As the core of cathode materials,sensitive metals play important roles in the optimization of acetate production from carbon dioxide(CO_(2))in microbial electrochemical system(MES).In this work,iron(Fe),copper(Cu),and...As the core of cathode materials,sensitive metals play important roles in the optimization of acetate production from carbon dioxide(CO_(2))in microbial electrochemical system(MES).In this work,iron(Fe),copper(Cu),and nickel(Ni)as sensitive metal cathode materials were evaluated for CO_(2) conversion in MES.The MES with Feelectrode as a promising electrode material demonstrated a superior CO_(2) reduction performance with a maximum acetate accumulation of 417.9±39.2 mg/L,which was 1.5 and 1.7 folds higher than that in the Ni-electrode and Cu-electrode groups,respectively.Furthermore,an outstanding electron recovery efficiency of 67.7%was shown in the Fe-electrode group.The electron transfer between electrode-suspended sludge was systematically cross-evaluated by the electrochemical behavior and extracellular polymeric substances.The Fe-electrode group had the highest electron transfer rate with 0.194 s-1(k_(app)),which was 17.6 and 21.5 times higher than that of the Cu-and Ni-electrode groups,respectively.Fe-electrode was beneficial for reducing electrochemical impedance between the electrode and suspended sludge.Additionally,redox substances in extracellular polymeric substances of the Fe-electrode group were increased,implying more favorable electron transport dynamics.Simultaneously,enrichments of functional bacteria Acetoanerobium and increased key enzymes involved in the carbonyl pathway of the Fe-electrode group were observed,which also promoted CO_(2) conversion in MES.This study provides a perspective on evaluating the promising sensitive metal electrode material for the process of CO_(2) valorization in MES and offers a reference for the subsequent electrode modification.展开更多
The methanol oxidation reaction(MOR)to formic acid offers a promising alternative to the anodic oxygen evolution reaction(OER)in water electrolysis.However,the development of efficient and cost-effective catalysts rem...The methanol oxidation reaction(MOR)to formic acid offers a promising alternative to the anodic oxygen evolution reaction(OER)in water electrolysis.However,the development of efficient and cost-effective catalysts remains a primary challenge.In this study,an enhancement in catalytic MOR performance is achieved through the incorporation of Mn atoms with unsaturated t_(2g)orbitals into Ni_(3)Se_(4).Comprehensive experimental analyses and theoretical calculations reveal that substituting Ni with Mn induces strong electron-withdrawing effects,effectively modulating the local coordination environment of the metal centers.The presence of Mn also elongates Ni–Se(O)bonds,which reduces eg orbital occupancy and modifies the spin state of the material.Electrochemical measurements demonstrate that electrodes based on this optimized material exhibit a high spin state and deliver excellent catalytic activity,achieving a MOR current density up to∼190 mA cm^(−2)at 1.6 V.This performance enhancement is attributed to the favorable electronic configuration and reduced reaction energy barriers associated with the high-spin state.展开更多
Efficiency of C-C bond coupling in highly inert CO_(2)is relatively low,which severely limits its efficient conversion to acetate.Here,we successfully developed a highly stable NF@CoMn_(2)O_(4)@Cu_(2)O-Ag bimetallic a...Efficiency of C-C bond coupling in highly inert CO_(2)is relatively low,which severely limits its efficient conversion to acetate.Here,we successfully developed a highly stable NF@CoMn_(2)O_(4)@Cu_(2)O-Ag bimetallic active site catalyst by anchoring Ag on the Cu_(2)O surface.In this catalyst,the Co^(3+)/Mn^(3+)-Mn^(4+)removes excess electrons from the Cu+sites via strong electronic interactions,preventing the reduction of Cu_(2)O to metallic Cu^(0),which ensures the NF@CoMn_(2)O_(4)@Cu_(2)O-Ag exhibits a high resistance to deactivation.The Cu+active sites of NF@CoMn_(2)O_(4)@Cu_(2)O-Ag efficiently electroreduce CO_(2)to the*COatop intermediate,while the Ag active sites efficiently electroreduce CO_(2)to the^(*)CO_(bridge)intermediate.The proximity of Cu+/Ag bimetallic sites shortens the distance for C-C bond coupling between the*COatop and^(*)CO_(bridge)intermediates,facilitating the efficient electrocatalytic coupling of CO_(2)to synthesize acetate.DFT analysis indicates that theΔG required for C-C bond coupling on the short-distance Cu+/Ag bimetallic sites of NF@CoMn_(2)O_(4)@Cu_(2)O-Ag is significantly lower than that of NF@CoMn_(2)O_(4)@Cu_(2)O,enabling a high Faradaic efficiency of 64.97%for acetate production at-0.3 V vs.RHE.This study provides an effective strategy for the rational design of synergistic catalysis between heterometallic catalytic sites to efficiently achieve C-C coupling for the synthesis of C2+products.展开更多
Electrocatalysis,a form of heterogeneous catalysis,is closely associated with both catalyst properties and the catalyst/electrolyte interfacial microenvironment.Herein,we rationally design and synthesize a unique PdCu...Electrocatalysis,a form of heterogeneous catalysis,is closely associated with both catalyst properties and the catalyst/electrolyte interfacial microenvironment.Herein,we rationally design and synthesize a unique PdCu nano-sea urchins(PdCu NSUs)featured with high-curvature nanotips,by which the interfacial microenvironment is expected to be tailored to the electrocatalytic reactions.PdCu NSUs exhibit excellent activity for ethanol electrooxidation,with a specific activity of 4.11 mA cm^(-2)and a mass activity of 2.24 mAμg_(Pd)^(-1),and a high Faraday efficiency(FE)of 96.4%toward acetic acid.COMSOL finite element simulations confirm that the unique nanotips could induce a local electric field due to the accumulation of positive charges in the nanotips,resulting in enrichment of OH^(-)at the catalyst surface to promote the formation of Pd-OH_(ads),a species required by ethanol dehydrogenation.Furthermore,DFT calculations and in-situ electrochemical Fourier transform infrared spectroscopy discover that the d-band center of Pd significantly downshifts in PdCu alloy,which facilitates the desorption of the produced acetic acid.This work provides a new electrocata lytic material with high-curvature nanotips,and also clarifies how the material morphology,by inducing local electric fields,affects the interfacial microenvironment and thus the catalytic activity and selectivity.展开更多
Direct conversion of methane into C1 oxygenates under mild condition with high selectivity is a desired goal in the field of energy and chemistry.But it still remains a great challenge due to the intrinsic inertness o...Direct conversion of methane into C1 oxygenates under mild condition with high selectivity is a desired goal in the field of energy and chemistry.But it still remains a great challenge due to the intrinsic inertness of methane originating from strong C-H bonds(104 kcal/mol),low solubility in the solvent,and poor selectivity.Herein,we present a direct single-step conversion of methane to formic acid(HCOOH)using molecular oxygen(O_(2)) as the oxidant under gentle conditions on a decatungstate-doped porous cerium metal-organic framework(Ce-MOF),W_(10)@Ce-bpdc.The HCOOH yield of W_(10)@Ce-bpdc-2 was 155μmol/gcatat room temperature in 12 h.The process and mechanism of conversion of methane to HCOOH was revealed by spectroscopic characteristics and controlled experiments.In the presence of light,O_(2)was converted to H_(2)O_(2)by catalyst and then to·OH radicals in solution,which interact with methane and undergo intermediates to produce HCOOH.Our experiment provides a new way to catalyze methane in combination with MOF and polyoxometalates(POMs).展开更多
The electrocatalytic oxidation of glycerol toward formic acid is one of the most promising pathways for transformation and utilization of glycerol.Herein,a series of well-defined Ni_(n)(SR)_(2n) nanoclusters(n=4,5,6;d...The electrocatalytic oxidation of glycerol toward formic acid is one of the most promising pathways for transformation and utilization of glycerol.Herein,a series of well-defined Ni_(n)(SR)_(2n) nanoclusters(n=4,5,6;denoted as Ni NCs)were prepared for the electrocatalytic glycerol oxidation toward formic acid,in which Ni_(6)-PET-50CV afforded the most excellent electrocatalytic performance with a high formic acid selectivity of 93% and a high glycerol conversion of 86%.This was attributed to the lowest charge transfer impedance and the most rapid reaction kinetics.Combined electrochemical measurements and X-ray absorption fine structure measurements revealed that the structures of Ni NCs remained intact after CV scanning pretreatment and electrocatalysis via forming the Ni–O bond.Additionally,the kinetic studies and in-situ Fourier transformed infrared suggested a sequential oxidation mechanism,in which the main reaction steps of glycerol→glyceraldehyde→glyceric acid were very rapid to produce a high selectivity of formic acid even though the low glycerol conversion.This work presents an opportunity to study Ni NCs for the efficient electrocatalytic oxidation of biomass-derived polyhydroxyl platform molecules to produce value-added carboxylic acids.展开更多
Electrocatalysis has emerged as a sustainable approach for the selective oxidation of fatty alcohols to fatty acids,circumventing the environmental concerns associated with conventional routes.However,the low aqueous ...Electrocatalysis has emerged as a sustainable approach for the selective oxidation of fatty alcohols to fatty acids,circumventing the environmental concerns associated with conventional routes.However,the low aqueous solubility of hydrophobic fatty alcohols presents a major challenge.While nickel hydroxide(Ni(OH)_(2))serves as a cost-effective catalyst for alcohol oxidation,its hydrophilic nature limits substrate accessibility and mass transport,causing sluggish kinetics and competing oxygen evolution.Herein,we propose a hydrophobic interface engineering strategy via co-electrodeposition of Ni(OH)_(2)with polytetrafluoroethylene(PTFE),fabricating the composite electrode(ED-Ni(OH)_(2)-PTFE).The optimized electrode achieves 95%Faradaic efficiency for octanoic acid at 1.5 V vs.RHE,with a production rate 2–3 times higher than pristine Ni(OH)_(2).Mechanistic studies combining in situ Raman spectroscopy,fluorescence imaging,and coarse-grained molecular dynamics simulations reveal that PTFE selectively enriches octanol at the electrode-electrolyte interface by modulating interfacial hydrophobicity.A continuous-flow microreactor integrating anodic octanol oxidation with cathodic hydrogen evolution reduces cell voltage by~100 m V,achieving simultaneous fatty acid and hydrogen production.This work highlights the critical role of hydrophobic interfacial microenvironment design in organic electrosynthesis,offering a promising strategy for upgrading fatty alcohols under mild conditions.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
基金supported by the Science and Technology Commission of Shanghai Municipality Foundation(No.22230710500)the Interdisciplinary joint research project of Tongji University(No.2023-3-YB-07).
文摘As the core of cathode materials,sensitive metals play important roles in the optimization of acetate production from carbon dioxide(CO_(2))in microbial electrochemical system(MES).In this work,iron(Fe),copper(Cu),and nickel(Ni)as sensitive metal cathode materials were evaluated for CO_(2) conversion in MES.The MES with Feelectrode as a promising electrode material demonstrated a superior CO_(2) reduction performance with a maximum acetate accumulation of 417.9±39.2 mg/L,which was 1.5 and 1.7 folds higher than that in the Ni-electrode and Cu-electrode groups,respectively.Furthermore,an outstanding electron recovery efficiency of 67.7%was shown in the Fe-electrode group.The electron transfer between electrode-suspended sludge was systematically cross-evaluated by the electrochemical behavior and extracellular polymeric substances.The Fe-electrode group had the highest electron transfer rate with 0.194 s-1(k_(app)),which was 17.6 and 21.5 times higher than that of the Cu-and Ni-electrode groups,respectively.Fe-electrode was beneficial for reducing electrochemical impedance between the electrode and suspended sludge.Additionally,redox substances in extracellular polymeric substances of the Fe-electrode group were increased,implying more favorable electron transport dynamics.Simultaneously,enrichments of functional bacteria Acetoanerobium and increased key enzymes involved in the carbonyl pathway of the Fe-electrode group were observed,which also promoted CO_(2) conversion in MES.This study provides a perspective on evaluating the promising sensitive metal electrode material for the process of CO_(2) valorization in MES and offers a reference for the subsequent electrode modification.
基金financially supported by the Sichuan Science and Technology Program (Grant No. 2025NSFSC0139)the China Postdoctoral Science Foundation (Grant No.2023MD734228)+10 种基金funding from Generalitat de Catalunya 2021SGR00457supported by MCIN with funding from European Union NextGenerationEU(PRTR-C17.I1)by Generalitat de Catalunya (In-CAEM Project)the support from the project AMaDE(PID2023-149158OB-C43)funded by MCIN/AEI/10.13039/501100011033/by “ERDF A way of making Europe”by the “European Union”supported by the Severo Ochoa program from Spanish MCIN/AEI (Grant No.:CEX2021-001214-S)funded by the CERCA Programme/Generalitat de Catalunyaperformed in the framework of Universitat Autònoma de Barcelona Materials Science PhD programfunding from the CSC-UAB PhD scholarship program. ICN2 is founding member of e-DREAM[87]
文摘The methanol oxidation reaction(MOR)to formic acid offers a promising alternative to the anodic oxygen evolution reaction(OER)in water electrolysis.However,the development of efficient and cost-effective catalysts remains a primary challenge.In this study,an enhancement in catalytic MOR performance is achieved through the incorporation of Mn atoms with unsaturated t_(2g)orbitals into Ni_(3)Se_(4).Comprehensive experimental analyses and theoretical calculations reveal that substituting Ni with Mn induces strong electron-withdrawing effects,effectively modulating the local coordination environment of the metal centers.The presence of Mn also elongates Ni–Se(O)bonds,which reduces eg orbital occupancy and modifies the spin state of the material.Electrochemical measurements demonstrate that electrodes based on this optimized material exhibit a high spin state and deliver excellent catalytic activity,achieving a MOR current density up to∼190 mA cm^(−2)at 1.6 V.This performance enhancement is attributed to the favorable electronic configuration and reduced reaction energy barriers associated with the high-spin state.
文摘Efficiency of C-C bond coupling in highly inert CO_(2)is relatively low,which severely limits its efficient conversion to acetate.Here,we successfully developed a highly stable NF@CoMn_(2)O_(4)@Cu_(2)O-Ag bimetallic active site catalyst by anchoring Ag on the Cu_(2)O surface.In this catalyst,the Co^(3+)/Mn^(3+)-Mn^(4+)removes excess electrons from the Cu+sites via strong electronic interactions,preventing the reduction of Cu_(2)O to metallic Cu^(0),which ensures the NF@CoMn_(2)O_(4)@Cu_(2)O-Ag exhibits a high resistance to deactivation.The Cu+active sites of NF@CoMn_(2)O_(4)@Cu_(2)O-Ag efficiently electroreduce CO_(2)to the*COatop intermediate,while the Ag active sites efficiently electroreduce CO_(2)to the^(*)CO_(bridge)intermediate.The proximity of Cu+/Ag bimetallic sites shortens the distance for C-C bond coupling between the*COatop and^(*)CO_(bridge)intermediates,facilitating the efficient electrocatalytic coupling of CO_(2)to synthesize acetate.DFT analysis indicates that theΔG required for C-C bond coupling on the short-distance Cu+/Ag bimetallic sites of NF@CoMn_(2)O_(4)@Cu_(2)O-Ag is significantly lower than that of NF@CoMn_(2)O_(4)@Cu_(2)O,enabling a high Faradaic efficiency of 64.97%for acetate production at-0.3 V vs.RHE.This study provides an effective strategy for the rational design of synergistic catalysis between heterometallic catalytic sites to efficiently achieve C-C coupling for the synthesis of C2+products.
基金financially supported by the Major Fundamental Research of Natural Science Foundation of Shandong Province(ZR2022ZD10)National Natural Science Foundation of China(22478211,22372017)+2 种基金Postdoctoral Fellowship Program of CPSF(GZC20231193)Liaoning Binhai Laboratory(LBLG-2024-10)Qingdao Postdoctoral Applied Research Project(QDBSH20240102068)。
文摘Electrocatalysis,a form of heterogeneous catalysis,is closely associated with both catalyst properties and the catalyst/electrolyte interfacial microenvironment.Herein,we rationally design and synthesize a unique PdCu nano-sea urchins(PdCu NSUs)featured with high-curvature nanotips,by which the interfacial microenvironment is expected to be tailored to the electrocatalytic reactions.PdCu NSUs exhibit excellent activity for ethanol electrooxidation,with a specific activity of 4.11 mA cm^(-2)and a mass activity of 2.24 mAμg_(Pd)^(-1),and a high Faraday efficiency(FE)of 96.4%toward acetic acid.COMSOL finite element simulations confirm that the unique nanotips could induce a local electric field due to the accumulation of positive charges in the nanotips,resulting in enrichment of OH^(-)at the catalyst surface to promote the formation of Pd-OH_(ads),a species required by ethanol dehydrogenation.Furthermore,DFT calculations and in-situ electrochemical Fourier transform infrared spectroscopy discover that the d-band center of Pd significantly downshifts in PdCu alloy,which facilitates the desorption of the produced acetic acid.This work provides a new electrocata lytic material with high-curvature nanotips,and also clarifies how the material morphology,by inducing local electric fields,affects the interfacial microenvironment and thus the catalytic activity and selectivity.
基金supported by the National Natural Science Foundation of China (Nos. 92261118, 92161103, 22071180)。
文摘Direct conversion of methane into C1 oxygenates under mild condition with high selectivity is a desired goal in the field of energy and chemistry.But it still remains a great challenge due to the intrinsic inertness of methane originating from strong C-H bonds(104 kcal/mol),low solubility in the solvent,and poor selectivity.Herein,we present a direct single-step conversion of methane to formic acid(HCOOH)using molecular oxygen(O_(2)) as the oxidant under gentle conditions on a decatungstate-doped porous cerium metal-organic framework(Ce-MOF),W_(10)@Ce-bpdc.The HCOOH yield of W_(10)@Ce-bpdc-2 was 155μmol/gcatat room temperature in 12 h.The process and mechanism of conversion of methane to HCOOH was revealed by spectroscopic characteristics and controlled experiments.In the presence of light,O_(2)was converted to H_(2)O_(2)by catalyst and then to·OH radicals in solution,which interact with methane and undergo intermediates to produce HCOOH.Our experiment provides a new way to catalyze methane in combination with MOF and polyoxometalates(POMs).
文摘The electrocatalytic oxidation of glycerol toward formic acid is one of the most promising pathways for transformation and utilization of glycerol.Herein,a series of well-defined Ni_(n)(SR)_(2n) nanoclusters(n=4,5,6;denoted as Ni NCs)were prepared for the electrocatalytic glycerol oxidation toward formic acid,in which Ni_(6)-PET-50CV afforded the most excellent electrocatalytic performance with a high formic acid selectivity of 93% and a high glycerol conversion of 86%.This was attributed to the lowest charge transfer impedance and the most rapid reaction kinetics.Combined electrochemical measurements and X-ray absorption fine structure measurements revealed that the structures of Ni NCs remained intact after CV scanning pretreatment and electrocatalysis via forming the Ni–O bond.Additionally,the kinetic studies and in-situ Fourier transformed infrared suggested a sequential oxidation mechanism,in which the main reaction steps of glycerol→glyceraldehyde→glyceric acid were very rapid to produce a high selectivity of formic acid even though the low glycerol conversion.This work presents an opportunity to study Ni NCs for the efficient electrocatalytic oxidation of biomass-derived polyhydroxyl platform molecules to produce value-added carboxylic acids.
基金Financial supports from the National Natural Science Foundation(No.21991104 and No.22,278,235)。
文摘Electrocatalysis has emerged as a sustainable approach for the selective oxidation of fatty alcohols to fatty acids,circumventing the environmental concerns associated with conventional routes.However,the low aqueous solubility of hydrophobic fatty alcohols presents a major challenge.While nickel hydroxide(Ni(OH)_(2))serves as a cost-effective catalyst for alcohol oxidation,its hydrophilic nature limits substrate accessibility and mass transport,causing sluggish kinetics and competing oxygen evolution.Herein,we propose a hydrophobic interface engineering strategy via co-electrodeposition of Ni(OH)_(2)with polytetrafluoroethylene(PTFE),fabricating the composite electrode(ED-Ni(OH)_(2)-PTFE).The optimized electrode achieves 95%Faradaic efficiency for octanoic acid at 1.5 V vs.RHE,with a production rate 2–3 times higher than pristine Ni(OH)_(2).Mechanistic studies combining in situ Raman spectroscopy,fluorescence imaging,and coarse-grained molecular dynamics simulations reveal that PTFE selectively enriches octanol at the electrode-electrolyte interface by modulating interfacial hydrophobicity.A continuous-flow microreactor integrating anodic octanol oxidation with cathodic hydrogen evolution reduces cell voltage by~100 m V,achieving simultaneous fatty acid and hydrogen production.This work highlights the critical role of hydrophobic interfacial microenvironment design in organic electrosynthesis,offering a promising strategy for upgrading fatty alcohols under mild conditions.
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.
