Comprehensive Summary Cu-catalyzed electrochemical CO_(2)reduction reaction(CO_(2)RR)and CO reduction reaction(CORR)are of great interest due to their potential to produce carbon-neutral and value-added multicarbon(C2...Comprehensive Summary Cu-catalyzed electrochemical CO_(2)reduction reaction(CO_(2)RR)and CO reduction reaction(CORR)are of great interest due to their potential to produce carbon-neutral and value-added multicarbon(C2+)chemicals.In practice,CO_(2)RR and CORR are typically operated at industrially relevant current densities,making the process exothermal.Although the increased operation temperature is known to affect the performance of CO_(2)RR and CORR,the relationship between temperatures and kinetic parameters was not clearly elaborated,particularly in zero-gap reactors.In this study,we detail the effect of the temperature on Cu-catalyzed CO_(2)RR and CORR.Our electrochemical and operando spectroscopic studies show that high temperatures increase the activity of CO_(2)RR to CO and CORR to C2H4 by enhancing the mass transfer of CO_(2)and CO.As the rates of these two processes are highly influenced by reactant diffusion,elevating the operating temperature results in high local CO_(2)and CO availability to accelerate product formation.Consequently,the*CO coverage in both cases increases at higher temperatures.However,under CO_(2)RR conditions,*CO desorption is more favorable than carbon-carbon(C—C)coupling thermodynamically at high temperatures,causing the reduction in the Faradaic efficiency(FE)of C_(2)H_(4).In CORR,the high-temperature-augmented CO diffusion overcomes the unfavorable adsorption thermodynamics,increasing the probability of C—C coupling.展开更多
In this study, MWNT and alumina nanopowder were used as a ruthenium catalyst support for the conversion of carbon monoxide to methane. Metal foam structures were employed to support such catalytic systems, offering in...In this study, MWNT and alumina nanopowder were used as a ruthenium catalyst support for the conversion of carbon monoxide to methane. Metal foam structures were employed to support such catalytic systems, offering interesting possibilities for commercial applications due to low-pressure drop; excellent flow characteristic and heat transfer properties. Prior to the ruthenium impregnation, the MWNT surface was initially modified by means of metal cation activation and surface adsorption of anionic surfactant. The decoration processes using both surface modifications promoted the deposition of ruthenium with a mean 2 nm diameter. The use of nickel as a nucleating center enhanced the Ru nanoparticle density on the CNT surface compared to the Ru/CNT catalyst prepared by excess solution impregnation. As a reducing agent, ethylene glycol completely converted Ru2＋ to Ru0as confirmed by an EDS/TEM analysis. Among the prepared catalysts, Ru/AI203-CNTs prepared by Ni2＋ activation showed the best performance for the hydrogenation reaction. This is interpreted in terms of the higher ruthenium nanoparticle exposure on the nanostructured catalyst, as a result of the better MWNT dispersion in the MWNT/Al2O3 mixture.展开更多
The synthesis of high-value multi-carbon products through the electrochemical reduction of carbon monoxide(COER) is one of the promising avenues for carbon utilization and energy storage,in which searching for efficie...The synthesis of high-value multi-carbon products through the electrochemical reduction of carbon monoxide(COER) is one of the promising avenues for carbon utilization and energy storage,in which searching for efficient electrocatalysts that exhibit moderate CO intermediate binding strength and low kinetic barrier for C-C coupling is a key issue.Herein,by means of comprehensive density functional theory(DFT) computations,we theoretically designed three synergistic coupling catalysts by co-doping transition metal(TM=Fe,Co and Ni) and boron(B) into the two-dimensional black phosphorene(BP),namely TMB@BP for COER to C_(2) products.DFT computations and ab initio molecular dynamics simulations reveal the good stability and high feasibility of these proposed TM-B@BP catalysts for practical applications and future experimental synthesis.More interestingly,high-value ethylene(C_(2)H_(4)),ethane(C_(2)H_(6)) and ethanol(C_(2)H_(5)OH) products can be obtained on these three designed electrocatalysts with ultra-small limiting potentials(-0.20~-0.41 V) and low kinetic energy barriers of C-C coupling(0.52~0.91 eV).Meanwhile,the competitive one-carbon(C_(1)) products and hydrogen evolution reaction can also be effectively suppressed.The promising activity and selectivity of these three designed electrocatalysts render them ideal candidates for CO electroreduction,thus providing a cost-effective opportunity to achieve a sustainable production of high value C_(2) chemicals and fuels.展开更多
Electrochemical CO_(2)reduction reaction(CO_(2)RR)has attracted considerable attention in the recent decade for its critical role in the storage of renewable energy and fulfilling of the carbon cycle,and catalysts wit...Electrochemical CO_(2)reduction reaction(CO_(2)RR)has attracted considerable attention in the recent decade for its critical role in the storage of renewable energy and fulfilling of the carbon cycle,and catalysts with varying morphology and modification strategies have been studied to improve the CO_(2)RR activity and selectivity.However,most of the achievements are focused on preliminary reduction products such as CO and HCOOH.Development and research on electrochemical CO reduction reaction(CORR)are considered to be more promising to achieve multicarbon products and a better platform to understand the mechanism of C-C formation.In this review,we introduce the current achievements of CO_(2)RR and emphasize the potential of CORR.We provide a summary of how electrolysis environment,electrode substrates,and cell design affect the performance of CORR catalysts in order to offer a guideline of standard operating conditions for CORR research.The composition-structure-activity relationships for CORR catalysts studied in H-cells and gas-phase flow cells are separately analyzed to give a comprehensive understanding of the development of catalyst design.Finally,the reaction mechanism,latest progress,major challenges and potential opportunities of CORR are also analyzed to provide a critical overview for further performance improvement of CORR.展开更多
基金supported by the National Natural Science Foundation of China(22179088)the Natural Science Foundation of Jiangsu Province of China(BK20210699)+2 种基金the National Natural Science Fund for Excellent Young Scientists Fund Program(Overseas)the Program for Jiangsu Specially-Appointed Professors,the Program of Soochow Innovation and Entrepreneurship Leading Talents(ZXL2022450)the start-up supports of Soochow University,Suzhou Key Laboratory of Functional Nano&Soft Materials,the Collaborative Innovation Center of Suzhou Nano Science&Technology,the 111 Project,the Joint International Research Laboratory of Carbon-Based Functional Materials and Devices.
文摘Comprehensive Summary Cu-catalyzed electrochemical CO_(2)reduction reaction(CO_(2)RR)and CO reduction reaction(CORR)are of great interest due to their potential to produce carbon-neutral and value-added multicarbon(C2+)chemicals.In practice,CO_(2)RR and CORR are typically operated at industrially relevant current densities,making the process exothermal.Although the increased operation temperature is known to affect the performance of CO_(2)RR and CORR,the relationship between temperatures and kinetic parameters was not clearly elaborated,particularly in zero-gap reactors.In this study,we detail the effect of the temperature on Cu-catalyzed CO_(2)RR and CORR.Our electrochemical and operando spectroscopic studies show that high temperatures increase the activity of CO_(2)RR to CO and CORR to C2H4 by enhancing the mass transfer of CO_(2)and CO.As the rates of these two processes are highly influenced by reactant diffusion,elevating the operating temperature results in high local CO_(2)and CO availability to accelerate product formation.Consequently,the*CO coverage in both cases increases at higher temperatures.However,under CO_(2)RR conditions,*CO desorption is more favorable than carbon-carbon(C—C)coupling thermodynamically at high temperatures,causing the reduction in the Faradaic efficiency(FE)of C_(2)H_(4).In CORR,the high-temperature-augmented CO diffusion overcomes the unfavorable adsorption thermodynamics,increasing the probability of C—C coupling.
文摘In this study, MWNT and alumina nanopowder were used as a ruthenium catalyst support for the conversion of carbon monoxide to methane. Metal foam structures were employed to support such catalytic systems, offering interesting possibilities for commercial applications due to low-pressure drop; excellent flow characteristic and heat transfer properties. Prior to the ruthenium impregnation, the MWNT surface was initially modified by means of metal cation activation and surface adsorption of anionic surfactant. The decoration processes using both surface modifications promoted the deposition of ruthenium with a mean 2 nm diameter. The use of nickel as a nucleating center enhanced the Ru nanoparticle density on the CNT surface compared to the Ru/CNT catalyst prepared by excess solution impregnation. As a reducing agent, ethylene glycol completely converted Ru2＋ to Ru0as confirmed by an EDS/TEM analysis. Among the prepared catalysts, Ru/AI203-CNTs prepared by Ni2＋ activation showed the best performance for the hydrogenation reaction. This is interpreted in terms of the higher ruthenium nanoparticle exposure on the nanostructured catalyst, as a result of the better MWNT dispersion in the MWNT/Al2O3 mixture.
基金supported by the National Natural Science Foundation of China (NSFC, Nos. 51972312 and U20A20242)the Natural Science Foundation of Liaoning Province of China (No. 2020-MS-003)。
文摘The synthesis of high-value multi-carbon products through the electrochemical reduction of carbon monoxide(COER) is one of the promising avenues for carbon utilization and energy storage,in which searching for efficient electrocatalysts that exhibit moderate CO intermediate binding strength and low kinetic barrier for C-C coupling is a key issue.Herein,by means of comprehensive density functional theory(DFT) computations,we theoretically designed three synergistic coupling catalysts by co-doping transition metal(TM=Fe,Co and Ni) and boron(B) into the two-dimensional black phosphorene(BP),namely TMB@BP for COER to C_(2) products.DFT computations and ab initio molecular dynamics simulations reveal the good stability and high feasibility of these proposed TM-B@BP catalysts for practical applications and future experimental synthesis.More interestingly,high-value ethylene(C_(2)H_(4)),ethane(C_(2)H_(6)) and ethanol(C_(2)H_(5)OH) products can be obtained on these three designed electrocatalysts with ultra-small limiting potentials(-0.20~-0.41 V) and low kinetic energy barriers of C-C coupling(0.52~0.91 eV).Meanwhile,the competitive one-carbon(C_(1)) products and hydrogen evolution reaction can also be effectively suppressed.The promising activity and selectivity of these three designed electrocatalysts render them ideal candidates for CO electroreduction,thus providing a cost-effective opportunity to achieve a sustainable production of high value C_(2) chemicals and fuels.
基金Changli Li acknowledges financial funding from National Natural Science Foundation of China(No.22002191)Qinghua Liu acknowledges funding from the National Natural Science Foundation of China(U1932212 and 11875257).
文摘Electrochemical CO_(2)reduction reaction(CO_(2)RR)has attracted considerable attention in the recent decade for its critical role in the storage of renewable energy and fulfilling of the carbon cycle,and catalysts with varying morphology and modification strategies have been studied to improve the CO_(2)RR activity and selectivity.However,most of the achievements are focused on preliminary reduction products such as CO and HCOOH.Development and research on electrochemical CO reduction reaction(CORR)are considered to be more promising to achieve multicarbon products and a better platform to understand the mechanism of C-C formation.In this review,we introduce the current achievements of CO_(2)RR and emphasize the potential of CORR.We provide a summary of how electrolysis environment,electrode substrates,and cell design affect the performance of CORR catalysts in order to offer a guideline of standard operating conditions for CORR research.The composition-structure-activity relationships for CORR catalysts studied in H-cells and gas-phase flow cells are separately analyzed to give a comprehensive understanding of the development of catalyst design.Finally,the reaction mechanism,latest progress,major challenges and potential opportunities of CORR are also analyzed to provide a critical overview for further performance improvement of CORR.
