Electrochemical Reduction of Carbon Dioxide to Methanol by Direct Injection of Electrons into Immobilized Enzymes on a Modified Electrode

We present results for direct bio‐electrocatalytic reduction of CO(2) to C(1) products using electrodes with immobilized enzymes. Enzymatic reduction reactions are well known from biological systems where CO(2) is selectively reduced to formate, formaldehyde, or methanol at room temperature and ambient pressure. In the past, the use of such enzymatic reductions for CO(2) was limited due to the necessity of a sacrificial co‐enzyme, such as nicotinamide adenine dinucleotide (NADH), to supply electrons and the hydrogen equivalent. The method reported here in this paper operates without the co‐enzyme NADH by directly injecting electrons from electrodes into immobilized enzymes. We demonstrate the immobilization of formate, formaldehyde, and alcohol dehydrogenases on one‐and‐the‐same electrode for direct CO(2) reduction. Carbon felt is used as working electrode material. An alginate–silicate hybrid gel matrix is used for the immobilization of the enzymes on the electrode. Generation of methanol is observed for the six‐electron reduction with Faradaic efficiencies of around 10 %. This method of immobilization of enzymes on electrodes offers the opportunity for electrochemical application of enzymatic electrodes to many reactions in which a substitution of the expensive sacrificial co‐enzyme NADH is desired.