CO_(2)-to-formate electrosynthesis with high selectivity and stability has been a long-sought objective.Unfortunately,most catalysts undergo structural and valence state changes due to surface oxidation during operati...CO_(2)-to-formate electrosynthesis with high selectivity and stability has been a long-sought objective.Unfortunately,most catalysts undergo structural and valence state changes due to surface oxidation during operation or storage,resulting in decreased catalytic performance.Herein,we report a efficient and stable BiIn@Cu-foam electrode through the in-situ regeneration of Bi^(0) active sites to renew the surface activation.The electronic structure of Bi site can be regulated by introducing In,thereby enhancing the adsorption strength of*OCHO.The optimized electrode exhibits over 90%FE_(formate)at a wide potential window(-0.9–-2.2 V),and formation rate for 3.15 mM cm^(-1)h^(-1).Especially,the electrode can maintain the high performance at continuously electrolysis for more than 300 h,or for more than 50 cycles,even repeated operation and storage for more than 2 years.This work provides a promising candidate and new insight to construct industrially viable stable Bi-based catalyst for formate electrosynthesis.展开更多
Fast scan voltammetry is an efficient tool to distinguish oxidative/reductive adsorp- tion/desorption from that for bulk reaction. In this work, we provide a methodology that the isotherm of oxidative/reductive adsorp...Fast scan voltammetry is an efficient tool to distinguish oxidative/reductive adsorp- tion/desorption from that for bulk reaction. In this work, we provide a methodology that the isotherm of oxidative/reductive adsorption desorption processes at electrode surface can be obtained using just one solution with relatively low reactant concentration, by taking the advantage of varying the potential scan rate （relative of the diffusion rate） to tune the adsorption rate and proper mathematic treatment. The methodology is demonstrated by taking acetate adsorption at Pt（lll） in acidic solution as an example. The possibility for extension of this method toward mechanistic studies of complicated electrocatalytic reactions is also given.展开更多
Surface chemistry modification represents a promising strategy to tailor the adsorption and activation of reaction intermediates for enhancing activity.Herein,we designed a surface oxygen-injection strategy to tune th...Surface chemistry modification represents a promising strategy to tailor the adsorption and activation of reaction intermediates for enhancing activity.Herein,we designed a surface oxygen-injection strategy to tune the electronic structure of SnS_(2) nanosheets,which showed effectively enhanced electrocatalytic activity and selectivity of CO_(2) reduction to formate and syngas(CO and H_(2)).The oxygen-injection SnS_(2) nanosheets exhibit a remarkable Faradaic efficiency of 91.6%for carbonaceous products with a current density of 24.1 mA cm^(−2) at−0.9 V vs RHE,including 83.2%for formate production and 16.5%for syngas with the CO/H_(2) ratio of 1:1.By operando X-ray absorption spectroscopy,we unravel the in situ surface oxygen doping into the matrix during reaction,thereby optimizing the Sn local electronic states.Operando synchrotron radiation infrared spectroscopy along with theoretical calculations further reveals that the surface oxygen doping facilitated the CO_(2) activation and enhanced the affinity for HCOO*species.This result demonstrates the potential strategy of surface oxygen injection for the rational design of advanced catalysts for CO_(2) electroreduction.展开更多
To solve the excessive emission of CO_(2) caused by the excessive use of fossil fuels and the corre‐sponding environmental problems,such as the greenhouse effect and climate warming,electrocat‐alytic CO_(2) reductio...To solve the excessive emission of CO_(2) caused by the excessive use of fossil fuels and the corre‐sponding environmental problems,such as the greenhouse effect and climate warming,electrocat‐alytic CO_(2) reduction to liquid fuel with high selectivity is of huge significance for energy conversion and storge.Indium has been considered as a promising and attractive metal for the reduction of CO_(2) to formate.However,the current issues,such as low selectivity and current activity,largely limit the industrial application for electrocatalytic CO_(2) reduction,the design optimization of the catalyst structure and composition is extremely important.Herein,we develop a facile strategy to regulate surface In–O of In@InO_(x) core‐shell nanoparticles and explore the structure‐performance relation‐ship for efficient CO_(2)‐to‐formate conversion though air calcination and subsequent in situ electro‐chemical reconstruction,discovering that the surface In–O is beneficial to stabilize the CO_(2) interme‐diate and generate formate.The optimized AC‐In@InO_(x)‐CNT catalyst exhibits a C1 selectivity up to 98%and a formate selectivity of 94%as well as a high partial formate current density of 32.6 mA cm^(-2).Furthermore,the catalyst presents an excellent stability for over 25 h with a limited activity decay,outperforming the previously reported In‐based catalysts.These insights may open up op‐portunities for exploiting new efficient catalysts by manipulating their surface.展开更多
Molecular adsorption of formate and carboxyl on stoichiometric CeO2（111） and CeO2（110） surfaces was studied using periodic density functional theory （DFT＋U） calculations. Two distinguishable adsorption modes （...Molecular adsorption of formate and carboxyl on stoichiometric CeO2（111） and CeO2（110） surfaces was studied using periodic density functional theory （DFT＋U） calculations. Two distinguishable adsorption modes （strong and weak） of formate are identified. The bidentate configuration is more stable than the monodentate adsorption configuration. Both formate and carboxyl bind at the more open CeO2（110） surface are stronger. The calculated vibrational frequencies of two adsorbed species are consistent with the experimental measurements. Fi- nally, the effects of U parameters on the adsorption of formate and carboxyl over both CeO2 surfaces were investigated. We found that the geometrical configurations of two adsorbed species are not affected by different U parameters （U = 0, 5, and 7）. However, the calculated ad- sorption energy of carboxyl pronouncedly increases with the U value while the adsorption energy of formate only slightly changes （〈0.2 eV）. The Bader charge analysis shows the opposite charge transfer occurs for formate and carboxyl adsorption where the adsorbed formate is neg- atively charge while the adsorbed carboxyl is positively charged. Interestingly, with the increasing U parameter, the amount of charge is also increased.展开更多
CO_(2) electrochemical reduction(CO_(2)ER)is an important research area for carbon neutralization.However,available catalysts for CO_(2) reduction are still characterized by limited stability and activity.Recently,met...CO_(2) electrochemical reduction(CO_(2)ER)is an important research area for carbon neutralization.However,available catalysts for CO_(2) reduction are still characterized by limited stability and activity.Recently,metallic bismuth(Bi)has emerged as a promising catalyst for CO_(2) ER.Herein,we report the solid cathode electroreduction of commercial micronized Bi2O3as a straightforward approach for the preparation of nanostructured Bi.At-1.1 V versus reversible hydrogen electrode in a KHCO3aqueous electrolyte,the resulting nanostructure Bi delivers a formate current density of~40 mA·cm^(-2) with a current efficiency of~86%,and the formate selectivity reaches97.6% at-0.78 V.Using nanosized Bi2O3as the precursor can further reduce the primary particle sizes of the resulting Bi,leading to a significantly increased formate selectivity at relatively low overpotentials.The high catalytic activity of nanostructured Bi is attributable to the ultrafine and interconnected Bi nanoparticles in the nanoporous structure,which exposes abundant active sites for CO_(2) electrocatalytic reduction.展开更多
基金supported by the National Natural Science Foundation of China(22238013 and 22178393)Postdoctoral Science Foundation of Central South University(320808)+1 种基金Natural Science Foundation of Hunan Province(2023JJ40706)the High Performance Computing Center of Central South University。
文摘CO_(2)-to-formate electrosynthesis with high selectivity and stability has been a long-sought objective.Unfortunately,most catalysts undergo structural and valence state changes due to surface oxidation during operation or storage,resulting in decreased catalytic performance.Herein,we report a efficient and stable BiIn@Cu-foam electrode through the in-situ regeneration of Bi^(0) active sites to renew the surface activation.The electronic structure of Bi site can be regulated by introducing In,thereby enhancing the adsorption strength of*OCHO.The optimized electrode exhibits over 90%FE_(formate)at a wide potential window(-0.9–-2.2 V),and formation rate for 3.15 mM cm^(-1)h^(-1).Especially,the electrode can maintain the high performance at continuously electrolysis for more than 300 h,or for more than 50 cycles,even repeated operation and storage for more than 2 years.This work provides a promising candidate and new insight to construct industrially viable stable Bi-based catalyst for formate electrosynthesis.
基金This work was supported by one Hundred Talents＇ Program of the Chinese Academy of Science, the National Natural Science Foundation of China （No.20773116, No.21273215, and No.J1030412）, and 973 Program from theMinistry of Science and Technology of China （No.2010CB923302）. Many Thanks to Prof. Shen Ye from Hokkaido university for the help in establishing techniques for single crystalline electro- chemistry.
文摘Fast scan voltammetry is an efficient tool to distinguish oxidative/reductive adsorp- tion/desorption from that for bulk reaction. In this work, we provide a methodology that the isotherm of oxidative/reductive adsorption desorption processes at electrode surface can be obtained using just one solution with relatively low reactant concentration, by taking the advantage of varying the potential scan rate （relative of the diffusion rate） to tune the adsorption rate and proper mathematic treatment. The methodology is demonstrated by taking acetate adsorption at Pt（lll） in acidic solution as an example. The possibility for extension of this method toward mechanistic studies of complicated electrocatalytic reactions is also given.
基金This work was supported by National Natural Science Foundation of China(Grants No.12025505)China Ministry of Science and Technology(2017YFA0208300)+2 种基金Youth Innovation Promotion Association CAS(CX2310007007 and CX2310000091)Open Fund Project of State Key Laboratory of Environmentally Friendly Energy Materials(20kfhg08)We would thank NSRL and SSRF for the synchrotron beam time.The calculations were performed on the supercomputing system in the Supercomputing Center of University of Science and Technology of China.
文摘Surface chemistry modification represents a promising strategy to tailor the adsorption and activation of reaction intermediates for enhancing activity.Herein,we designed a surface oxygen-injection strategy to tune the electronic structure of SnS_(2) nanosheets,which showed effectively enhanced electrocatalytic activity and selectivity of CO_(2) reduction to formate and syngas(CO and H_(2)).The oxygen-injection SnS_(2) nanosheets exhibit a remarkable Faradaic efficiency of 91.6%for carbonaceous products with a current density of 24.1 mA cm^(−2) at−0.9 V vs RHE,including 83.2%for formate production and 16.5%for syngas with the CO/H_(2) ratio of 1:1.By operando X-ray absorption spectroscopy,we unravel the in situ surface oxygen doping into the matrix during reaction,thereby optimizing the Sn local electronic states.Operando synchrotron radiation infrared spectroscopy along with theoretical calculations further reveals that the surface oxygen doping facilitated the CO_(2) activation and enhanced the affinity for HCOO*species.This result demonstrates the potential strategy of surface oxygen injection for the rational design of advanced catalysts for CO_(2) electroreduction.
文摘To solve the excessive emission of CO_(2) caused by the excessive use of fossil fuels and the corre‐sponding environmental problems,such as the greenhouse effect and climate warming,electrocat‐alytic CO_(2) reduction to liquid fuel with high selectivity is of huge significance for energy conversion and storge.Indium has been considered as a promising and attractive metal for the reduction of CO_(2) to formate.However,the current issues,such as low selectivity and current activity,largely limit the industrial application for electrocatalytic CO_(2) reduction,the design optimization of the catalyst structure and composition is extremely important.Herein,we develop a facile strategy to regulate surface In–O of In@InO_(x) core‐shell nanoparticles and explore the structure‐performance relation‐ship for efficient CO_(2)‐to‐formate conversion though air calcination and subsequent in situ electro‐chemical reconstruction,discovering that the surface In–O is beneficial to stabilize the CO_(2) interme‐diate and generate formate.The optimized AC‐In@InO_(x)‐CNT catalyst exhibits a C1 selectivity up to 98%and a formate selectivity of 94%as well as a high partial formate current density of 32.6 mA cm^(-2).Furthermore,the catalyst presents an excellent stability for over 25 h with a limited activity decay,outperforming the previously reported In‐based catalysts.These insights may open up op‐portunities for exploiting new efficient catalysts by manipulating their surface.
基金supported by the Laboratory Directed Research and Development(LDRD) Project of the Pacific Northwest National Laboratory(PNNL)The computations were performed using the Molecular Science Computing Facility in the William R.Wiley Environmental Molecular Sciences Laboratory (EMSL)+1 种基金a U.S.Department of Energy national scientific user facility located at PNNL in Richland,WashingtonPart of the computing time was also granted by the National Energy Research Scientific Computing Center(NERSC)
文摘Molecular adsorption of formate and carboxyl on stoichiometric CeO2（111） and CeO2（110） surfaces was studied using periodic density functional theory （DFT＋U） calculations. Two distinguishable adsorption modes （strong and weak） of formate are identified. The bidentate configuration is more stable than the monodentate adsorption configuration. Both formate and carboxyl bind at the more open CeO2（110） surface are stronger. The calculated vibrational frequencies of two adsorbed species are consistent with the experimental measurements. Fi- nally, the effects of U parameters on the adsorption of formate and carboxyl over both CeO2 surfaces were investigated. We found that the geometrical configurations of two adsorbed species are not affected by different U parameters （U = 0, 5, and 7）. However, the calculated ad- sorption energy of carboxyl pronouncedly increases with the U value while the adsorption energy of formate only slightly changes （〈0.2 eV）. The Bader charge analysis shows the opposite charge transfer occurs for formate and carboxyl adsorption where the adsorbed formate is neg- atively charge while the adsorbed carboxyl is positively charged. Interestingly, with the increasing U parameter, the amount of charge is also increased.
基金financially supported by the National Natural Science Foundation of China(Nos.22072110 and 21872107)the Key Research and Development Projects of Hubei Province,China(2022BAA083)。
文摘CO_(2) electrochemical reduction(CO_(2)ER)is an important research area for carbon neutralization.However,available catalysts for CO_(2) reduction are still characterized by limited stability and activity.Recently,metallic bismuth(Bi)has emerged as a promising catalyst for CO_(2) ER.Herein,we report the solid cathode electroreduction of commercial micronized Bi2O3as a straightforward approach for the preparation of nanostructured Bi.At-1.1 V versus reversible hydrogen electrode in a KHCO3aqueous electrolyte,the resulting nanostructure Bi delivers a formate current density of~40 mA·cm^(-2) with a current efficiency of~86%,and the formate selectivity reaches97.6% at-0.78 V.Using nanosized Bi2O3as the precursor can further reduce the primary particle sizes of the resulting Bi,leading to a significantly increased formate selectivity at relatively low overpotentials.The high catalytic activity of nanostructured Bi is attributable to the ultrafine and interconnected Bi nanoparticles in the nanoporous structure,which exposes abundant active sites for CO_(2) electrocatalytic reduction.
