An Artificial Co‐enzyme Based on the Viologen Skeleton for Highly Efficient CO₂ Reduction to Formic Acid with Formate Dehydrogenase

Formate dehydrogenase (FDH) is an attractive catalyst for the reduction of CO 2 because CO 2 is converted to formic acid by FDH at room temperature under normal pressure in neutral aqueous solution. The reduced form of methylviologen acts as an artificial co‐enzyme for FDH in the conversion of CO 2 to formic acid. To improve the catalytic activity of FDH in reducing CO 2 , viologen derivatives with ionic groups were synthesized as effective artificial co‐enzymes for FDH. We used enzyme kinetic analysis to assess the effect of the ionic amino or carboxyl functional groups in the reduced form of the viologen derivatives on the catalytic activity of FDH with respect to the reduction of CO 2 . By using 1,1′‐diaminoethyl‐4,4′‐bipyridinium salt, which is the reduced form of a viologen derivative with two amino groups, we optimized the reduction of CO 2 to formic acid with FDH. The catalytic efficiency value ( k cat / K m ) of the reduced form of 1,1′‐diaminoethyl‐4,4′‐bipyridinium salt was estimated to be more than 560 times larger than that of the natural co‐enzyme NADH. From the analysis result, the CO 2 reduction was influenced by the ionic group of the viologen derivative.