随着全球工业化进程的快速发展,日益增多的人类活动不仅加速化石燃料的消耗,还会导致温室气体二氧化碳(CO2)的大量排放.同时,CO2也是廉价、无毒无害、储量丰富的C1资源,将其转化为有价值的化学品具有碳资源合理利用和环境保护的双重意义...随着全球工业化进程的快速发展,日益增多的人类活动不仅加速化石燃料的消耗,还会导致温室气体二氧化碳(CO2)的大量排放.同时,CO2也是廉价、无毒无害、储量丰富的C1资源,将其转化为有价值的化学品具有碳资源合理利用和环境保护的双重意义.近年来,采用电化学方法温和条件下还原CO2为重要化学品和燃料引起广泛关注.其中,探索廉价电催化剂,高效催化还原CO2为C2产物仍是一个具有挑战性的课题.铜基催化剂由于自身低成本和可还原CO2为多种碳氢产物的优点而备受关注.然而,铜基电催化材料具有选择性差、失活严重和效率低等缺点,并且在电催化还原CO2过程中需要较高的过电位,反应过程中会受到氢气析出副反应的影响.为了得到一种化学性质稳定、高电流密度和高选择性等优点的材料在电催化CO2还原中得到了广泛的研究.然而,单纯的铜催化剂对CO2分子的活化以及反应中间体的吸附能力较低,导致了铜基材料催化剂电催化CO2还原活性及选择性较低.因此,开发出可实际应用的高效率和高选择性的电极材料是当前该技术研究中亟待解决的关键科学问题.近年来,铜基二元合金在电催化CO2还原反应中受到广泛关注.由于二元金属的电子结构和各元素的电子结合能发生变化,其催化活性明显优于单金属催化剂.因此,铜基双金属合金在提高CO2还原产物选择性方面具有广阔的前景.本文采用低温还原的方法制备了一系列不同组成的Cu-Sb双金属合金,系统研究了一系列不同配比的Cu-Sb双金属合金对电催化还原CO2为乙烯的影响.研究发现,当Cu/Sb比例为10/1(Cu10-Sb1)时,可有效提高乙烯的法拉第效率及电流密度.当以0.1 M KCl水溶液作为电解液,电位为-1.19 V vs.RHE时,乙烯的法拉第效率和电流密度分别为49.73%和28.5 mA cm-2.实验结果表明,Cu-Sb双金属合金催化剂优异的催化性能主要源于适宜的电子态、良好的CO2吸附性能、较大的电化学比表面积和较高的电子传输速率.迄今,用Cu-Sb作为催化剂进行电催化还原CO2制乙烯尚未见报道.展开更多
The CuO/CeO_(2) composites with strong metal-support interaction were synthesised,which can efficiently electroreduct CO_(2)to C(2)H_(4).The Faradaic efficiency(FE)of C_(2)H_(4) could reach 50.5%with a current density...The CuO/CeO_(2) composites with strong metal-support interaction were synthesised,which can efficiently electroreduct CO_(2)to C(2)H_(4).The Faradaic efficiency(FE)of C_(2)H_(4) could reach 50.5%with a current density of 18 mA cm^(-2).The strong metal-support interaction could not only enhance the adsorption and activation of CO_(2),but also can stablize the CuO.展开更多
Electrocatalytic CO_(2)reduction(ECR)offers an attractive approach to realizing carbon neutrality and producing valuable chemicals and fuels using CO_(2)as the feedstock.However,the lack of cost-effective electrocatal...Electrocatalytic CO_(2)reduction(ECR)offers an attractive approach to realizing carbon neutrality and producing valuable chemicals and fuels using CO_(2)as the feedstock.However,the lack of cost-effective electrocatalysts with better performances has seriously hindered its application.Herein,a one-step co-electrodeposition method was used to introduce Zn,a metal with weak^(*)CO binding energy,into Cu to form Cu/Zn intermetallic catalysts(Cu/Zn IMCs).It was shown that,using an H-cell,the high Faradaic efficiency of C_(2+)hydrocarbons/alcohols()could be achieved in ECR by adjusting the surface metal components and the applied potential.In suitable conditions,FEC_(2+)and current density could be as high as 75%and 40 mA/cm^(2),respectively.Compared with the Cu catalyst,the Cu/Zn IMCs have a lower interfacial charge transfer resistance and a larger electrochemically active surface area(ECSA),which accelerate the reaction.Moreover,the^(*)CO formed on Zn sites can move to Cu sites due to its weak binding with*CO,and thus enhance the C–C coupling on the Cu surface to form C_(2+)products.展开更多
文摘随着全球工业化进程的快速发展,日益增多的人类活动不仅加速化石燃料的消耗,还会导致温室气体二氧化碳(CO2)的大量排放.同时,CO2也是廉价、无毒无害、储量丰富的C1资源,将其转化为有价值的化学品具有碳资源合理利用和环境保护的双重意义.近年来,采用电化学方法温和条件下还原CO2为重要化学品和燃料引起广泛关注.其中,探索廉价电催化剂,高效催化还原CO2为C2产物仍是一个具有挑战性的课题.铜基催化剂由于自身低成本和可还原CO2为多种碳氢产物的优点而备受关注.然而,铜基电催化材料具有选择性差、失活严重和效率低等缺点,并且在电催化还原CO2过程中需要较高的过电位,反应过程中会受到氢气析出副反应的影响.为了得到一种化学性质稳定、高电流密度和高选择性等优点的材料在电催化CO2还原中得到了广泛的研究.然而,单纯的铜催化剂对CO2分子的活化以及反应中间体的吸附能力较低,导致了铜基材料催化剂电催化CO2还原活性及选择性较低.因此,开发出可实际应用的高效率和高选择性的电极材料是当前该技术研究中亟待解决的关键科学问题.近年来,铜基二元合金在电催化CO2还原反应中受到广泛关注.由于二元金属的电子结构和各元素的电子结合能发生变化,其催化活性明显优于单金属催化剂.因此,铜基双金属合金在提高CO2还原产物选择性方面具有广阔的前景.本文采用低温还原的方法制备了一系列不同组成的Cu-Sb双金属合金,系统研究了一系列不同配比的Cu-Sb双金属合金对电催化还原CO2为乙烯的影响.研究发现,当Cu/Sb比例为10/1(Cu10-Sb1)时,可有效提高乙烯的法拉第效率及电流密度.当以0.1 M KCl水溶液作为电解液,电位为-1.19 V vs.RHE时,乙烯的法拉第效率和电流密度分别为49.73%和28.5 mA cm-2.实验结果表明,Cu-Sb双金属合金催化剂优异的催化性能主要源于适宜的电子态、良好的CO2吸附性能、较大的电化学比表面积和较高的电子传输速率.迄今,用Cu-Sb作为催化剂进行电催化还原CO2制乙烯尚未见报道.
基金supported by the National Key Research and Development Program of China(2017YFA0403102)National Natural Science Foundation of China(21573073,21733011)+1 种基金Beijing Municipal Science&Technology Commission(Z191100007219009)the Chinese Academy of Sciences(QYZDY-SSW-SLH013)。
文摘The CuO/CeO_(2) composites with strong metal-support interaction were synthesised,which can efficiently electroreduct CO_(2)to C(2)H_(4).The Faradaic efficiency(FE)of C_(2)H_(4) could reach 50.5%with a current density of 18 mA cm^(-2).The strong metal-support interaction could not only enhance the adsorption and activation of CO_(2),but also can stablize the CuO.
基金supported by the National Key R&D Program of China(Grant No.2020YFA0710201)the China Postdoctoral Science Foundation(Grant No.2023M731096)+1 种基金the National Natural Science Foundation of China(Grant Nos.22022307,22121002,and 21890761)the Research Funds of Happiness Flower ECNU(Grant No.2020ST2203).
文摘Electrocatalytic CO_(2)reduction(ECR)offers an attractive approach to realizing carbon neutrality and producing valuable chemicals and fuels using CO_(2)as the feedstock.However,the lack of cost-effective electrocatalysts with better performances has seriously hindered its application.Herein,a one-step co-electrodeposition method was used to introduce Zn,a metal with weak^(*)CO binding energy,into Cu to form Cu/Zn intermetallic catalysts(Cu/Zn IMCs).It was shown that,using an H-cell,the high Faradaic efficiency of C_(2+)hydrocarbons/alcohols()could be achieved in ECR by adjusting the surface metal components and the applied potential.In suitable conditions,FEC_(2+)and current density could be as high as 75%and 40 mA/cm^(2),respectively.Compared with the Cu catalyst,the Cu/Zn IMCs have a lower interfacial charge transfer resistance and a larger electrochemically active surface area(ECSA),which accelerate the reaction.Moreover,the^(*)CO formed on Zn sites can move to Cu sites due to its weak binding with*CO,and thus enhance the C–C coupling on the Cu surface to form C_(2+)products.
