Covalent organic frameworks comprising cobalt porphyrins for catalytic CO2 reduction in water
Covalent organic frameworks comprising cobalt porphyrins for catalytic CO2 reduction in water
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DOI：
10.1126/science.aac8343
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发表时间：
2015-09-11
期刊：
影响因子：
56.9
通讯作者：
Chang, Christopher J.
中科院分区：
文献类型：
--
作者：
Lin, Song;Diercks, Christian S.;Chang, Christopher J.
将二氧化碳（CO2）转化为一氧化碳（CO）和其他增值碳产品是清洁能源研究的重要挑战。本文报道了以钴卟啉催化剂为构筑单元，通过亚胺键连接的共价有机骨架（COFs）的模块化优化，制备了一种用于CO2水溶液电化学还原为CO的催化材料，该催化剂表现出高的法拉第效率（90%）和转换数（高达290，000，初始转换频率为9400小时（-1）），过电位为-0.55伏，相当于与分子钴络合物相比活性提高了26倍，24小时内没有降解。X射线吸收数据揭示了COF环境对催化钴中心电子结构的影响。
Conversion of carbon dioxide (CO2) to carbon monoxide (CO) and other value-added carbon products is an important challenge for clean energy research. Here we report modular optimization of covalent organic frameworks (COFs), in which the building units are cobalt porphyrin catalysts linked by organic struts through imine bonds, to prepare a catalytic material for aqueous electrochemical reduction of CO2 to CO. The catalysts exhibit high Faradaic efficiency (90%) and turnover numbers (up to 290,000, with initial turnover frequency of 9400 hour(-1)) at pH 7 with an overpotential of -0.55 volts, equivalent to a 26-fold improvement in activity compared with the molecular cobalt complex, with no degradation over 24 hours. X-ray absorption data reveal the influence of the COF environment on the electronic structure of the catalytic cobalt centers.