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：Wenjin Li Yanxin Gao Xuan Sun Lei Wan Haishuo Ji Hang Luo Yao Tian Hao Song Geng Wu Liyun Zhang 

机构地区：[1]State Key Laboratory of Medicinal Chemical Biology,College of Life Science,Nankai University,Tianjin,People's Republic of China [2]State Key Laboratory of Microbial Metabolism,The Joint International Research Laboratory of Metabolic&Developmental Sciences,School of Life Science and Biotechnology,Shanghai Jiao Tong University,Shanghai,People's Republic of China [3]Max Planck Institute for Chemical Energy Conversion,Mülheim an der Ruhr,Germany [4]Frontier Science Center for Synthetic Biology,Key Laboratory of Systems Bioengineering,School of Chemical Engineering and Technology,Tianjin University,Tianjin,People's Republic of China

出　　处：《Carbon Energy》2023年第5期152-164,共13页碳能源（英文）

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).

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 energy.Herein,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 conditions.Upon adding substrates,the signals transform into a specific redox center that engages in catalytic electron transport.ClFDH catalyzes rapid and efficient reversible interconversion between CO_(2) and formate in the presence of substrates.The 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(vs.standard hydrogen electrode)is recorded as 99.3%in a 2-h reaction.Inhibition experiments and theoretical modeling disclose interesting pathways for CO_(2) entry,formate exit,and OCN−competition,suggesting an oxidation-state-dependent binding mechanism of catalysis.Our results provide a different perspective for understanding the catalytic mechanism of FDH and original insights into the design of synthetic catalysts.

关 键 词：BIOELECTROCATALYSIS BIOFUEL CO_(2)conversion formate dehydrogenase iron-sulfur cluster 

分 类 号：O64[理学—物理化学]