Carbon monoliths with programmable valence bands as de novo anodes for additive-free coupling of alcohols into acetals

Abstract Designing functional and reusable electrode materials to replace homogeneous versions of scarifying additives or mediators in electrochemical organic synthesis is of great importance for both the fundamental academics and practical production of various useful compounds. Herein, we rediscover the function of nitrogen-doped carbon monoliths (NxC) as de novo anode materials to trigger a new reaction path for the synthesis of acetals from the direct coupling of alcohols without the assistance of any mediator, oxidant, acid, or organic ligand. The lowered valence bands of carbon monoliths induced by doping nitrogen are of key importance for polarizing and activating the pre-adsorbed O−H groups of benzyl alcohol molecules to boost the high Faradaic efficiency (71% at 1.8 V versus Ag/AgCl) and reusability of NxC anodes, meeting the requirements of green chemistry.