Reversible interconversion of carbon dioxide and formate by an electroactive enzyme.

TitleReversible interconversion of carbon dioxide and formate by an electroactive enzyme.
Publication TypeJournal Article
Year of Publication2008
AuthorsReda, T, Plugge, CM, Abram, NJ, Hirst, J
JournalProc Natl Acad Sci U S A
Volume105
Issue31
Pagination10654-8
Date Published2008 Aug 05
ISSN1091-6490
KeywordsCarbon Dioxide, Catalysis, Deltaproteobacteria, Electrochemistry, Electrodes, Formate Dehydrogenases, Formates, Kinetics, Models, Molecular, Oxidation-Reduction
Abstract

Carbon dioxide (CO(2)) is a kinetically and thermodynamically stable molecule. It is easily formed by the oxidation of organic molecules, during combustion or respiration, but is difficult to reduce. The production of reduced carbon compounds from CO(2) is an attractive proposition, because carbon-neutral energy sources could be used to generate fuel resources and sequester CO(2) from the atmosphere. However, available methods for the electrochemical reduction of CO(2) require excessive overpotentials (are energetically wasteful) and produce mixtures of products. Here, we show that a tungsten-containing formate dehydrogenase enzyme (FDH1) adsorbed to an electrode surface catalyzes the efficient electrochemical reduction of CO(2) to formate. Electrocatalysis by FDH1 is thermodynamically reversible--only small overpotentials are required, and the point of zero net catalytic current defines the reduction potential. It occurs under thoroughly mild conditions, and formate is the only product. Both as a homogeneous catalyst and on the electrode, FDH1 catalyzes CO(2) reduction with a rate more than two orders of magnitude faster than that of any known catalyst for the same reaction. Formate oxidation is more than five times faster than CO(2) reduction. Thermodynamically, formate and hydrogen are oxidized at similar potentials, so formate is a viable energy source in its own right as well as an industrially important feedstock and a stable intermediate in the conversion of CO(2) to methanol and methane. FDH1 demonstrates the feasibility of interconverting CO(2) and formate electrochemically, and it is a template for the development of robust synthetic catalysts suitable for practical applications.

DOI10.1073/pnas.0801290105
Alternate JournalProc. Natl. Acad. Sci. U.S.A.
Citation Key10.1073/pnas.0801290105
PubMed ID18667702
PubMed Central IDPMC2491486
Grant ListMC_U105663141 / / Medical Research Council / United Kingdom