Bioelectrochemical synthesis of gluconate by glucose oxidase immobilized in a ferrocene based redox hydrogel

The integration of redox enzymes on electrode surfaces enables the use of renewable energy for highly specific bioelectrochemical synthesis. Herein, we investigate the oxidation of glucose to gluconic acid on a bioanode, combining electrochemical and enzymatic components. Gluconic acid is a valuable chemical widely used in the industry. The bioanode consists of a redox hydrogel film of polyethylenimine (PEI) containing ferrocene (Fc) as a mediator, glycerol diglycidyl ether (GDGE) as a cross-linker, and the enzyme glucose oxidase (GOx). Optimization of the enzyme and cross-linker loading in the redox film led to faradaic efficiencies up to 96 ± 5 % for gluconate. The oxygen-free setup was highly stable for quantitative electrosynthesis, yielding gluconate concentrations of 6.4 ± 0.25 mmol L^-1. Moreover, this catalase-free anaerobic system showed no production of H₂O₂ within 24 h, thereby eliminating the deactivation of the GOx caused by H₂O₂ and a high enzyme performance, with a turnover frequency (TOF) of 5 x10^-3 s⁻¹. This is the first quantitative bioelectrosynthesis of gluconate in an entirely anaerobic environment with electrode stability of at least 8 h.