Defects Induced in Situ Reconstruction of CdS with Oxygen‐Tolerance Up to 23% in the Photocatalytic CO 2 Reduction

Abstract Direct driving the photocatalytic reduction of CO 2 from air or flue gas to produce value‐added chemicals and fuels is very challenging due to the suppressing effect of the more favorable thermodynamically oxygen reduction reaction (ORR). Herein, we presented a novel oxygen‐involved reconstruction pathway on a unique defective CdS‐D in the photocatalytic reduction of CO 2 . The material is highly tolerant to O 2 and generates 2766.7 µmol g −1 h −1 of CO under visible light irradiation in the presence of up to 23% content of O 2 . Intriguingly, instead of inhibiting the performance of CO 2 reduction, the presence of oxygen positively promotes it, CO generation rate is up to 5124 µmol g −1 h −1 after multiple experimental cycles. The meticulously structural analysis reveals that the CdS‐D with abundant defects tended to accumulate photogenerated holes, and S 2− is oxidized to SO 4 2− in the presence of oxygen to produce Cd 2 SO 4 (OH) 2 as the active center for preferable CO 2 adsorption and inhibit the O 2 adsorption, which is the root cause for the high tolerance of oxygen in CO 2 reduction (CO 2 RR). This work reveals a unique reconstruction process of sulfides photo corrosion, which provides a new idea for realizing the direct conversion of low‐concentration CO 2 by omitting expensive carbon capture or purification in industrial carbon resource utilization.