单分散Cu-TCPP/Cu_(2)O杂化微球:一种具有优异电还原CO_(2)产C_(2)性能的级联电催化剂  

Monodispersed Cu-TCPP/Cu_(2)O Hybrid Microspheres:A Superior Cascade Electrocatalyst Toward CO_(2) Reduction to C_(2) Products

作　　者：万紫轩 Aidar Kuchkaev Dmitry Yakhvarov 康雄武 Zi-Xuan Wan;Aidar Kuchkaev;Dmitry Yakhvarov;Xiong-Wu Kang(New Energy Research Institute,School of Environment and Energy,South China University of Technology,Higher Education Mega Center,Guangzhou,510006,Guangdong,China;Arbuzov Institute of Organic and Physical Chemistry,FRC Kazan Scientific Center of RAS,Arbuzov Street 8,Kazan,420088,Russian Federation;Alexander Butlerov Institute of Chemistry,Kazan Federal University,Kremlyovskaya Street 18,Kazan,420008,Russian Federation)

机构地区：[1]华南理工大学环境与能源学院新能源研究所,广东广州510006 [2]阿尔布佐夫有机与物理化学研究所,俄罗斯联邦喀山420088 [3]喀山联邦大学亚历山大·巴特列罗夫化学研究所,俄罗斯联邦喀山420008

出　　处：《电化学（中英文）》2024年第1期36-45,共10页Journal of Electrochemistry

基　　金：supported by the National Natural Science Foundation of China (No. U2032151)。

摘　　要：高效电还原CO_(2)(ECR)为有价值的多碳产物是解决CO_(2)排放问题的有效解决方案。基于卟啉的金属有机框架(MOFs)具有多孔结构和有序的活性位点,有望提高ECR生成多碳产物的选择性。本文制备了由铜-四(4-羧基)卟啉(Cu-TCPP)和Cu_(2)O组成的有机/无机杂化Cu-TCPP@Cu_(2)O电催化剂,其中TCPP在调控形貌方面起着重要作用。ECR过程中原位形成的Cu与Cu-TCPP(Cu-TCPP@Cu)结合可以抑制析氢,富集CO中间体,促进C-C偶联生成C2产物。多孔碳(PC)负载的Cu-TCPP@Cu在PC上被还原为Cu纳米簇,同时对C2产物具有较高的ECR活性和选择性。催化剂在–1.0 V时(相对于可逆氢电极),C_(2)产物法拉第效率为62.3%,部分电流密度为83.4 mA·cm^(-2),是纯Cu_(2)O和TCPP的7.6倍和13.1倍。本论文研究了催化剂形貌和杂化结构如何提高ECR生C_(2)产物的选择性,为高性能ECR催化剂的设计提供了新思路。The electrochemical conversion of carbon dioxide(CO_(2))into valuable chemicals is a feasible way to mitigate the negative impacts of overmuch CO_(2) emissions.Porphyrin-based metal organic frameworks(MOFs)are expected to be used for selective and efficient electrochemical CO_(2) reduction(ECR)with porous structure and ordered active sites.Herein,we report the synthesis of a monodispersed and spherical organic/inorganic hybrid Cu-TCPP@Cu_(2)O elec-trocatalyst composed of Cu-TCPP(TCPP=tetrakis(4-carboxyphenyl)porphyrin)and Cu_(2)O,where TCPP plays significant roles in regulating the morphology.In-situ formed Cu during ECR process in combination with Cu-TCPP(Cu-TCPP@Cu)can suppress hydrogen evolution,enrich CO intermediate and promote CeC coupling toward C_(2) products.The Cu-TCPP@Cu supported on porous carbon(PC)showed ultrafine Cu nanoclusters on PC,and dis-played high ECR activity and selectivity toward C_(2) products,with a C_(2) faradaic efficiency of 62.3%at-1.0 V versus the reversible hydrogen electrode and a C_(2) partial current density of 83.4 mA·cm^(-2),which is 7.6 times and 13.1 times those of pure Cu_(2)O and TCPP,respectively.The morphology and hybrid structure of the catalyst were studied to improve the selectivity of ECR to produce C_(2) products,which provides a new idea for the design of high-performance ECR catalyst.

关 键 词：有机/无机杂化电催化剂 四(4-羧基)卟啉 氧化亚铜 级联电催化剂 

分 类 号：TQ426[化学工程]