Advances in Biomimetic Photoelectrocatalytic Reduction of Carbon Dioxide

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.