Chloroplast-like porous bismuth-based core–shell structure for high energy efficiency CO2 electroreduction  

具有类叶绿体多孔核壳结构的铋基催化剂用于高效CO2电还原

作　　者：Yi-Rong Wang Ru-Xin Yang Yifa Chen Guang-Kuo Gao Yu-Jie Wang Shun-Li Li Ya-Qian Lan 王艺蓉;杨汝欣;陈宜法;高广阔;王玉洁;李顺利;兰亚乾(Jiangsu Collaborative Innovation Centre of Biomedical Functional Materials,Jiangsu Key Laboratory of New Power Batteries,School of Chemistry and Materials Science,Nanjing Normal University,Nanjing 210023,China)

机构地区：[1]Jiangsu Collaborative Innovation Centre of Biomedical Functional Materials,Jiangsu Key Laboratory of New Power Batteries,School of Chemistry and Materials Science,Nanjing Normal University,Nanjing 210023,China

出　　处：《Science Bulletin》2020年第19期1635-1642,M0003,M0004,共10页科学通报（英文版）

基　　金：financially supported by the National Natural Science Foundation of China(21622104,21871142 and 21901122);the Natural Science Foundation of Jiangsu Province of China(BK20171032);the Natural Science Research of Jiangsu Higher Education Institutions of China(17KJB150025 and 19KJB150011);Projects funded by China Postdoctoral Science Foundation(2018 M630572 and 2019 M651873);Priority Academic Program Development of Jiangsu Higher Education Institutions;the Foundation of Jiangsu Collaborative Innovation Center of Biomedical Functional Materials。

摘　　要：Electrochemical CO2 reduction reaction(CO2RR)to formate is economically viable considering the energy input and market value.Through learning nature,a series of chloroplast-like porous bismuth-based core–shell(CPBC)materials have been designed.In these materials,the porous carbon can enrich and transfer CO2 to the core–shell Bi@Bi2O3 in CO2 reduction process,during which Bi2O3 layer can be transformed into activated metastable layer to efficiently convert CO2 into formate and Bi can provide abundant electrons.Based on this,superior performances for most of important parameters in CO2 RR can be achieved and best of them,CPBC-1 presents remarkable Faradaic efficiency(FEformate>94%)over a wide potential range(-0.65 to-1.0 V)with high catalysis durability(>72 h).Noteworthy,its maximum energy efficiency is as high as 76.7%at-0.7 V,the highest one in reported bismuth-based materials.This work opens novel perspectives in designing nature-inspired CO2RR electrocatalysts.二氧化碳的过量排放引发了一系列的环境和能源问题.如何将CO2转化为我们生活所需的能源产品对于人类社会的发展具有重大意义.从能量输入和市场价值等方面考虑,利用电化学方法将CO2电还原为甲酸是一种较为理想且绿色的解决途径.本文设计合成了一系列具有类叶绿体多孔核壳结构的铋基催化剂(简写为CPBC-x)用于CO2电还原.在电催化过程中,CPBC-x外层的多孔碳可以将CO2富集并转移到催化中心Bi@Bi2O3中,Bi可以提供电子,Bi2O3可以转化为高活性的亚稳态,高效地将CO2电催化转化为甲酸.CPBC-x表现出很好的化学稳定性和优异的电催化活性,其中,CPBC-1在较宽的电位范围(-0.65^-1.0 V)内法拉第效率可以达到94%以上,其能量效率在-0.7 V下高达76.7%,是目前已报道的铋基材料中能量效率最高的.此外,这类催化剂具有良好的催化稳定性,能够保持高催化效率循环使用72 h以上.这一工作为新型CO2电还原催化剂的设计和制备提供了新思路.

关 键 词：Chloroplast-like porous structure Bi-based activated metastable layer CO2 electroreduction High energy efficiency Formate 

分 类 号：O643.36[理学—物理化学] X701[理学—化学]