Nitrogen vacancy-induced spin polarization of ultrathin zinc porphyrin nanosheets for efficient photocatalytic CO reduction.

Metalloporphyrin compounds have excellent electron transfer and visible light absorption ability, demonstrating broad application prospects in the field of photocatalysis. In this work, the nitrogen vacancies (NVs) were successfully introduced into zinc porphyrin (ZnTCPP) ultrathin nanosheets through surface N plasma treatment, which is environmentally friendly and can react in low temperatures. Furthermore, the prepared nitrogen vacancies-zinc porphyrin (NVs-ZnTCPP) materials exhibited excellent photocatalytic CO reduction activity and selectivity, specifically, the CO production rate of ZnTCPP-1 (N plasma treatment, 1 min) achieved as high as 12.5 µmol gh, which is about 2.7 times greater than that of untreated ZnTCPP. Based on the experimental and density functional theory calculation (DFT) results, it is found that the promoted photocatalytic performance of NVs-ZnTCPP could be mainly attributed to nitrogen vacancy-induced spin polarization by reducing the reaction barriers and inhibiting the recombination of photoexcited carriers. This work provides a new perspective for the construction of vacancy-based metalloporphyrin, and further explores the intrinsic mechanism between the electron spin property and the performance of the photocatalyst.