Al2O3‐coated BiVO4 Photoanodes for Photoelectrocatalytic Regioselective C−H Activation of Aromatic Amines

Photoelectrochemistry is becoming an innovative approach to organic synthesis. Generally, the current photoelectrocatalytic organic transformations suffer from limited reaction type, low conversion efficiency and poor stability. Herein, we develop efficient and stable photoelectrode materials using metal oxide protective layer, with a focus on achieving regioselective activation of amine compounds. Notably, our photoelectrochemistry process is implemented under mild reaction conditions and does not involve any directing groups, transition metals or oxidants. The results demonstrate that beyond photocatalysis and electrocatalysis, photoelectrocatalysis exhibits high efficiency, remarkable repeatability and good functional group tolerance, highlighting its great potential for applications. A novel approach for the regioselective activation of aromatic amines C−H bonds is reported using a BiVO4 photoanode coated with an ultrathin Al2O3 protective layer, overcoming the problems of low reactivity and poor stability in photoelectrocatalytic organic synthesis. The deposition of Al2O3 enables maintaining stable photocurrent and the yield of the target product dramatically increases from 48 % to 84 %. Beyond high efficiency and excellent repeatability, this photoelectrocatalytic strategy exhibits good functional group tolerance and environmental friendliness, making it promising for sustainable organic transformations.