)RR).Herein,we employ freestanding porous carbon fibers(PCNF)as an efficacious and stable support for the uniformly distributed SnO_(2)nanoparticles(SnO_(2)PCNF),thereby capitalizing on the synergistic support effect that arises from their strong interaction.On one hand,the interaction between the SnO_(2)nanoparticles and the carbon support optimizes the electronic configuration of the active centers.This interaction leads to a noteworthy shift of the d-band center toward stronger intermediate adsorption energy,consequently lowering the energy barrier associated with CO_(2)reduction.As a result,the Sn O_(2)PCNF realizes a remarkable CO_(2)RR performance with excellent selectivity towards formate(98.1%).On the other hand,the porous carbon fibers enable the uniform and stable dispersion of SnO_(2)nanoparticles,and this superior porous structure of carbon supports can also facilitate the exposure of the SnO_(2)nanoparticles on the reaction interface to a great extent.Consequently,adequate contact between active sites,reactants,and electrolytes can significantly increase the metal utilization,eventually bringing forth a remarkable7.09 A/mg mass activity.This work might provide a useful idea for improving the utilization rate of metals in numerous electrocatalytic reactions.
基金the support of this research by the Nat ional Natural Science Foundation of China(22179035)the Hei-longjiang Provincial Natural Science Foundation Joint Fund Cultivation Project(PL2024B012)the Fundamental Research Funds for the Universities of Heilongjiang Province(2023-KYYWF-1440)。
文摘Although the potential of microenvironment modulation to enhance electricity-driven CO_(2)reduction has been recognized,substantial challenges remain,particularly in effectively integrating multiple favorable microenvironments.Herein,we synthesize CeO_(2)with abundant oxygen vacancies to effectively disperse and anchor small-sized Ag_(2)O nanoparticles(Ag_(2)O/Vo-CeO_(2)).Vo-CeO_(2)acts as a multifunctional modulator,regulating both the reaction microenvironment and the electronic structure of Ag sites,thereby boosting CO_(2)reduction(CO_(2)RR)efficiency.Its strong CO_(2)adsorption and H_(2)O dissociation capabilities facilitate the supply of CO_(2)and active^(*)H species to Ag sites.The electron-withdrawing effect of VoCeO_(2)induces polarization at interfacial Ag sites,generating Agd+species that enhance CO_(2)affinity and activation.Moreover,the electronic coupling between Vo-CeO_(2)and Ag upshifts the d-band center of Ag,optimizing COOH binding and lowering the thermodynamic barrier of the potential-determining step.Ag_(2)O/Vo-CeO_(2)delivers a consistently high Faraday efficiency(FE)of over 99% for CO production even at industrially current density(up to 365 mA cm^(-2)herein),and the operational potential window spans an astonishing 1700 m V(FE>95%).The unprecedented activity,which overcomes the trade-off between the selectivity and current density for CO_(2)RR,outperforms state-of-the-art Ag-based catalysts reported to date.These findings offer a promising pathway to develop robust CO_(2)RR catalysts and present an engineering strategy for constructing the optimal microenvironment of active sites via the synergistic effects of multifunctional modulation.
基金financially supported by the National Natural Science Foundation of China (52173173, 22403047)Natural Science Foundation of Jiangsu Province (BK20220051)+2 种基金Jiangsu Province Carbon Peak and Neutrality Innovation Program (Industry tackling on prospect and key technology) (BE2022031-4, BE2022002-3)The Natural Foundation of Jiangsu Higher Education Institutions of China (23KJB430021)State Key Laboratory of Materials-Oriented Chemical Engineering (No.SKL-MCE-24A16)
文摘Pulsed electrolysis for CO_(2)reduction reaction has emerged as an effective method to enhance catalyst efficiency and optimize product selectivity.However,challenges remain in understanding the mechanisms of surface transformation under pulsed conditions.In this study,using in-situ time-resolved surface-enhanced Raman spectroscopy and differential electrochemical mass spectroscopy,we found local pH at the surface and Cu–O–C species that was generated during the anodic pulse played a key role in pulsed electrolysis.During the pulsed oxidation,an oxidation layer first formed,depleting OH–and lowering the local pH.When the pH was below 8.4,HCO_(3)–transformed the oxidation layer to a nanometer-thick Cu–O–C species,which is a highly reactive catalyst.In the reduction pulse,about 7.4%of the surface Cu–O–C was transformed into CO and CuOx species,enhancing CO_(2)reduction activity.Even in Ar-saturated 0.1 M KHCO_(3),through a Cu–O–C intermediate,a Faradaic efficiency of 0.17%for bicarbonate reduction to CO was observed.Our findings highlight the crucial role of the anodic pulse process in improving CO_(2)reduction activity.
文摘The Ni single-atom catalyst dispersed on nitrogen doped graphene support has attracted much interest due to the high selectivity in electro-catalyzing CO_(2)reduction to CO,yet the chemical inertness of the metal center renders it to exhibit electrochemical activity only under high overpotentials.Herein,we report P-and S-doped Ni single-atom catalysts,i.e.symmetric Ni_(1)/PN_(4)and asymmetric Ni1/SN_(3)C can exhibit high catalytic activity of CO_(2)reduction with stable potential windows.It is revealed that the key intermediate*COOH in CO_(2)electroreduction is stabilized by heteroatom doping,which stems from the upward shift of the axial d_(z2)orbital of the active metal Ni atom.Furthermore,we investigate the potential-dependent free energetics and dynamic properties at the electrochemical interface on the Ni1/SN3C catalyst using ab initio molecular dynamics simulations with a full explicit solvent model.Based on the potential-dependent microkinetic model,we predict that S-atom doped Ni SAC shifts the onset potential of CO_(2)electroreduction from–0.88 to–0.80 V vs.RHE,exhibiting better activity.Overall,this work provides an in-depth understanding of structure-activity relationships and atomic-level electrochemical interfaces of catalytic systems,and offers insights into the rational design of heteroatom-doped catalysts for targeted catalysis.
基金financially supported by the National Natural Science Foundation of China(No.22375019)Beijing Institute of Technology Research Fund Program for Young Scholars(No.3090012221909)
文摘CO_(2)electroreduction(CO_(2)RR)represents a promising negative-carbon technology,which is in urgent need for efficient and high-selectivity catalysts.Here,a support control strategy is employed for precise surface engineering of charge-asymmetry nanocluster catalyst(CuZnSCN),in which zinc and copper atoms together form a metal cluster loaded on sulfur and nitrogen co-etched carbon matrix.The synergistic promotion mechanism of CO_(2)RR by Cu–Zn atom interactions and sulfur–nitrogen atom doping was investigated.A CO partial current density of 74.1 mA cm^(-2)was achieved in an alkaline electrolyte,as well as a considerable CO Faraday efficiency of 97.7%.In situ XAS(X-ray absorption spectroscopy)showed that the stabilization of Cu^(+)and Zn^(2+)species in the nanoclusters and doped sulfur atoms during the CO_(2)RR process contributes to the sustained adsorption of protons and the generation and conversion of the CO.This work verifies the possibility of metal-support and intermetallic interactions to synergistically enhance electrochemical catalytic performance and provides ideas for further bimetallic cluster catalyst development.
基金supported by the Fundamental Research Funds for the Central Universities(22120230104).
文摘By manipulating the distribution of surface electrons,defect engineering enables effective control over the adsorption energy between adsorbates and active sites in the CO_(2)reduction reaction(CO_(2)RR).Herein,we report a hollow indium oxide nanotube containing both oxygen vacancy and sulfur doping(V_o-Sx-In_(2)O_(3))for improved CO_(2)-to-HCOOH electroreduction and Zn-CO_(2)battery.The componential synergy significantly reduces the*OCHO formation barrier to expedite protonation process and creates a favorable electronic micro-environment for*HCOOH desorption.As a result,the CO_(2)RR performance of Vo-Sx-In_(2)O_(3)outperforms Pure-In_(2)O_(3)and V_o-In_(2)O_(3),where V_o-S53-In_(2)O_(3)exhibits a maximal HCOOH Faradaic efficiency of 92.4%at-1,2 V vs.reversible hydrogen electrode(RHE)in H-cell and above 92%over a wide window potential with high current density(119.1 mA cm^(-2)at-1.1 V vs.RHE)in flow cell.Furthermore,the rechargeable Zn-CO_(2)battery utilizing V_o-S53-In_(2)O_(3)as cathode shows a high power density of 2.29 mW cm^(-2)and a long-term stability during charge-discharge cycles.This work provides a valuable perspective to elucidate co-defective catalysts in regulating the intermediates for efficient CO_(2)RR.
基金supported by the National Natural Science Foundation of China(52301259 and 22208019)the Research Fund Program for Young Scholars of Beijing Institute of Technology。
文摘Electrochemical carbon dioxide reduction reaction(CO_(2)RR)converts CO_(2) into valuable chemicals by consuming renewable electricity at mild conditions,making it a promising approach to achieving carbon neutrality.However,the reaction of CO_(2) with hydroxide ions to form carbonates leads to low carbon utilization and energy efficiency in near-neutral or alkaline CO_(2)RR.The high concentration of protons in acidic media can effectively mitigate carbonate formation and deposition,thereby significantly minimizing carbon loss and energy consumption.Unfortunately,hydrogen evolution reaction(HER)is more kinetically favorable than CO_(2)RR in acidic media.Herein,we comprehensively overview recent progress in acidic CO_(2)RR and propose two strategies derived from the competing reaction pathways of HER and CO_(2)RR:one focuses on regulating the H+mass transport,while the other aims to modulate the intrinsic kinetic activity of CO_(2)RR.The two strategies are designed to compete for the limited active sites on the catalyst surface,inhibit side reactions,and enhance the activity and selectivity of CO_(2)RR.The representative approaches include modulating the interface electric field,constructing a local alkaline environment,and regulating competing adsorption sites.Finally,we also review the technical challenges and future perspectives of acidic CO_(2)RR coupled with membrane electrode assemblies(MEAs).
文摘The p-block metal(In,Sn,Bi,etc.)-based electrocatalysts have exhibited excellent activity in the electrocatalytic CO_(2)reduction(ECR)to formate.However,the rapid decrease in catalytic activity caused by catalyst reconstruction and agglomeration under ECR conditions significantly restricts their practical applications.Herein,we developed a sulfur anchoring strategy to stabilize the high-density sub-3 nm In_(2)S_(3)nanoparticles on sulfur-doped porous carbon substrates(i-In_(2)S_(3)/S-C)for formate production.Systematic characterizations evidenced that the as-prepared catalyst exhibited a strong metal sulfide-support interaction(MSSI),which effectively regulated the electronic states of In_(2)S_(3),achieving a high formate Faradaic efficiency of 91%at−0.95 V vs.RHE.More importantly,the sulfur anchoring effectively immobilized the sub-3 nm In_(2)S_(3)nanoparticles to prevent them from agglomeration.It enabled the catalysts to exhibit much higher durability than the In_(2)S_(3)samples without sulfur anchoring,demonstrating that the strong MSSI and fast charge transfer on the catalytic interface could significantly promote the structural stability of In_(2)S_(3)catalysts.These results provide a viable approach for developing efficient and stable electrocatalysts for CO_(2)reduction.
