Spin-polarized chiral ZnIn2S4 for targeted solar-driven CO2 reduction to acetic acid

Abstract

Acetic acid, an important industrial chemical, is a key target product for CO2 reduction due to its dual role in carbon utilization and chemical feedstock supply. Although photocatalytic CO2 reduction (PCCR) can generate acetic acid alongside other multicarbon products, its yield is typically low, limited by competing reactions and inefficient C-C coupling. Herein, we report a chiral mesostructured ZnIn2S4 (CMZI) photocatalyst that achieves a remarkable acetic acid yield of 962 {umol g-1 h-1 with a high selectivity of 97.3 %. This yield is ten times higher than the current highest reported value, while attaining state-of-the-art selectivity10. The remarkable productivity arises from synergistic effect between chiral structure and sulfur (S) sites of CMZI. Chirality-induced spin polarization in CMZI stabilizes the key triplet OCCO intermediate, significantly promoting C-C coupling efficiency. Theoretical calculations reveal that the S sites on {102} crystal facets of ZnIn2S4 exhibit thermodynamic and kinetic preferences for acetic acid formation. This work offers critical insights into catalytic strategies for CO2 reduction toward the efficient and scalable synthesis of various multicarbon products.