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Developing highly efficient and stable photocatalysts is an effective method to achieve CO2 photocatalytic reduction. Herein, PI/WO3 aerogel photocatalyst was prepared by chemical amide reaction coupled with an ethanol supercritical drying technique. The novel aerogel photocatalysts exhibit excellent photocatalytic performance for reducing CO2 into CO. In particular, PI/WO3-10 aerogel photocatalyst shows the highest yield of CO (5.72 μmol g–1 h–1), which is ca 11-fold higher than that of the pristine PI aerogel. The high CO2 reduction activity can be attributed to the Z-scheme structure, which enhances the separation of photo-generated electron – holes, and induces H2O oxidation on WO3 nanosheets and CO2 reduction on PI aerogel. The photocatalytic reaction mechanism of CO2 when using PI/WO3 aerogel photocatalyst is proposed. [ABSTRACT FROM AUTHOR]