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
The scaling-up of electrochemical CO_(2)reduction requires circumventing the CO_(2)loss as carbonates under alkaline conditions.Zero-gap MEA cell configurations with a proton exchange membrane represent an alternative...The scaling-up of electrochemical CO_(2)reduction requires circumventing the CO_(2)loss as carbonates under alkaline conditions.Zero-gap MEA cell configurations with a proton exchange membrane represent an alternative solution in a pure acidic system,but the catalyst layer in direct contact with the hydrated proton environment usually leads to H_(2)evolution dominating.Herein,we show that polydimethyldiallyl-ammonium-chloride-coated Ag(Ag@PDDA)electrode exhibits outstanding performance with a FE of 86%,a single-pass conversion of 72%,and a stability of 28 h for CO production in pure-acid MEA compared with ammonium poly(N-methyl-piperidine-co-pterphenyl)decorated Ag(Ag/QAPPT)and cetyltrimethylammonium bromide decorated Ag(Ag/CTAB).The in situ ATR-SEIRAS reveal that PDDA creates a positive charge-rich protective outer layer and an N-rich hybrid inner layer,which not only suppresses the migration of H+during the electrolysis process and blocks the direct contact between H2O and Ag catalyst,but also promotes the generation from CO_(2)to*COOH in a pure-acid system.This work highlights the importance of polyelectrolyte engineering in regulating the electrocatalytic interface and accelerates the development of proton exchange membrane CO_(2)electrolysis.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
The electrocatalytic reduction of carbon dioxide(CO_(2)RR)to valuable products presents a promising solution for addressing global warming and enhancing renewable energy storage.Herein,we construct a novel Ni_(3)ZnC_(...The electrocatalytic reduction of carbon dioxide(CO_(2)RR)to valuable products presents a promising solution for addressing global warming and enhancing renewable energy storage.Herein,we construct a novel Ni_(3)ZnC_(0.7)/Ni heterostructure electrocatalyst,using an electrospinning strategy to prepare metal particles uniformly loaded on nitrogen-doped carbon nanofibers(CNFs).The incorporation of zinc(Zn)into nickel(Ni)catalysts optimizes the adsorption of CO_(2)intermediates,balancing the strong binding affinity of Ni with the comparatively weaker affinity of Zn,which mitigates over-activation.The electron transfer within the Ni_(3)ZnC_(0.7)/Ni@CNFs system facilitates rapid electron transfer to CO_(2),resulting in great performance with a faradaic efficiency for CO(FECO)of nearly 90%at−0.86 V versus the reversible hydrogen electrode(RHE)and a current density of 17.51 mA cm^(−2)at−1.16 V versus RHE in an H-cell.Furthermore,the catalyst exhibits remarkable stability,maintaining its crystal structure and morphology after 50 h of electrolysis.Moreover,the Ni_(3)ZnC_(0.7)/Ni@CNFs is used in the membrane electrode assembly reactor(MEA),which can achieve a FECO of 91.7%at a cell voltage of−3 V and a current density of 200 mA cm−2 at−3.9 V,demonstrating its potential for practical applications in CO_(2)reduction.展开更多
Cu electrocatalysts have been demonstrated to have unique ability to reduce CO_(2)to various high value-added C_(2) products like ethylene and alcohols.However,realizing high selectivity of C_(2) products are still a ...Cu electrocatalysts have been demonstrated to have unique ability to reduce CO_(2)to various high value-added C_(2) products like ethylene and alcohols.However,realizing high selectivity of C_(2) products are still a main challenge due to complex CO_(2)electroreduction pathways and small opportunity of Csingle bondC coupling reactions.Here,we found the origin of enhanced CO_(2)electroreduction reaction activity and product selectivity towards C_(2) products and Csingle bondC coupling mechanism at halogen atoms-adsorbed Cu/H_(2)O interfaces,the corresponding CO_(2)electroreduction evolution mechanisms at the halogen atoms-modified Cu/H_(2)O interfaces are systematically studied via theoretical modeling and calculations.The calculated results indicate that halide anions modifications are beneficial to CO dimerization into OCCO dimer,especially Cl^(-)-adsorbed Cu(111)/H_(2)O interface has the optimum activity and selectivity towards OCCO dimer,subsequent Cl-adsorbed Cu(111)/H_(2)O interface can selectively reduce CO_(2)into C_(2)H_(4) product.The function relationship between adsorption free energy of Cl atom and electrode potential explain why the adsorption of Cl^(-)can enhance selectivity of C_(2)H_(4) product.The determinations of onset potentials indicate that electroreduction pathways of CO_(2)towards C_(2)H_(4) product are facile to take place and further explain the origin of the significantly enhanced CO production activity and C_(2)H_(4) product selectivity.This work on selective realization of CO_(2)electroreduction towards C_(2)H_(4) product via Cl^(-)-modified Cu(111)/H_(2)O interface provide a theoretical guideline for how to selectively realize other high value-added C_(2) products.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
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
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
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
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
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
The efficient production of acetate through electrochemical CO_(2)reduction reaction(eCO_(2)RR)with low energy consumption has consistently been a challenging yet extremely significant task.Current catalysts suffered ...The efficient production of acetate through electrochemical CO_(2)reduction reaction(eCO_(2)RR)with low energy consumption has consistently been a challenging yet extremely significant task.Current catalysts suffered from high energy consumption and low relative purity of acetate product.Herein,we report ultrasmall Cu_(2)O nanoparticles with an average size of 2.5±0.09 nm immobilized on a conductive copper-based metal-organic framework(Cu-THQ)(denoted as Cu_(2)O@Cu-THQ),which attained a Faradaic efficiency of 65(3)%for acetate at a very low potential of-0.3 V vs.RHE with a current density of 10.5 m A/cm^(2).Importantly,as there are no other liquid phase products such as formate,methanol or ethanol,the relative purity of the obtained acetate product was as high as 100%.Taking into account the relative purity of the liquid product,current density,and energy consumption,the performance for electroreduction of CO_(2)to acetate of Cu_(2)O@Cu-THQ is not only much higher than that of the commercial Cu_(2)O nanoparticles,but also higher than those of all reported catalysts.Operando infrared spectroscopy and theoretical calculations indicated that the synergy effect between Cu-THQ and Cu_(2)O promoted the e CO_(2)RR to yield acetate.Specifically,the hydroxyl group on the organic ligand THQ in the Cu-THQ formed hydrogen bond interactions with the key C_(2)intermediates(*CH_(2)COOH and*HOCCOH)adsorbed on Cu_(2)O,which played a crucial role in stabilizing the key C_(2)intermediates and thus reduced the formation energy of the key C_(2) intermediates.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
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 steps of NO_(3)^(-)adsorption,deoxygenation,nitrogen species hydrogenation and ammonia desorption are vital for electrocatalytic nitrate reduction(NO_(3)^(-)RR)to ammonia,and lowering their Gibbs free energy chan...The steps of NO_(3)^(-)adsorption,deoxygenation,nitrogen species hydrogenation and ammonia desorption are vital for electrocatalytic nitrate reduction(NO_(3)^(-)RR)to ammonia,and lowering their Gibbs free energy change(ΔG)is the essential approach for improving NO_(3)^(-)RR.The copper-based alloys are considered as the outstanding catalysts thanks to the tunable d-band center,reconstruction and synergistic effect of multiple metal atoms in the past decades.Here,we synthesized a single-phase coppernickel alloy by electrodeposition and optimized itsΔG during NO_(3)^(-)RR through tuning the electrodeposition potential to regulate the metal component ratio.The atomic ratio of Ni/Cu in CuNi alloys is gradually increased as the negative shift of deposition potential from-1.0 to-1.2 V versus SCE,thus achieving the fast modulation of intermediate adsorption energy for NO_(3)^(-)RR.According to density functional theory,profited by a strong NO_(3)^(-)adsorption and a weak NH_(3)desorption energy barrier,the optimized CuNi alloy(Cu_(3)Ni_(1)/CF)exhibits an ideal ammonia yield of 364.1μmol cm^(-2)h^(-1)and Faradaic efficiency of 92.25%at-0.23 V versus RHE.Further applying Cu_(3)Ni_(1)/CF as the cathode material,a novel Znnitrate battery exhibits a maximum power density of5.85 mW cm^(-2)with a NH_(3)yield of 92.50μmol cm^(-2)h^(-1)and Faradaic efficiency of 99.15%at 20 mA cm^(-2)for NH_(3)production.This work not only offers a rational design concept with clear guidance for efficient modulation of intermediate adsorption free energy on alloy catalysts prepared by electrodeposition,but also provides the further understanding for efficient developments of NO_(3)^(-)RR and Zn-based batteries.展开更多
The electrochemical reduction of carbon monoxide (COER) to high-value multicarbon (C_(2+)) products is an emerging strategy for artificial carbon fixation and renewable energy storage. However, the slow kinetics of th...The electrochemical reduction of carbon monoxide (COER) to high-value multicarbon (C_(2+)) products is an emerging strategy for artificial carbon fixation and renewable energy storage. However, the slow kinetics of the C–C coupling reaction remains a significant obstacle in achieving both high activity and selectivity for C_(2+) production. In this study, we demonstrated the use of defect engineering to promote COER towards C_(2+) products by introducing single chlorine vacancy (SVCl) into two-dimensional (2D) non-noble transition metal dichlorides (TMCl_(2)). Density functional theory (DFT) calculations revealed that SVCl in TMCl_(2) exhibits low formation energies and high stability, ensuring its feasibility for synthesis and application in electrocatalysis. The introduction of three-coordinated, unsaturated metal sites substantially enhances the catalytic activity of TMCl_(2), facilitating effective CO activation. Notably, SVCl-engineered CoCl_(2) and NiCl_(2) nanosheets exhibit superior performance in COER, with SVCl@CoCl_(2) showing catalytic activity for ethanol and propanol production, and SVCl@NiCl_(2) favoring ethanol production due to a lower limiting potential and smaller kinetic barrier for C–C coupling. Consequently, defective 2D TMCl_(2) nanosheets represent a highly promising platform for converting CO into value-added C_(2+) products, warranting further experimental investigation into defect engineering for CO conversion.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
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financial support of the National Natural Science Foundation of China(NSFC)(52394202,52021004,52301232,and 52476056)the Natural Science Foundation of Chongqing Province(2024NSCQ-MSX1109).
文摘The scaling-up of electrochemical CO_(2)reduction requires circumventing the CO_(2)loss as carbonates under alkaline conditions.Zero-gap MEA cell configurations with a proton exchange membrane represent an alternative solution in a pure acidic system,but the catalyst layer in direct contact with the hydrated proton environment usually leads to H_(2)evolution dominating.Herein,we show that polydimethyldiallyl-ammonium-chloride-coated Ag(Ag@PDDA)electrode exhibits outstanding performance with a FE of 86%,a single-pass conversion of 72%,and a stability of 28 h for CO production in pure-acid MEA compared with ammonium poly(N-methyl-piperidine-co-pterphenyl)decorated Ag(Ag/QAPPT)and cetyltrimethylammonium bromide decorated Ag(Ag/CTAB).The in situ ATR-SEIRAS reveal that PDDA creates a positive charge-rich protective outer layer and an N-rich hybrid inner layer,which not only suppresses the migration of H+during the electrolysis process and blocks the direct contact between H2O and Ag catalyst,but also promotes the generation from CO_(2)to*COOH in a pure-acid system.This work highlights the importance of polyelectrolyte engineering in regulating the electrocatalytic interface and accelerates the development of proton exchange membrane CO_(2)electrolysis.
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financial support from the Natural Science Foundation of Yancheng(YCBK2024004)the Basic Research Program of Jiangsu(BK20251089)the“Scientific and Technical Innovation Action Plan”Basic Research Field of Shanghai Science and Technology Committee(19JC1410500).
文摘The electrocatalytic reduction of carbon dioxide(CO_(2)RR)to valuable products presents a promising solution for addressing global warming and enhancing renewable energy storage.Herein,we construct a novel Ni_(3)ZnC_(0.7)/Ni heterostructure electrocatalyst,using an electrospinning strategy to prepare metal particles uniformly loaded on nitrogen-doped carbon nanofibers(CNFs).The incorporation of zinc(Zn)into nickel(Ni)catalysts optimizes the adsorption of CO_(2)intermediates,balancing the strong binding affinity of Ni with the comparatively weaker affinity of Zn,which mitigates over-activation.The electron transfer within the Ni_(3)ZnC_(0.7)/Ni@CNFs system facilitates rapid electron transfer to CO_(2),resulting in great performance with a faradaic efficiency for CO(FECO)of nearly 90%at−0.86 V versus the reversible hydrogen electrode(RHE)and a current density of 17.51 mA cm^(−2)at−1.16 V versus RHE in an H-cell.Furthermore,the catalyst exhibits remarkable stability,maintaining its crystal structure and morphology after 50 h of electrolysis.Moreover,the Ni_(3)ZnC_(0.7)/Ni@CNFs is used in the membrane electrode assembly reactor(MEA),which can achieve a FECO of 91.7%at a cell voltage of−3 V and a current density of 200 mA cm−2 at−3.9 V,demonstrating its potential for practical applications in CO_(2)reduction.
基金supported by the Natural Science Foundation of Hunan Province(No.2025JJ50059)Key Program of Hunan University of Arts and Science(No.23ZZ03)Aid Program for Science and Technology Innovative Research Team in Higher Educational Institutions of Hunan Province and National Natural Science Foundation of China(No.21303048).
文摘Cu electrocatalysts have been demonstrated to have unique ability to reduce CO_(2)to various high value-added C_(2) products like ethylene and alcohols.However,realizing high selectivity of C_(2) products are still a main challenge due to complex CO_(2)electroreduction pathways and small opportunity of Csingle bondC coupling reactions.Here,we found the origin of enhanced CO_(2)electroreduction reaction activity and product selectivity towards C_(2) products and Csingle bondC coupling mechanism at halogen atoms-adsorbed Cu/H_(2)O interfaces,the corresponding CO_(2)electroreduction evolution mechanisms at the halogen atoms-modified Cu/H_(2)O interfaces are systematically studied via theoretical modeling and calculations.The calculated results indicate that halide anions modifications are beneficial to CO dimerization into OCCO dimer,especially Cl^(-)-adsorbed Cu(111)/H_(2)O interface has the optimum activity and selectivity towards OCCO dimer,subsequent Cl-adsorbed Cu(111)/H_(2)O interface can selectively reduce CO_(2)into C_(2)H_(4) product.The function relationship between adsorption free energy of Cl atom and electrode potential explain why the adsorption of Cl^(-)can enhance selectivity of C_(2)H_(4) product.The determinations of onset potentials indicate that electroreduction pathways of CO_(2)towards C_(2)H_(4) product are facile to take place and further explain the origin of the significantly enhanced CO production activity and C_(2)H_(4) product selectivity.This work on selective realization of CO_(2)electroreduction towards C_(2)H_(4) product via Cl^(-)-modified Cu(111)/H_(2)O interface provide a theoretical guideline for how to selectively realize other high value-added C_(2) products.
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.
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 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 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 Key Research and Development Program of China(No.2021YFA1500401)National Natural Science Foundation of China(NSFC,Nos.21821003,22371304+3 种基金223B2123)Fundamental Research Funds for the Central Universities,Sun Yat-Sen University(No.24lgzy006)Science and Technology Innovation Special Support Project of Guangdong Province,China(No.STKJ2023078)the Guangzhou Science and Technology Program(No.SL2023A04J01767)。
文摘The efficient production of acetate through electrochemical CO_(2)reduction reaction(eCO_(2)RR)with low energy consumption has consistently been a challenging yet extremely significant task.Current catalysts suffered from high energy consumption and low relative purity of acetate product.Herein,we report ultrasmall Cu_(2)O nanoparticles with an average size of 2.5±0.09 nm immobilized on a conductive copper-based metal-organic framework(Cu-THQ)(denoted as Cu_(2)O@Cu-THQ),which attained a Faradaic efficiency of 65(3)%for acetate at a very low potential of-0.3 V vs.RHE with a current density of 10.5 m A/cm^(2).Importantly,as there are no other liquid phase products such as formate,methanol or ethanol,the relative purity of the obtained acetate product was as high as 100%.Taking into account the relative purity of the liquid product,current density,and energy consumption,the performance for electroreduction of CO_(2)to acetate of Cu_(2)O@Cu-THQ is not only much higher than that of the commercial Cu_(2)O nanoparticles,but also higher than those of all reported catalysts.Operando infrared spectroscopy and theoretical calculations indicated that the synergy effect between Cu-THQ and Cu_(2)O promoted the e CO_(2)RR to yield acetate.Specifically,the hydroxyl group on the organic ligand THQ in the Cu-THQ formed hydrogen bond interactions with the key C_(2)intermediates(*CH_(2)COOH and*HOCCOH)adsorbed on Cu_(2)O,which played a crucial role in stabilizing the key C_(2)intermediates and thus reduced the formation energy of the key C_(2) intermediates.
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.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 National Natural Science Foundation of China(No.U22A20253)High-level Talent Doctoral Scientific Research Foundation of Zhoukou Normal University(No.ZKNUC2023027)Young and Middle-Aged Backbone Teachers of Zhoukou Normal University
文摘The steps of NO_(3)^(-)adsorption,deoxygenation,nitrogen species hydrogenation and ammonia desorption are vital for electrocatalytic nitrate reduction(NO_(3)^(-)RR)to ammonia,and lowering their Gibbs free energy change(ΔG)is the essential approach for improving NO_(3)^(-)RR.The copper-based alloys are considered as the outstanding catalysts thanks to the tunable d-band center,reconstruction and synergistic effect of multiple metal atoms in the past decades.Here,we synthesized a single-phase coppernickel alloy by electrodeposition and optimized itsΔG during NO_(3)^(-)RR through tuning the electrodeposition potential to regulate the metal component ratio.The atomic ratio of Ni/Cu in CuNi alloys is gradually increased as the negative shift of deposition potential from-1.0 to-1.2 V versus SCE,thus achieving the fast modulation of intermediate adsorption energy for NO_(3)^(-)RR.According to density functional theory,profited by a strong NO_(3)^(-)adsorption and a weak NH_(3)desorption energy barrier,the optimized CuNi alloy(Cu_(3)Ni_(1)/CF)exhibits an ideal ammonia yield of 364.1μmol cm^(-2)h^(-1)and Faradaic efficiency of 92.25%at-0.23 V versus RHE.Further applying Cu_(3)Ni_(1)/CF as the cathode material,a novel Znnitrate battery exhibits a maximum power density of5.85 mW cm^(-2)with a NH_(3)yield of 92.50μmol cm^(-2)h^(-1)and Faradaic efficiency of 99.15%at 20 mA cm^(-2)for NH_(3)production.This work not only offers a rational design concept with clear guidance for efficient modulation of intermediate adsorption free energy on alloy catalysts prepared by electrodeposition,but also provides the further understanding for efficient developments of NO_(3)^(-)RR and Zn-based batteries.
基金financially supported by the International Partnership Program of the Chinese Academy of Sciences(No.172GJHZ2022010MI)the Natural Science Funds for Distinguished Young Scholars of Heilongjiang Province(No.JC2018004).
文摘The electrochemical reduction of carbon monoxide (COER) to high-value multicarbon (C_(2+)) products is an emerging strategy for artificial carbon fixation and renewable energy storage. However, the slow kinetics of the C–C coupling reaction remains a significant obstacle in achieving both high activity and selectivity for C_(2+) production. In this study, we demonstrated the use of defect engineering to promote COER towards C_(2+) products by introducing single chlorine vacancy (SVCl) into two-dimensional (2D) non-noble transition metal dichlorides (TMCl_(2)). Density functional theory (DFT) calculations revealed that SVCl in TMCl_(2) exhibits low formation energies and high stability, ensuring its feasibility for synthesis and application in electrocatalysis. The introduction of three-coordinated, unsaturated metal sites substantially enhances the catalytic activity of TMCl_(2), facilitating effective CO activation. Notably, SVCl-engineered CoCl_(2) and NiCl_(2) nanosheets exhibit superior performance in COER, with SVCl@CoCl_(2) showing catalytic activity for ethanol and propanol production, and SVCl@NiCl_(2) favoring ethanol production due to a lower limiting potential and smaller kinetic barrier for C–C coupling. Consequently, defective 2D TMCl_(2) nanosheets represent a highly promising platform for converting CO into value-added C_(2+) products, warranting further experimental investigation into defect engineering for CO conversion.
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.
