Direct detection of a single[4Fe-4S]cluster in a tungsten-containing enzyme:Electrochemical conversion of CO_(2) into formate by formate dehydrogenase
作者机构：State Key Laboratory of Medicinal Chemical BiologyCollege of Life ScienceNankai UniversityTianjinPeople's Republic of China State Key Laboratory of Microbial MetabolismThe Joint International Research Laboratory of Metabolic&Developmental SciencesSchool of Life Science and BiotechnologyShanghai Jiao Tong UniversityShanghaiPeople's Republic of China Max Planck Institute for Chemical Energy ConversionMülheim an der RuhrGermany Frontier Science Center for Synthetic BiologyKey Laboratory of Systems BioengineeringSchool of Chemical Engineering and TechnologyTianjin UniversityTianjinPeople's Republic of China
出 版 物：《Carbon Energy》 (碳能源（英文）)
年 卷 期：2023年第5卷第5期
页 面：152-164页
核心收录：
学科分类：081704[工学-应用化学] 07[理学] 070304[理学-物理化学(含∶化学物理)] 08[工学] 0817[工学-化学工程与技术] 0703[理学-化学]
基 金：support from the National Key Research and Development Program of China (No.2020YFA0907300) the National Natural Science Foundation of China (No.22077069) the Natural Science Foundation of Tianjin (19JCZDJC33400) the Fundamental Research Funds for the Central Universities,Nankai University (63201111)
主 题：bioelectrocatalysis biofuel CO_(2)conversion formate dehydrogenase iron-sulfur cluster
摘 要：The conversion of CO_(2) into fuels and valuable chemicals is one of the central topics to combat climate change and meet the growing demand for renewable ***,we show that the formate dehydrogenase from Clostridium ljungdahlii(ClFDH)adsorbed on electrodes displays clear characteristic voltammetric signals that can be assigned to the reduction and oxidation potential of the[4Fe-4S]^(2+/+)cluster under nonturnover *** adding substrates,the signals transform into a specific redox center that engages in catalytic electron *** catalyzes rapid and efficient reversible interconversion between CO_(2) and formate in the presence of *** turnover frequency of electrochemical CO_(2) reduction is determined as 1210 s^(-1) at 25℃ and pH 7.0,which can be further enhanced up to 1786 s^(-1) at 50℃.The Faradaic efficiency at−0.6 V(*** hydrogen electrode)is recorded as 99.3%in a 2-h *** experiments and theoretical modeling disclose interesting pathways for CO_(2) entry,formate exit,and OCN−competition,suggesting an oxidation-state-dependent binding mechanism of *** results provide a different perspective for understanding the catalytic mechanism of FDH and original insights into the design of synthetic catalysts.
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