Direct electron transfer-type four-way bioelectrocatalysis of CO2/formate and NAD+/NADH redox couples by tungsten-containing formate dehydrogenase adsorbed on gold nanoparticle-embedded mesoporous carbon electrodes modified with 4-mercaptopyridine

Autor: Kento Sakai, Yuki Kitazumi, Kazuyoshi Takagi, Osamu Shirai, Kenji Kano
Jazyk: angličtina
Rok vydání: 2017
Předmět:
Zdroj: Electrochemistry Communications, Vol 84, Iss, Pp 75-79 (2017)
ISSN: 1388-2481
Popis: Tungsten-containing formate dehydrogenase from Methylobacterium extorquens AM1 (FoDH1) catalyzes formate oxidation with NAD+. FoDH1 shows little direct communication with carbon electrodes, including mesoporous Ketjen Black-modified glassy carbon electrode (KB/GCE); however, it shows well-defined direct electron transfer (DET)-type bioelectrocatalysis of carbon dioxide reduction, formate oxidation, NAD+ reduction, and NADH oxidation on gold nanoparticle (AuNP)-embedded KB/GCE treated with 4-mercaptopyridine. Microscopic measurements reveal that the AuNPs (d=5nm) embedded on the KB surface are uniformly dispersed. Electrochemical data indicate that the pyridine moiety on the AuNPs plays important roles in facilitating the interfacial electron transfer kinetics and increasing the probability of productive orientation of FoDH1. The formal potential of the electrochemical communication site, which is most probably an ion‑sulfur cluster, is evaluated as −0.591±0.005V vs. Ag|AgCl|sat. KCl from Nernst analysis of the steady-state catalytic waves. Keywords: Gold nanoparticle, Mesoporous carbon electrode, Direct electron transfer, Formate dehydrogenase, Bioelectrocatalysis, 4-Mercaptopyridine
Databáze: OpenAIRE