Electroenzymatic C1 Fixation to Glycine via Dithiothreitol Regeneration on Functionalized 1T'-MoS₂

Electroenzymatic synthesis, merges the versatility of electrocatalysis with the specificity of enzymology, offering a sustainable strategy for chemical manufacturing. However, the practical application of this approach is often limited by inefficient and incompatible electron transfer between the electrode and enzymes. Here, we present an integrated electroenzymatic platform for the efficient synthesis of glycine from C1 feedstock by establishing an efficient and biocompatible route for electrochemical regeneration of dithiothreitol (DTT) as a redox mediator. We identify 1T'-MoS₂ as a highly active electrocatalyst for the reduction of disulfide bonds, specifically regenerating DTT via a potential-dependent dual-pathway mechanism. Covalent functionalization of the 1T'-MoS₂ catalyst further enhances its performance through precise interfacial microenvironment engineering. Critically, this electrochemical regeneration system is fully biocompatible, enabling its seamless integration with a downstream chemoenzymatic cascade for glycine synthesis. The mild operating conditions preserve enzyme integrity, ensuring sustained high catalytic activity and achieving a 2-fold enhancement in glycine production up to 12.2 mM over 9 h. This work establishes a sustainable platform for C1 valorization by synergistically coupling electrocatalytic and chemoenzymatic processes, providing a generalizable platform for renewable energy-driven biomanufacturing.