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电催化二氧化碳还原反应是将温室气体转化为高附加值燃料和化学品的重要途径，催化剂活性位点的电子结构从根本上决定其电催化性能。本文设计并合成了一类二维金属卟啉共价有机框架/石墨烯异质结构(M-COF/graphene)，该体系金属活性中心的局域配位结构明确均一，且在框架内周期性有序排布。电催化二氧化碳还原结果表明，Co-COF/graphene的催化性能明显优于Ni-COF/graphene，在-0.66 V vs. RHE下，其生成CO的法拉第效率达85%，同时分电流密度为7 mA cm-2。结合原位衰减全反射-表面增强红外吸收光谱，进一步揭示了反应过程中催化剂与*CO中间体的相互作用，为单位点催化剂的结构设计提供了新策略。
Abstract：Electrocatalytic carbon dioxide reduction reaction (CO2RR) is an important approach to convert greenhouse gases into high-value-added fuels and chemicals. The electronic structure of the active sites in catalysts fundamentally determines their electrocatalytic performance. In this work， a series of two-dimensional metalloporphyrin-based covalent organic framework–graphene heterostructures (M-COF/graphene) are designed and synthesized. These materials feature well-defined and homogeneous local coordination environments of the metal active centers， which are periodically arranged within the framework. The electrocatalytic CO2RR results demonstrate that Co-COF/graphene exhibits excellent CO2 reduction capability， achieving a CO Faradaic efficiency of 85% with a partial current density of 7 mA cm-2 at -0.66 V vs. RHE. Furthermore， in-situ ATR-SEIRAS reveals the interaction between the catalyst and the CO intermediate during the reaction， providing a new strategy for the structural design of single-site catalysts.
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基本信息:
DOI：10.16026/j.cnki.iea.2026010031
中图分类号:O643.36;X701
引用信息:
[1]武艺洁,周锡庚,张黎明.二维金属卟啉共价有机框架/石墨烯异质结构的电催化CO_(2)还原性能研究[J].离子交换与吸附().DOI:10.16026/j.cnki.iea.2026010031.
基金信息:
国家重点研发计划（项目号2024YFB4006800）; 国家自然科学基金（项目号22272029，22472036）; 上海市科学技术委员会（项目号22520711100，22ZR1415700，23ZR1406900）
2026-05-18
2026-05-18
2026-05-18