Electroenzymatic Cascades for Nitrogen Upgrading: Beyond Ammonia Towards Value‐Added Nitrogen Chemicals

ABSTRACT The global transition toward sustainable chemical manufacturing demands technologies that leverage natural carbon and nitrogen cycles while minimizing reliance on sacrificial reagents and fossil resources. These biogeochemical cycles are fundamental to life, and enzymes catalyze many of their key transformations. Bioelectrochemical, specifically electroenzymatic, systems offer a promising route to sustainable synthesis by enabling selective redox transformations powered by electricity. However, whereas carbon‐cycle enzymes are now well established in bioelectrochemical synthesis, enzymes from the nitrogen cycle remain comparatively underexplored. Moreover, the nitrogen cycle alone does not access many value‐added nitrogen‐containing products, which require additional C‐N bond formation and organic functionalization steps. In this review, we survey electroenzymatic systems that not only produce ammonia but also upgrade inorganic nitrogen into higher‐value chemicals. We highlight single enzyme systems and multi‐enzyme cascades that combine nitrogen‐cycle enzymes with auxiliary biocatalysts such as amine dehydrogenases, transaminases, oxidoreductases, and nitrile hydratases to generate amines, amides, amino acids, hydrazine derivatives, and other nitrogen‐containing organic compounds. Despite recent progress, only a few studies report the electroenzymatic synthesis of value‐added nitrogen products. We therefore identify the key scientific and engineering challenges, outline the advances needed in enzyme‐electrode interfaces and cascade design, and argue that electroenzymatic nitrogen upgrading is a promising yet underdeveloped approach for future sustainable manufacturing of nitrogen‐based chemicals.