HIGHLIGHTS • Flower-like CeO 2 nanoparticles enhance the performance of CuO nanoparticle/Cu. • The system benefits from the heterojunction between p-type CuO and n-type CeO 2. • The selective reduction of CO 2 to methanol on the target catalyst is studied.

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Emerging photoelectrocatalysis (PEC) systems synergize the advantages of electrocatalysis (EC) and photocatalysis (PC) and are considered a green and efficient approach to CO 2 conversion. However, improving the selectivity and conversion rate remains a major challenge. Strategies mimicking natural photosynthesis provide a prospective way to convert CO 2 with high efficiency. Herein, several typical strategies are described for constructing biomimetic photoelectric functional interfaces; such interfaces include metal cocatalysts/semiconductors, small molecules/semiconductors, molecular catalysts/semiconductors, MOFs/semiconductors, and microorganisms/semiconductors. The biomimetic PEC interface must have enhanced CO 2 adsorption capacity, preferentially activate CO 2 , and have an efficient conversion ability; with these properties, it can activate C=O bonds effectively and promote electron transfer and C-C coupling to convert CO 2 to single-carbon or multicarbon products. Interfacial electron transfer and proton coupling on the biomimetic PEC interface are also discussed to clarify the mechanism of CO 2 reduction. Finally, the existing challenges and perspectives for biomimetic photoelectrocatalytic CO 2 reduction are presented.

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