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The level of carbon dioxide (CO2) in the atmosphere has now reached 420 ppm and new methods are necessary to help combat global warming and climate change. Formate dehydrogenases (FDHs) are microbial enzymes that have a natural capability to convert CO2 to formate (HCO2) via reversible redox catalysis. Formate is a commodity chemical, and can be reduced further enzymatically to formaldehyde and methanol, but it is the FDH-catalyzed conversion of CO2 that is the key step towards valorisation of CO2 to chemicals. This chapter will focus on the recent progress and understanding of the function of FDHs and discuss critical features in relation to their efficient use in practical CO2 reduction.

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