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
Electrocatalytic conversion of carbon dioxide(CO_(2))into formate offers a sustainable pathway to mitigate environmental degradation and the energy crisis.Tin(Sn)-based materials are promising electrocatalysts for CO_...Electrocatalytic conversion of carbon dioxide(CO_(2))into formate offers a sustainable pathway to mitigate environmental degradation and the energy crisis.Tin(Sn)-based materials are promising electrocatalysts for CO_(2)reduction to formate;however,their efficiency is limited by weak CO_(2)adsorption and activation,as well as sluggish reaction kinetics.In this work,we designed an intercrossing nanoporous Cu_(6)Sn_(5)/Sn intermetallic heterojunction via a scalable alloying-etching protocol.The resulting Cu_(6)Sn_(5)/Sn catalyst with abundant interfacial sites exhibited enhanced formate selectivity(60.79%)at−0.93 V versus the reversible hydrogen electrode(RHE),together with a high partial current density of 12.56 mA/cm^(2)and stable operation for 16 h.The modulated electronic structure of Cu_(6)Sn_(5)coupled with the robust interfacial interaction between Sn and Cu_(6)Sn_(5)synergistically promoted CO_(2)adsorption and activation,thereby improving CO_(2)reduction reaction(CO_(2)RR)performance.Electrochemical measurements and in situ infrared spectroscopy confirmed that the dual-phase interfaces facilitate H_(2)O decomposition and the generation of abundant*H intermediates,which in turn accelerate the protonation of CO_(2)to formate.This work highlights a scalable strategy for constructing intermetallic heterojunction catalysts that combine facile synthesis,reproducibility,and superior catalytic activity for CO_(2)RR.展开更多
Electrochemical CO_(2) reduction is a sustainable method for producing fuels and chemicals using renewable energy sources.Sn is a widely employed catalyst for formate production,with its performance closely influenced...Electrochemical CO_(2) reduction is a sustainable method for producing fuels and chemicals using renewable energy sources.Sn is a widely employed catalyst for formate production,with its performance closely influenced by the catalyst ink formulations and reac-tion conditions.The present study explores the influence of catalyst loading,current density,and binder choice on Sn-based CO_(2) reduc-tion systems.Decreasing catalyst loading from 10 to 1.685 mg·cm^(-2) and increasing current density in highly concentrated bicarbonate solutions significantly enhances formate selectivity,achieving 88%faradaic efficiency(FE)at a current density of−30 mA·cm^(-2) with a cathodic potential of−1.22 V vs.reversible hydrogen electrode(RHE)and a catalyst loading of 1.685 mg·cm^(-2).This low-loading strategy not only reduces catalyst costs but also enhances surface utilization and suppresses the hydrogen evolution reaction.Nafion enhances formate production when applied as a surface coating rather than pre-mixed in the ink,as evidenced by improved faradaic efficiency and lower cathodic potentials.However,this performance still does not match that of binder-free systems because Sn-based catalysts intrinsic-ally exhibit high catalytic activity,making the binder contribution less significant.Although modifying the electrode surface with binders leads to blocked active sites and increased resistance,polyvinylidene fluoride(PVDF)remains promising because of its stability,strength,and conductivity,achieving up to 72%FE to formate at−30 mA·cm^(-2) and−1.66 V vs.RHE.The findings of this research reveal method-ologies for optimizing the catalyst ink formulations and binder utilization to enhance the conversion of CO_(2) to formate,thereby offering crucial insights for the development of a cost-efficient catalyst for high-current-density operations.展开更多
Recycling of indium secondary resources to prepare indium-based electrocatalysts for efficient CO_(2)reduction has been a promising strategy to bridge the gap between indium recycling and utilization.Herein,the chemis...Recycling of indium secondary resources to prepare indium-based electrocatalysts for efficient CO_(2)reduction has been a promising strategy to bridge the gap between indium recycling and utilization.Herein,the chemisorption of metal cations in indium tin oxide(ITO)etching wastewater by iminodiacetic groups of commercial D401 resin successfully achieves nearly 100%indium recovery and also fulfills wastewater emission standards.Theoretical calculation unveils that metallic indium over In_(2)O_(3)support(In/In_(2)O_(3))possesses the lowest energy barrier for electrochemical reduction of CO_(2)to formate.Such an In/In_(2)O_(3)is hence constructed by air annealing the metal cation-adsorbed resin and post in situ electrochemical reconstruction upon CO_(2)reduction.The In/In_(2)O_(3)derived from the ITO etching wastewater exhibits exceptional electrocatalytic CO_(2)-to-formate performance as current efficiency is higher than 92%throughout 145 h galvanostatic electrolysis at-250 mA cm^(-2).The rational integration of metallurgy and material for indium recycling and utilization adds knowledge on designing In-based electrocatalysts,contributing to addressing indium scarcity and carbon-neutral challenge.展开更多
Metal-nitrogen-carbon(M-N-C)single-atom catalysts are widely utilized in various energy-related catalytic processes,offering a highly efficient and cost-effective catalytic system with significant potential.Recently,c...Metal-nitrogen-carbon(M-N-C)single-atom catalysts are widely utilized in various energy-related catalytic processes,offering a highly efficient and cost-effective catalytic system with significant potential.Recently,curvature-induced strain has been extensively demonstrated as a powerful tool for modulating the catalytic performance of M-N-C catalysts.However,identifying optimal strain patterns using density functional theory(DFT)is computationally intractable due to the high-dimensional search space.Here,we developed a graph neural network(GNN)integrated with an advanced topological data analysis tool-persistent homology-to predict the adsorption energy response of adsorbate under proposed curvature patterns,using nitric oxide electroreduction(NORR)as an example.Our machine learning model achieves high accuracy in predicting the adsorption energy response to curvature,with a mean absolute error(MAE)of 0.126 eV.Furthermore,we elucidate general trends in curvature-modulated adsorption energies of intermediates across various metals and coordination environments.We recommend several promising catalysts for NORR that exhibit significant potential for performance optimization via curvature modulation.This methodology can be readily extended to describe other non-bonded interactions,such as lattice strain and surface stress,providing a versatile approach for advanced catalyst design.展开更多
Metallene has been widely considered as an advanced electrocatalytic material due to its large specific surface area and highly active reaction sites.Herein,we design and synthesize ultrathin rhodium metallene(Rh ML)w...Metallene has been widely considered as an advanced electrocatalytic material due to its large specific surface area and highly active reaction sites.Herein,we design and synthesize ultrathin rhodium metallene(Rh ML)with abundant wrinkles to supply surface-strained Rh sites for driving acetonitrile electroreduction to ethylamine(AER).The electrochemical tests indicate that Rh ML shows an ethylamine yield rate of 137.1 mmol gcat^(-1) h^(-1) in an acidic solution,with stability lasting up to 200 h.Theoretical calculations reveal that Rh ML with wrinkle-induced compressive strain not only shows a lower energy barrier in the rate-determining step but also facilitates the ethylamine desorption process compared to wrinkle-free Rh ML and commercial Rh black.The assembled electrolyzer with bifunctional Rh ML shows an electrolysis voltage of 0.41 V at 10 mA cm^(-2),enabling simultaneous ethylamine production and hydrazine waste treatment.Furthermore,the voltage of an assembled hybrid zinc-acetonitrile battery can effectively drive this electrolyzer to achieve the dual AER process.This study provides guidance for improving the catalytic efficiency of surface atoms in two-dimensional materials,as well as the electrochemical synthesis technology for series-connected battery-electrolyzer systems.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
Developing Sn,nitrogen-doped carbon catalysts(Sn-NC)for efficient CO_(2) electroreduction(CO_(2)RR)to CO remains a great challenge.Here,we employed a defective hierarchical porous graphene nanomesh to anchor the singl...Developing Sn,nitrogen-doped carbon catalysts(Sn-NC)for efficient CO_(2) electroreduction(CO_(2)RR)to CO remains a great challenge.Here,we employed a defective hierarchical porous graphene nanomesh to anchor the single atomic tin-nitrogen sites(A-Sn-NGM)for effective CO_(2) electroreduction.The synthesized A-Sn-NGM typically showed remarkable CO_(2)RR activity towards CO production,which achieved a maximum CO Faradaic efficiency(FECO)of 98.7%and a turnover frequency of 5117.4 h^(−1) at a potential of−0.6 V(vs.RHE).Further analysis proves that the increased activity to CO production of A-Sn-NGM derives from the enlarged roughness and enhanced intrinsic activity.Density-functional theory(DFT)calculations indicate that the adjacent carbon defects anchored Sn-Nx coordination sites can markedly inhibit the competing hydrogen evolution reaction(HER)and lower the energy barrier for the formation of *COOH intermediates as compared to bulk Sn-Nx sites without carbon defects.This work provides a reliable method by engineering the carbon support to improve the CO_(2)RR performance for single-atom catalysts.展开更多
Atomic hydrogen(H∗)plays a crucial role in electrochemical reduction technology towards various environmental and energy applications,but suffers from low utilization efficiency arisen from the undesirable H-H dimeriz...Atomic hydrogen(H∗)plays a crucial role in electrochemical reduction technology towards various environmental and energy applications,but suffers from low utilization efficiency arisen from the undesirable H-H dimerization and the competitive adsorption between water molecule with reactants on the traditional adjacent catalytic sites.Herein,we anchored Pd single atoms on the naturally formed titanium oxide of titanium foam to construct Pd_(1)-O-Ti dual-site electrocatalyst with spatially isolated water dissociation and H∗utilization site,which synchronously inhibits the H-H dimerization and the competitive adsorption of water molecule and targeted reactants.Experiments and theoretical calculations revealed that the Ti-O sites could synergistically dissociate water to H∗,which overflowed to nearby Pd single-atom sites for designed reduction reactions and utilization benefiting from the hydrogen spillover ability of titanium oxide substrate.These Pd_(1)-O-Ti dual sites delivered almost 100%bromate reduction efficiency with a rate constant of 1.57 h^(-1),far superior to those of Pdn-O-Ti with adjacent Pd sites(0.52 h^(-1)),Pd_(1)-N-C with single sites(0.04 h^(-1))and commercial Pd/C(0.18 h^(-1)),respectively.This study sheds light on the importance of integrating synergistic active sites for complicated electrochemical reactions,and provide new insights in improving H∗ utilization for environmental remediation.展开更多
Food production demand is constantly growing,entailing a proportional increment in fertilisers and pharmaceuticals use,which are eventually introduced to the environment,leading,among others,to an imbalance in the nit...Food production demand is constantly growing,entailing a proportional increment in fertilisers and pharmaceuticals use,which are eventually introduced to the environment,leading,among others,to an imbalance in the nitrogen cycle.Electrochemical nitrate reduction reaction is a delocalised route for nitrates elimination and green ammonia production.In the present study,we carry out nitrates electroreduction over a commercial MoS_(2)catalyst,focusing on optimising selected input factors affecting the reaction.Concretely,Doehlert design of experiment and response surface methodology are employed to find the proper combination of supporting salt concentration in the electrolyte,applied potential,and catalyst loading at the working electrode,with the overall aim to boost Faradaic efficiency(FE)and ammonia production.As a matter of fact,varying these input factors,the obtained FE values ranged from∼2%to∼80%,highlighting the strength of the newly conceived approach.Moreover,our multivariate strategy allows the quantification of each factor effect and elucidates hidden interactions between them.Finally,successful extended durability tests are performed for 100 h at both FE and productivity(P)optimal conditions.In parallel,cell electrodes are characterised by in-depth structural,morphological,and surface techniques,before and after ageing,overall demonstrating the outstanding stability of the proposed electrochemical reactor.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
The utilization of covalent organic frameworks(COFs)holds great potential for achieving tailorable tuning of catalytic performance through bottom-up modulation of the reticular structure.In this work,we show that a si...The utilization of covalent organic frameworks(COFs)holds great potential for achieving tailorable tuning of catalytic performance through bottom-up modulation of the reticular structure.In this work,we show that a single-point structural alteration in the linkage within a nickel phthalocyanine(NiPc)-based series effectively modulates the catalytic performance of the COFs in electrochemical CO_(2)reduction reaction(CO_(2)RR).A Ni Pc-based COF series with three members which possess the same Ni Pc unit but different linkages,including piperazine,dioxin,and dithiine,have been constructed by nucleophilic aromatic substitution reaction between octafluorophthalocyanine nickel and tetrasubstituted benzene linkers with different bridging groups.Among these COFs,the dioxin-linked COF showed the best activity of CO_(2)RR with a current density of CO(j_(CO))=-27.99 m A cm^(-2)at-1.0 V(versus reversible hydrogen electrode,RHE),while the COF with piperazine linkage demonstrated an excellent selectivity of Faradaic efficiency for CO(FECO)up to 90.7%at a pretty low overpotential of 0.39 V.In addition,both a high FECO value close to 100%and a reasonable jCO of-8.20 m A cm^(-2)at the potential of-0.8 V(versus RHE)were obtained by the piperazine-linked COF,making it one of the most competitive candidates among COF-based materials.Mechanistic studies exhibited that single-point structural alteration could tailor the electron density in Ni sites and alter the interaction between the active sites and the key intermediates adsorbed and desorbed,thereby tuning the electrochemical performance during CO_(2)RR process.展开更多
Ammonia is a key industry raw material for fertilizers and the electro-reduction of N_(2)(NRR)can be served as a promising method.It is urgently needed to discover advanced catalysts while the lack of design principle...Ammonia is a key industry raw material for fertilizers and the electro-reduction of N_(2)(NRR)can be served as a promising method.It is urgently needed to discover advanced catalysts while the lack of design principles still hinders the high-throughput screen of efficient candidates.Herein,we have provided an up-to-date review of NRR catalysts mainly on theoretical works and highlighted the latest achievements on descriptors,which can be served as valid guidance of optimal catalysts.The descriptors are classified with adsorption energy and the corresponding derived ones,which can screen the NRR catalysts from various aspects.Finally,the challenges and opportunities in the descriptor field are presented.展开更多
The copper-based electrocatalysts feature attractive potentials of converting CO_(2)into multi-carbon(C_(2+))products,while the instability of Cu-O often induces the reduction of Cu^(+)/Cu^(0) catalytic sites at the c...The copper-based electrocatalysts feature attractive potentials of converting CO_(2)into multi-carbon(C_(2+))products,while the instability of Cu-O often induces the reduction of Cu^(+)/Cu^(0) catalytic sites at the cathode and refrains the capability of stable electrolysis especially at high powers.In this work,we developed an Erbium(Er)oxide-modified Cu(Er-O-Cu)catalyst with enhanced covalency of Cu-O and more stable active sites.The f-p-d coupling strengthens the covalency of Cu-O,and the stability of Cu^(+)sites under electroreduction condition is critical for promoting the C-C coupling and improving the C_(2+)product selectivity.As a result,the Er-O-Cu sites exhibited a high Faradaic efficiency of C_(2+)products(FEC_(2+))of 86%at 2200 mA cm^(-2),and a peak partial current density of|j_(C2+)|of 1900 mA cm^(-2),comparable to the best reported values for the CO_(2)-to-C_(2+)electroreduction.The CO_(2)electrolysis by the Er-O-Cu sites was further scaled up to 100 cm^(2)to achieve high-power(~200 W)electrolysis with ethylene production rate of 16 mL min^(-1).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
Copper(Cu)-based catalysts show significant potential for producing high value-added C_(2+)products in electrocatalytic CO_(2)/CO reduction reactions(CO(2)RR).However,the structural reconfiguration during operation po...Copper(Cu)-based catalysts show significant potential for producing high value-added C_(2+)products in electrocatalytic CO_(2)/CO reduction reactions(CO(2)RR).However,the structural reconfiguration during operation poses substantial challenges in identifying the intrinsic catalytic active site,especially under similar mass transport conditions.Herein,three typical and commercial Cu-based catalysts(Cu,CuO,and Cu_(2)O)are chosen as representatives to elucidate the structure-activity relationship of CORR in the membrane electrode assembly electrolyzer.Notably,only the Cu catalyst demonstrates the most suppression of hydrogen evolution reaction,thus achieving the highest FE of 86.7% for C_(2+)products at a current density of 500 mA cm^(-2) and maintaining a stable electrolysis over 110 h at a current of 200 mA cm^(-2).The influence of chemical valence state of Cu,electrochemical surface area,and local pH were firstly investigated and ruled out for the significant FE differences.Finally,based on the structure analysis from high resolution transmission electron microscope,OH-adsorption,in situ infrared spectroscopy and density functional theory calculations,it is suggested that the asymmetric C-C coupling(via ^(*)CHO and ^(*)CO)is the most probable reaction pathway for forming C_(2+)products,with Cu(100)-dominant grain boundaries(GBs)being the most favorable active sites.These findings provide deeper insights into the synergistic relationship between crystal facets and GBs in electrocatalytic systems.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
Electrochemical CO_(2) reduction reaction(CO_(2)RR),driven by renewable energy,offers a promising solution to mitigate increasing CO_(2) emissions and establish a carbon-neutral cycle.Copper is a highly selective and ...Electrochemical CO_(2) reduction reaction(CO_(2)RR),driven by renewable energy,offers a promising solution to mitigate increasing CO_(2) emissions and establish a carbon-neutral cycle.Copper is a highly selective and active catalyst for CO_(2)RR but suffers from structural reconstruction challenges.Hybrid organic/inorganic materials address these issues by offering customizable compositions and interfaces.Recently,Buonsanti’s team developed hybrid Cu@AlOx nanocrystals with tunable alumina shells via a colloidal atomic layer deposition approach,achieving stable and selective methane production during CO_(2)RR.Mechanistic studies reveal that the alumina shell stabilizes oxidized copper species through Cu^(2+)-O-Al motifs coordinated with AlO_(4) Lewis acid sites,reducing copper dissolution and structural reconstruction.This study provides key insights into the mechanism underlying stabilization,highlighting the critical role of Lewis acidity in preserving the structural integrity of the catalyst.This highlight review aims to inspire the development of other high-performance and stable catalysts through colloidal atomic layer deposition strategies.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 Natural Science Foundation of Shandong Province(No.ZR2023ME155)the project of“20 Items of University”of Jinan(No.202228046)the Tais-han Scholar Project of Shandong Province(Nos.tsqn202306226 and tsqn202211171).
文摘Electrocatalytic conversion of carbon dioxide(CO_(2))into formate offers a sustainable pathway to mitigate environmental degradation and the energy crisis.Tin(Sn)-based materials are promising electrocatalysts for CO_(2)reduction to formate;however,their efficiency is limited by weak CO_(2)adsorption and activation,as well as sluggish reaction kinetics.In this work,we designed an intercrossing nanoporous Cu_(6)Sn_(5)/Sn intermetallic heterojunction via a scalable alloying-etching protocol.The resulting Cu_(6)Sn_(5)/Sn catalyst with abundant interfacial sites exhibited enhanced formate selectivity(60.79%)at−0.93 V versus the reversible hydrogen electrode(RHE),together with a high partial current density of 12.56 mA/cm^(2)and stable operation for 16 h.The modulated electronic structure of Cu_(6)Sn_(5)coupled with the robust interfacial interaction between Sn and Cu_(6)Sn_(5)synergistically promoted CO_(2)adsorption and activation,thereby improving CO_(2)reduction reaction(CO_(2)RR)performance.Electrochemical measurements and in situ infrared spectroscopy confirmed that the dual-phase interfaces facilitate H_(2)O decomposition and the generation of abundant*H intermediates,which in turn accelerate the protonation of CO_(2)to formate.This work highlights a scalable strategy for constructing intermetallic heterojunction catalysts that combine facile synthesis,reproducibility,and superior catalytic activity for CO_(2)RR.
基金financially supported by a PhD Grant from VITO’s Strategic Research Funds(No.2310345).
文摘Electrochemical CO_(2) reduction is a sustainable method for producing fuels and chemicals using renewable energy sources.Sn is a widely employed catalyst for formate production,with its performance closely influenced by the catalyst ink formulations and reac-tion conditions.The present study explores the influence of catalyst loading,current density,and binder choice on Sn-based CO_(2) reduc-tion systems.Decreasing catalyst loading from 10 to 1.685 mg·cm^(-2) and increasing current density in highly concentrated bicarbonate solutions significantly enhances formate selectivity,achieving 88%faradaic efficiency(FE)at a current density of−30 mA·cm^(-2) with a cathodic potential of−1.22 V vs.reversible hydrogen electrode(RHE)and a catalyst loading of 1.685 mg·cm^(-2).This low-loading strategy not only reduces catalyst costs but also enhances surface utilization and suppresses the hydrogen evolution reaction.Nafion enhances formate production when applied as a surface coating rather than pre-mixed in the ink,as evidenced by improved faradaic efficiency and lower cathodic potentials.However,this performance still does not match that of binder-free systems because Sn-based catalysts intrinsic-ally exhibit high catalytic activity,making the binder contribution less significant.Although modifying the electrode surface with binders leads to blocked active sites and increased resistance,polyvinylidene fluoride(PVDF)remains promising because of its stability,strength,and conductivity,achieving up to 72%FE to formate at−30 mA·cm^(-2) and−1.66 V vs.RHE.The findings of this research reveal method-ologies for optimizing the catalyst ink formulations and binder utilization to enhance the conversion of CO_(2) to formate,thereby offering crucial insights for the development of a cost-efficient catalyst for high-current-density operations.
基金funding support from the National Key R&D Program of China(2023YFA1508001)the National Natural Science Foundation of China(22272120 and U2202251)+1 种基金the Hainan Province Science and Technology Special Fund(ZDYF2023SHFZ120)the Research Foundation of Marine Science and Technology Collaborative Innovation Center of Hainan University(XTCX2022HYB01)。
文摘Recycling of indium secondary resources to prepare indium-based electrocatalysts for efficient CO_(2)reduction has been a promising strategy to bridge the gap between indium recycling and utilization.Herein,the chemisorption of metal cations in indium tin oxide(ITO)etching wastewater by iminodiacetic groups of commercial D401 resin successfully achieves nearly 100%indium recovery and also fulfills wastewater emission standards.Theoretical calculation unveils that metallic indium over In_(2)O_(3)support(In/In_(2)O_(3))possesses the lowest energy barrier for electrochemical reduction of CO_(2)to formate.Such an In/In_(2)O_(3)is hence constructed by air annealing the metal cation-adsorbed resin and post in situ electrochemical reconstruction upon CO_(2)reduction.The In/In_(2)O_(3)derived from the ITO etching wastewater exhibits exceptional electrocatalytic CO_(2)-to-formate performance as current efficiency is higher than 92%throughout 145 h galvanostatic electrolysis at-250 mA cm^(-2).The rational integration of metallurgy and material for indium recycling and utilization adds knowledge on designing In-based electrocatalysts,contributing to addressing indium scarcity and carbon-neutral challenge.
基金supported by the Natural Science Foundation of Xiamen,China(3502Z202472001)the National Natural Science Foundation of China(22402163,22021001,21925404,T2293692,and 22361132532)。
文摘Metal-nitrogen-carbon(M-N-C)single-atom catalysts are widely utilized in various energy-related catalytic processes,offering a highly efficient and cost-effective catalytic system with significant potential.Recently,curvature-induced strain has been extensively demonstrated as a powerful tool for modulating the catalytic performance of M-N-C catalysts.However,identifying optimal strain patterns using density functional theory(DFT)is computationally intractable due to the high-dimensional search space.Here,we developed a graph neural network(GNN)integrated with an advanced topological data analysis tool-persistent homology-to predict the adsorption energy response of adsorbate under proposed curvature patterns,using nitric oxide electroreduction(NORR)as an example.Our machine learning model achieves high accuracy in predicting the adsorption energy response to curvature,with a mean absolute error(MAE)of 0.126 eV.Furthermore,we elucidate general trends in curvature-modulated adsorption energies of intermediates across various metals and coordination environments.We recommend several promising catalysts for NORR that exhibit significant potential for performance optimization via curvature modulation.This methodology can be readily extended to describe other non-bonded interactions,such as lattice strain and surface stress,providing a versatile approach for advanced catalyst design.
基金supported by the National Natural Science Foundation of China(22272103)the National Natural Science Foundation of China for the Youth(22309108,22202076)+3 种基金the Science and Technology Innovation Team of Shaanxi Province(2023-CX-TD-27)the China Postdoctoral Science Foundation(2023TQ0204)the Young Scientist Initiative Project of School of Materials Science and Engineering at Shaanxi Normal University(2024YSIP-MSE-SNNU008)Sanqin Scholars Innovation Teams in Shaanxi Province in China.
文摘Metallene has been widely considered as an advanced electrocatalytic material due to its large specific surface area and highly active reaction sites.Herein,we design and synthesize ultrathin rhodium metallene(Rh ML)with abundant wrinkles to supply surface-strained Rh sites for driving acetonitrile electroreduction to ethylamine(AER).The electrochemical tests indicate that Rh ML shows an ethylamine yield rate of 137.1 mmol gcat^(-1) h^(-1) in an acidic solution,with stability lasting up to 200 h.Theoretical calculations reveal that Rh ML with wrinkle-induced compressive strain not only shows a lower energy barrier in the rate-determining step but also facilitates the ethylamine desorption process compared to wrinkle-free Rh ML and commercial Rh black.The assembled electrolyzer with bifunctional Rh ML shows an electrolysis voltage of 0.41 V at 10 mA cm^(-2),enabling simultaneous ethylamine production and hydrazine waste treatment.Furthermore,the voltage of an assembled hybrid zinc-acetonitrile battery can effectively drive this electrolyzer to achieve the dual AER process.This study provides guidance for improving the catalytic efficiency of surface atoms in two-dimensional materials,as well as the electrochemical synthesis technology for series-connected battery-electrolyzer systems.
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(Nos.22208021 and 52225003)the 5·5 Engineering Research&Innovation Team Project of Beijing Forestry University(No.BLRC2023B04).
文摘Developing Sn,nitrogen-doped carbon catalysts(Sn-NC)for efficient CO_(2) electroreduction(CO_(2)RR)to CO remains a great challenge.Here,we employed a defective hierarchical porous graphene nanomesh to anchor the single atomic tin-nitrogen sites(A-Sn-NGM)for effective CO_(2) electroreduction.The synthesized A-Sn-NGM typically showed remarkable CO_(2)RR activity towards CO production,which achieved a maximum CO Faradaic efficiency(FECO)of 98.7%and a turnover frequency of 5117.4 h^(−1) at a potential of−0.6 V(vs.RHE).Further analysis proves that the increased activity to CO production of A-Sn-NGM derives from the enlarged roughness and enhanced intrinsic activity.Density-functional theory(DFT)calculations indicate that the adjacent carbon defects anchored Sn-Nx coordination sites can markedly inhibit the competing hydrogen evolution reaction(HER)and lower the energy barrier for the formation of *COOH intermediates as compared to bulk Sn-Nx sites without carbon defects.This work provides a reliable method by engineering the carbon support to improve the CO_(2)RR performance for single-atom catalysts.
基金supported by the National Natural Science Foundation of China(Nos.U22A20402,U21A20286,and 22102100)the Key Program of Shenzhen Science and Technology Commission(No.JCYJ20220818095601002)the Natural Science Foundation of Shanghai(No.22ZR1431700).
文摘Atomic hydrogen(H∗)plays a crucial role in electrochemical reduction technology towards various environmental and energy applications,but suffers from low utilization efficiency arisen from the undesirable H-H dimerization and the competitive adsorption between water molecule with reactants on the traditional adjacent catalytic sites.Herein,we anchored Pd single atoms on the naturally formed titanium oxide of titanium foam to construct Pd_(1)-O-Ti dual-site electrocatalyst with spatially isolated water dissociation and H∗utilization site,which synchronously inhibits the H-H dimerization and the competitive adsorption of water molecule and targeted reactants.Experiments and theoretical calculations revealed that the Ti-O sites could synergistically dissociate water to H∗,which overflowed to nearby Pd single-atom sites for designed reduction reactions and utilization benefiting from the hydrogen spillover ability of titanium oxide substrate.These Pd_(1)-O-Ti dual sites delivered almost 100%bromate reduction efficiency with a rate constant of 1.57 h^(-1),far superior to those of Pdn-O-Ti with adjacent Pd sites(0.52 h^(-1)),Pd_(1)-N-C with single sites(0.04 h^(-1))and commercial Pd/C(0.18 h^(-1)),respectively.This study sheds light on the importance of integrating synergistic active sites for complicated electrochemical reactions,and provide new insights in improving H∗ utilization for environmental remediation.
基金This project has received funding from the European Research Council (ERC) under the European Union’s Horizon 2020 research and innovation program (grant agreement No. 948769, project title: SuN_2rise)the 《HYDREAM》 project–funded by European Union-Next Generation EU–within the PRIN 2022 program (D.D. 104-02/02/2022 Ministero dell’Università e della Ricerca)supported by the European Union’s Horizon 2020 research and innovation programme under the Marie Skłodowska-Curie grant agreement no. 101107906
文摘Food production demand is constantly growing,entailing a proportional increment in fertilisers and pharmaceuticals use,which are eventually introduced to the environment,leading,among others,to an imbalance in the nitrogen cycle.Electrochemical nitrate reduction reaction is a delocalised route for nitrates elimination and green ammonia production.In the present study,we carry out nitrates electroreduction over a commercial MoS_(2)catalyst,focusing on optimising selected input factors affecting the reaction.Concretely,Doehlert design of experiment and response surface methodology are employed to find the proper combination of supporting salt concentration in the electrolyte,applied potential,and catalyst loading at the working electrode,with the overall aim to boost Faradaic efficiency(FE)and ammonia production.As a matter of fact,varying these input factors,the obtained FE values ranged from∼2%to∼80%,highlighting the strength of the newly conceived approach.Moreover,our multivariate strategy allows the quantification of each factor effect and elucidates hidden interactions between them.Finally,successful extended durability tests are performed for 100 h at both FE and productivity(P)optimal conditions.In parallel,cell electrodes are characterised by in-depth structural,morphological,and surface techniques,before and after ageing,overall demonstrating the outstanding stability of the proposed electrochemical reactor.
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(22305238)the Anhui Provincial Natural Science Foundation(2308085MB35)。
文摘The utilization of covalent organic frameworks(COFs)holds great potential for achieving tailorable tuning of catalytic performance through bottom-up modulation of the reticular structure.In this work,we show that a single-point structural alteration in the linkage within a nickel phthalocyanine(NiPc)-based series effectively modulates the catalytic performance of the COFs in electrochemical CO_(2)reduction reaction(CO_(2)RR).A Ni Pc-based COF series with three members which possess the same Ni Pc unit but different linkages,including piperazine,dioxin,and dithiine,have been constructed by nucleophilic aromatic substitution reaction between octafluorophthalocyanine nickel and tetrasubstituted benzene linkers with different bridging groups.Among these COFs,the dioxin-linked COF showed the best activity of CO_(2)RR with a current density of CO(j_(CO))=-27.99 m A cm^(-2)at-1.0 V(versus reversible hydrogen electrode,RHE),while the COF with piperazine linkage demonstrated an excellent selectivity of Faradaic efficiency for CO(FECO)up to 90.7%at a pretty low overpotential of 0.39 V.In addition,both a high FECO value close to 100%and a reasonable jCO of-8.20 m A cm^(-2)at the potential of-0.8 V(versus RHE)were obtained by the piperazine-linked COF,making it one of the most competitive candidates among COF-based materials.Mechanistic studies exhibited that single-point structural alteration could tailor the electron density in Ni sites and alter the interaction between the active sites and the key intermediates adsorbed and desorbed,thereby tuning the electrochemical performance during CO_(2)RR process.
基金supported by the National Natural Science Foundation of China(No.21603109)the Henan Joint Fund of the National Natural Science Foundation of China(No.U1404216)+2 种基金the Special Fund of Tianshui Normal University,China(No.CXJ2020-08)the Scientific Research Program Funded by Shaanxi Provincial Education Department(No.20JK0676)supported by Natural Science Basic Research Program of Shanxi(Nos.2022JQ-108,2022JQ-096).
文摘Ammonia is a key industry raw material for fertilizers and the electro-reduction of N_(2)(NRR)can be served as a promising method.It is urgently needed to discover advanced catalysts while the lack of design principles still hinders the high-throughput screen of efficient candidates.Herein,we have provided an up-to-date review of NRR catalysts mainly on theoretical works and highlighted the latest achievements on descriptors,which can be served as valid guidance of optimal catalysts.The descriptors are classified with adsorption energy and the corresponding derived ones,which can screen the NRR catalysts from various aspects.Finally,the challenges and opportunities in the descriptor field are presented.
基金the National Key Research and Development Program of China(2024YFB4106400,2024YFB4106401)the National Natural Science Foundation of China(22025502,U23A20552)。
文摘The copper-based electrocatalysts feature attractive potentials of converting CO_(2)into multi-carbon(C_(2+))products,while the instability of Cu-O often induces the reduction of Cu^(+)/Cu^(0) catalytic sites at the cathode and refrains the capability of stable electrolysis especially at high powers.In this work,we developed an Erbium(Er)oxide-modified Cu(Er-O-Cu)catalyst with enhanced covalency of Cu-O and more stable active sites.The f-p-d coupling strengthens the covalency of Cu-O,and the stability of Cu^(+)sites under electroreduction condition is critical for promoting the C-C coupling and improving the C_(2+)product selectivity.As a result,the Er-O-Cu sites exhibited a high Faradaic efficiency of C_(2+)products(FEC_(2+))of 86%at 2200 mA cm^(-2),and a peak partial current density of|j_(C2+)|of 1900 mA cm^(-2),comparable to the best reported values for the CO_(2)-to-C_(2+)electroreduction.The CO_(2)electrolysis by the Er-O-Cu sites was further scaled up to 100 cm^(2)to achieve high-power(~200 W)electrolysis with ethylene production rate of 16 mL min^(-1).
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.
文摘Copper(Cu)-based catalysts show significant potential for producing high value-added C_(2+)products in electrocatalytic CO_(2)/CO reduction reactions(CO(2)RR).However,the structural reconfiguration during operation poses substantial challenges in identifying the intrinsic catalytic active site,especially under similar mass transport conditions.Herein,three typical and commercial Cu-based catalysts(Cu,CuO,and Cu_(2)O)are chosen as representatives to elucidate the structure-activity relationship of CORR in the membrane electrode assembly electrolyzer.Notably,only the Cu catalyst demonstrates the most suppression of hydrogen evolution reaction,thus achieving the highest FE of 86.7% for C_(2+)products at a current density of 500 mA cm^(-2) and maintaining a stable electrolysis over 110 h at a current of 200 mA cm^(-2).The influence of chemical valence state of Cu,electrochemical surface area,and local pH were firstly investigated and ruled out for the significant FE differences.Finally,based on the structure analysis from high resolution transmission electron microscope,OH-adsorption,in situ infrared spectroscopy and density functional theory calculations,it is suggested that the asymmetric C-C coupling(via ^(*)CHO and ^(*)CO)is the most probable reaction pathway for forming C_(2+)products,with Cu(100)-dominant grain boundaries(GBs)being the most favorable active sites.These findings provide deeper insights into the synergistic relationship between crystal facets and GBs in electrocatalytic systems.
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.
基金supported by the National Natural Science Foundation of China(No.22101289)Hundred Talents Programs in Chinese Academy of Science,and the Ningbo S&T Innovation 2025 Major Special Program(No.2022Z205).
文摘Electrochemical CO_(2) reduction reaction(CO_(2)RR),driven by renewable energy,offers a promising solution to mitigate increasing CO_(2) emissions and establish a carbon-neutral cycle.Copper is a highly selective and active catalyst for CO_(2)RR but suffers from structural reconstruction challenges.Hybrid organic/inorganic materials address these issues by offering customizable compositions and interfaces.Recently,Buonsanti’s team developed hybrid Cu@AlOx nanocrystals with tunable alumina shells via a colloidal atomic layer deposition approach,achieving stable and selective methane production during CO_(2)RR.Mechanistic studies reveal that the alumina shell stabilizes oxidized copper species through Cu^(2+)-O-Al motifs coordinated with AlO_(4) Lewis acid sites,reducing copper dissolution and structural reconstruction.This study provides key insights into the mechanism underlying stabilization,highlighting the critical role of Lewis acidity in preserving the structural integrity of the catalyst.This highlight review aims to inspire the development of other high-performance and stable catalysts through colloidal atomic layer deposition strategies.
