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The application of binaphthyl Salen cobalt molecular catalyst modified BiVO4 photoanode belongs to the field of photoelectrocatalysis technology and organic synthesis cross. BiOI film is deposited on FTO conductive glass by electrochemical deposition method, and then is converted into BiVO4 photoanode substrate by calcination; 3-hydroxy substituted binaphthyl Salen cobalt molecular catalyst CoL is synthesized; CoL is loaded on the surface of BiVO4 by cyclic voltammetry electrodeposition to obtain a hybrid photoanode. The photoanode is applied to the photoelectrocatalytic olefin epoxidation reaction, water is used as oxygen source, and acetone-water is used as electrolyte. The strong interface coupling between the catalyst and BiVO4 is strengthened by the electrodeposition of the molecular catalyst strategy, and the interface charge transport efficiency, reaction conversion rate and selectivity are improved. The conversion rate of styrene reaches 99%, the selectivity of epoxide reaches more than 90%, and the stability is excellent. The application provides a new way for green and efficient synthesis of epoxide, and has wide application prospect.