The electronic configuration of central metal atoms in single-atom catalysts(SACs)is pivotal in electrochemical CO_(2) reduction reaction(eCO_(2)RR).Herein,chalcogen heteroatoms(e.g.,S,Se,and Te)were incorporated into...The electronic configuration of central metal atoms in single-atom catalysts(SACs)is pivotal in electrochemical CO_(2) reduction reaction(eCO_(2)RR).Herein,chalcogen heteroatoms(e.g.,S,Se,and Te)were incorporated into the symmetric nickel-nitrogen-carbon(Ni-N_(4)-C)configuration to obtain Ni-X-N_(3)-C(X:S,Se,and Te)SACs with asymmetric coordination presented for central Ni atoms.Among these obtained Ni-X-N_(3)-C(X:S,Se,and Te)SACs,Ni-Se-N_(3)-C exhibited superior eCO_(2)RR activity,with CO selectivity reaching~98% at-0.70 V versus reversible hydrogen electrode(RHE).The Zn-CO_(2) battery integrated with Ni-Se-N_(3)-C as cathode and Zn foil as anode achieved a peak power density of 1.82 mW cm^(-2) and maintained remarkable rechargeable stability over 20 h.In-situ spectral investigations and theoretical calculations demonstrated that the chalcogen heteroatoms doped into the Ni-N_(4)-C configuration would break coordination symmetry and trigger charge redistribution,and then regulate the intermediate behaviors and thermodynamic reaction pathways for eCO_(2)RR.Especially,for Ni-Se-N_(3)-C,the introduced Se atoms could significantly raise the d-band center of central Ni atoms and thus remarkably lower the energy barrier for the rate-determining step of ^(*)COOH formation,contributing to the promising eCO_(2)RR performance for high selectivity CO production by competing with hydrogen evolution reaction.展开更多
Photoelectrocatalysis(PEC)is a promising approach that can convert renewable solar energy into chemical energy,while most concern is concentrated on PEC water splitting to obtain high‐value‐added fuel—hydrogen.In p...Photoelectrocatalysis(PEC)is a promising approach that can convert renewable solar energy into chemical energy,while most concern is concentrated on PEC water splitting to obtain high‐value‐added fuel—hydrogen.In practice,more economic benefits can be produced based on PEC technique,such as H_(2)O oxidative H_(2)O_(2) synthesis,organic selective oxidation,organic pollutants degradation and CO_(2) reduction.Although there are plenty of excellent reviews focusing on the PEC water splitting system,the production of various high‐value‐added chemicals in PEC systems has not been discussed synthetically.This Account will focus on the production process of various high‐value‐added chemicals through PEC technology.The photoelectrode design,reaction environment and working mechanisms of PEC systems are also discussed in detail.We believe that this comprehensive Account of the expanded application of photoelectrocatalysis can add an inestimable impetus to the follow‐up development of this technology.展开更多
Electrochemical CO2 reduction reaction(CO2RR)powered by renewable electricity has emerged as the most promising technique for CO2 conversion,making it possible to realize a carbon‐neutral cycle.Highly efficient,robus...Electrochemical CO2 reduction reaction(CO2RR)powered by renewable electricity has emerged as the most promising technique for CO2 conversion,making it possible to realize a carbon‐neutral cycle.Highly efficient,robust,and cost‐effective catalysts are highly demanded for the near‐future practical applications of CO2RR.Previous studies on atomically dispersed metal‐nitrogen(M‐Nx)sites constituted of earth abundant elements with maximum atom‐utilization efficiency have demonstrated their performance towards CO2RR.This review summarizes recent advances on a variety of M‐Nx sites‐containing transition metal‐centered macrocyclic complexes,metal organic frameworks,and M‐Nx‐doped carbon materials for efficient CO2RR,including both experimental and theoretical studies.The roles of metal centers,coordinated ligands,and conductive supports on the intrinsic activity and selectivity,together with the importance of reaction conditions for improved performance are discussed.The mechanisms of CO2RR over these M‐Nx‐containing materials are presented to provide useful guidance for the rational design of efficient catalysts towards CO2RR.展开更多
Electrocatalytic CO_(2) reduction has attracted growing attention as a promising route to realize artificial carbon recycling.Proton transfer plays an essential role in CO_(2) reduction and dramatically impacts produc...Electrocatalytic CO_(2) reduction has attracted growing attention as a promising route to realize artificial carbon recycling.Proton transfer plays an essential role in CO_(2) reduction and dramatically impacts product distribution.However,the precise control of proton transfer during CO_(2) reduction remains challenging.In this study,we present a well-controlled proton transfer through the modification of several purines with similar molecular structures,and reveal a direct correlation between surface proton transfer capability and CO_(2) reduction selectivity over Cu electrode.With a moderate proton transfer capability,the guanine modification can remarkably boost CH_(4) production and suppress C2 products formation.In-situ ATR-SEIRAS suggests a weakened^(*)CO intermediate adsorption and a relatively low local pH environment after the guanine modification,which facilitates the^(*)CO protonation and detachment for CH_(4) generation.展开更多
Electrochemical CO2 reduction(ECR)represents a promising strategy for utilizing CO2,an industrial waste,as an abundant and cheap carbon source for organic synthesis as well as storing intermittent renewable electricit...Electrochemical CO2 reduction(ECR)represents a promising strategy for utilizing CO2,an industrial waste,as an abundant and cheap carbon source for organic synthesis as well as storing intermittent renewable electricity from renewable sources.Efficient electrocatalysts allowing CO2 to be reduced selectively and actively are crucial since the ECR is a complex and sluggish process producing a variety of products.Metal-organic frameworks(MOFs)and covalentorganic frameworks(COFs)have emerged as versatile materials applicable in many fields due to their unique properties including high surface areas and tunable pore channels.Besides,the emerging reticular chemistry makes tuning their features on the atomic/molecular levels possible,thereby lending credence to the prospect of their utilizations.Herein,an overview of recent progress in employing framework material-based catalysts,including MOFs,COFs and their derivatives,for ECR is provided.The pertinent challenges,future trends,and opportunities associated with those systems are also discussed.展开更多
The preparation of high-value fuels and chemicals through the electrochemical carbon dioxide reduction reaction(CDRR)is of great significance to the virtuous cycle of carbon dioxide.However,due to the high overpotenti...The preparation of high-value fuels and chemicals through the electrochemical carbon dioxide reduction reaction(CDRR)is of great significance to the virtuous cycle of carbon dioxide.However,due to the high overpotential involved in this reaction,high power consumption and high-cost noble-metal-based catalysts are required for driving this process.Herein,the electrochemical CDRR was achieved on biocompatible metal-free nitrogen,phosphorus co-doped carbon-based materials(NP-C)in the microbial fuel cell-microbial electrolysis cell(MFC-MEC)coupling system.As the bioelectrochemistry in MFC supplied power to drive the electrocatalysis in MEC,syngas was spontaneously produced from this coupling system without external energy input.With the NP-C materials as the excellent bifunctional electrocatalyst for the CDRR and oxygen reduction reaction(ORR),the current density of the MEC reached−0.52 mA cm^−2,and the Faradaic efficiencies(FEs)of CO and H2 were 60%and 40%,respectively,at a load resistance of 10Ω.Moreover,the CO/H2 product ratio can be changed by adjusting the load resistance,which will widely meet various demand of syngas usage in further reactions.This study provides a spontaneous and tunable production of syngas in biogas digesters via a electrochemical strategy.展开更多
Electrochemical reduction of CO_2 to CO is an interesting topic. In this work, we prepared metal-free electrodes by depositing graphene oxide(GO), multi-walled carbon nanotube(MWCNT), and GO/MWCNT composites on carbon...Electrochemical reduction of CO_2 to CO is an interesting topic. In this work, we prepared metal-free electrodes by depositing graphene oxide(GO), multi-walled carbon nanotube(MWCNT), and GO/MWCNT composites on carbon paper(CP) using electrophoretic deposition(EPD) method. The electrodes were characterized by different methods, such as X-ray diffraction(XRD) and X-ray photoelectron spectroscopy(XPS). The electrochemical reduction of CO_2 to CO was conducted on the electrodes in 1-butyl-3-methylimidazolium tetrafluoroborate([Bmim]BF4)/acetonitrile(Me CN) electrolyte, and the composition of the electrolyte influenced the reaction significantly. It was demonstrated that GO/MWCNT-CP electrode was very effective for the reaction in IL(90 wt%)/Me CN binary mixture, the Faradaic efficiency of CO and current density were even higher than those on Au and Ag electrodes in the same electrolyte.展开更多
文摘The electronic configuration of central metal atoms in single-atom catalysts(SACs)is pivotal in electrochemical CO_(2) reduction reaction(eCO_(2)RR).Herein,chalcogen heteroatoms(e.g.,S,Se,and Te)were incorporated into the symmetric nickel-nitrogen-carbon(Ni-N_(4)-C)configuration to obtain Ni-X-N_(3)-C(X:S,Se,and Te)SACs with asymmetric coordination presented for central Ni atoms.Among these obtained Ni-X-N_(3)-C(X:S,Se,and Te)SACs,Ni-Se-N_(3)-C exhibited superior eCO_(2)RR activity,with CO selectivity reaching~98% at-0.70 V versus reversible hydrogen electrode(RHE).The Zn-CO_(2) battery integrated with Ni-Se-N_(3)-C as cathode and Zn foil as anode achieved a peak power density of 1.82 mW cm^(-2) and maintained remarkable rechargeable stability over 20 h.In-situ spectral investigations and theoretical calculations demonstrated that the chalcogen heteroatoms doped into the Ni-N_(4)-C configuration would break coordination symmetry and trigger charge redistribution,and then regulate the intermediate behaviors and thermodynamic reaction pathways for eCO_(2)RR.Especially,for Ni-Se-N_(3)-C,the introduced Se atoms could significantly raise the d-band center of central Ni atoms and thus remarkably lower the energy barrier for the rate-determining step of ^(*)COOH formation,contributing to the promising eCO_(2)RR performance for high selectivity CO production by competing with hydrogen evolution reaction.
文摘Photoelectrocatalysis(PEC)is a promising approach that can convert renewable solar energy into chemical energy,while most concern is concentrated on PEC water splitting to obtain high‐value‐added fuel—hydrogen.In practice,more economic benefits can be produced based on PEC technique,such as H_(2)O oxidative H_(2)O_(2) synthesis,organic selective oxidation,organic pollutants degradation and CO_(2) reduction.Although there are plenty of excellent reviews focusing on the PEC water splitting system,the production of various high‐value‐added chemicals in PEC systems has not been discussed synthetically.This Account will focus on the production process of various high‐value‐added chemicals through PEC technology.The photoelectrode design,reaction environment and working mechanisms of PEC systems are also discussed in detail.We believe that this comprehensive Account of the expanded application of photoelectrocatalysis can add an inestimable impetus to the follow‐up development of this technology.
基金supported by the National Key R&D Program of China(2017YFA0700102)the National Natural Science Foundation of China(21573222 and 91545202)+1 种基金the Outstanding Youth Talent Project of Dalian(2017RJ03)the DMTO Project of Dalian Institute of Chemical Physics,CAS(DICP DMTO201702),the Strategic Priority Research Program of the Chinese Academy of Sciences(XDB17020200),the Youth Innovation Promotion Association,CAS(2015145)~~
文摘Electrochemical CO2 reduction reaction(CO2RR)powered by renewable electricity has emerged as the most promising technique for CO2 conversion,making it possible to realize a carbon‐neutral cycle.Highly efficient,robust,and cost‐effective catalysts are highly demanded for the near‐future practical applications of CO2RR.Previous studies on atomically dispersed metal‐nitrogen(M‐Nx)sites constituted of earth abundant elements with maximum atom‐utilization efficiency have demonstrated their performance towards CO2RR.This review summarizes recent advances on a variety of M‐Nx sites‐containing transition metal‐centered macrocyclic complexes,metal organic frameworks,and M‐Nx‐doped carbon materials for efficient CO2RR,including both experimental and theoretical studies.The roles of metal centers,coordinated ligands,and conductive supports on the intrinsic activity and selectivity,together with the importance of reaction conditions for improved performance are discussed.The mechanisms of CO2RR over these M‐Nx‐containing materials are presented to provide useful guidance for the rational design of efficient catalysts towards CO2RR.
文摘Electrocatalytic CO_(2) reduction has attracted growing attention as a promising route to realize artificial carbon recycling.Proton transfer plays an essential role in CO_(2) reduction and dramatically impacts product distribution.However,the precise control of proton transfer during CO_(2) reduction remains challenging.In this study,we present a well-controlled proton transfer through the modification of several purines with similar molecular structures,and reveal a direct correlation between surface proton transfer capability and CO_(2) reduction selectivity over Cu electrode.With a moderate proton transfer capability,the guanine modification can remarkably boost CH_(4) production and suppress C2 products formation.In-situ ATR-SEIRAS suggests a weakened^(*)CO intermediate adsorption and a relatively low local pH environment after the guanine modification,which facilitates the^(*)CO protonation and detachment for CH_(4) generation.
基金financially supported by the National Natural Science Foundation of China(21671096 and 11775105)Shenzhen Peacock Plan(KQTD2016022620054656)。
文摘Electrochemical CO2 reduction(ECR)represents a promising strategy for utilizing CO2,an industrial waste,as an abundant and cheap carbon source for organic synthesis as well as storing intermittent renewable electricity from renewable sources.Efficient electrocatalysts allowing CO2 to be reduced selectively and actively are crucial since the ECR is a complex and sluggish process producing a variety of products.Metal-organic frameworks(MOFs)and covalentorganic frameworks(COFs)have emerged as versatile materials applicable in many fields due to their unique properties including high surface areas and tunable pore channels.Besides,the emerging reticular chemistry makes tuning their features on the atomic/molecular levels possible,thereby lending credence to the prospect of their utilizations.Herein,an overview of recent progress in employing framework material-based catalysts,including MOFs,COFs and their derivatives,for ECR is provided.The pertinent challenges,future trends,and opportunities associated with those systems are also discussed.
基金the National Natural Science Foundation of China(21872147 and 21805277)the Natural Science Foundation of Fujian Province(2018J05030 and 2019J05152)+2 种基金the Key Research Program of Frontier Sciences,CAS(ZDBS-LYSLH028)DNL Cooperation Fund,CAS(DNL201924)the Strategic Priority Research Program,CAS(XDB20000000)。
文摘The preparation of high-value fuels and chemicals through the electrochemical carbon dioxide reduction reaction(CDRR)is of great significance to the virtuous cycle of carbon dioxide.However,due to the high overpotential involved in this reaction,high power consumption and high-cost noble-metal-based catalysts are required for driving this process.Herein,the electrochemical CDRR was achieved on biocompatible metal-free nitrogen,phosphorus co-doped carbon-based materials(NP-C)in the microbial fuel cell-microbial electrolysis cell(MFC-MEC)coupling system.As the bioelectrochemistry in MFC supplied power to drive the electrocatalysis in MEC,syngas was spontaneously produced from this coupling system without external energy input.With the NP-C materials as the excellent bifunctional electrocatalyst for the CDRR and oxygen reduction reaction(ORR),the current density of the MEC reached−0.52 mA cm^−2,and the Faradaic efficiencies(FEs)of CO and H2 were 60%and 40%,respectively,at a load resistance of 10Ω.Moreover,the CO/H2 product ratio can be changed by adjusting the load resistance,which will widely meet various demand of syngas usage in further reactions.This study provides a spontaneous and tunable production of syngas in biogas digesters via a electrochemical strategy.
基金supported by the National Natural Science Foundation of China (21403253, 21533011)
文摘Electrochemical reduction of CO_2 to CO is an interesting topic. In this work, we prepared metal-free electrodes by depositing graphene oxide(GO), multi-walled carbon nanotube(MWCNT), and GO/MWCNT composites on carbon paper(CP) using electrophoretic deposition(EPD) method. The electrodes were characterized by different methods, such as X-ray diffraction(XRD) and X-ray photoelectron spectroscopy(XPS). The electrochemical reduction of CO_2 to CO was conducted on the electrodes in 1-butyl-3-methylimidazolium tetrafluoroborate([Bmim]BF4)/acetonitrile(Me CN) electrolyte, and the composition of the electrolyte influenced the reaction significantly. It was demonstrated that GO/MWCNT-CP electrode was very effective for the reaction in IL(90 wt%)/Me CN binary mixture, the Faradaic efficiency of CO and current density were even higher than those on Au and Ag electrodes in the same electrolyte.
