Abstract

Electrolyzers combining CO2 reduction (CO2R) with organic substrate oxidation can produce fuel and chemical feedstocks with a relatively low energy requirement when compared to systems that source electrons from water oxidation. Here, we report an anodic hybrid assembly based on a (2,2,6,6‐tetramethylpiperidin‐1‐yl)oxyl (TEMPO) electrocatalyst modified with a silatrane‐anchor (STEMPO), which is covalently immobilized on a mesoporous indium tin oxide (meso ITO) scaffold for efficient alcohol oxidation (AlcOx). This molecular anode was subsequently combined with a cathode consisting of a polymeric cobalt phthalocyanine on carbon‐nanotubes to construct a hybrid, precious‐metal‐free coupled AlcOx –CO2R electrolyzer. After three hour electrolysis, glycerol is selectively oxidized to glyceraldehyde with a turnover number (TON) of 1000 and Faradaic efficiency (FE) of 83% and the cathode generated a stoichiometric amount of syngas with a CO:H2 ratio of 1.25±0.25 and an overall cobalt‐based TON of 894 with a FE of 82%. This prototype device inspires the design and implementation of nonconventional strategies for coupling CO2R to less energy demanding, and value‐added, oxidative chemistry.