Transferring strongly reducing electrons to bidentate-adsorbed CO<sub>2</sub> for efficient and selective formate photosynthesis.

Xu, Jingyi; Chen, Keda; Chong, Meichi; Jing, Jianfang; Leung, Michael K H; Li, Junshan; Zhu, Yongfa · Sci Adv · 2026

basic_science · Level V

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Abstract

The photocatalytic conversion of carbon dioxide into formate offers substantial economic value; however, it suffers from the inherent efficiency-selectivity trade-offs. Here, we introduce phthalocyanine polymer dots coexposed with defined phthalocyanine nitrogen (N<sub>pc</sub>) and phthalocyanine nitrogen-hydrogen (N<sub>pc</sub>─H) sites as promising photocatalysts, achieving synergistic enhancement in efficiency and selectivity. N<sub>pc</sub> sites act as electron nodes, directing photogenerated electrons from photosensitizers toward carbon dioxide-adsorbed phthalocyanine, boosting the reactive charge density by 6.5-fold. Concurrently, the N<sub>pc</sub>─H sites capture carbon dioxide via bidentate adsorption, triggering a carbon-selective protonation pathway for selective formate photosynthesis. Owing to the synergistic advantages, the photocatalyst achieves a record formate production rate of 15.89 millimoles per gram per hour with 98.8% selectivity under natural sunlight and quantum efficiencies exceeding 5% across a broad visible-light spectrum. By clarifying electron migration and proposing a unique carbon-selective protonation reaction mechanism, this work offers transformable guidelines for sustainable solar energy conversion and controllable photocatalytic carbon dioxide reduction.