Abstract
We report an organic redox‐polymer‐based electroenzymatic nitrogen fixation system using a metal‐free redox polymer, namely neutral‐red‐modified poly(glycidyl methacrylate‐co‐methylmethacrylate‐co‐poly(ethyleneglycol)methacrylate) with a low redox potential of −0.58 V vs. SCE. The stable and efficient electric wiring of nitrogenase within the redox polymer matrix enables mediated bioelectrocatalysis of N3 −, NO2 − and N2 to NH3 catalyzed by the MoFe protein via the polymer‐bound redox moieties distributed in the polymer matrix in the absence of the Fe protein. Bulk bioelectrosynthetic experiments produced 209±30 nmol NH3 nmol MoFe−1 h−1 from N2 reduction. 15N2 labeling experiments and NMR analysis were performed to confirm biosynthetic N2 reduction to NH3.
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