Steering artificial photosynthesis via photoinduced conversion of monometallic to bimetallic sites in FeCo nitroprussides.

Wang, Hao; Zhuang, Gui-Lin; Fan, Yingjie; Yin, Hua-Qing; Zhang, Wei; Wu, Zhe; Yao, Shuang; Lu, Tong-Bu et al. · Nat Commun · 2025

basic_science · Level V

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Abstract

Artificial photosynthesis provides an efficient strategy for solar energy storage via water splitting and CO<sub>2</sub> reduction, but it remains a challenge in tuning artificial photosynthesis between these two competing reactions. Herein, we demonstrate photoinduced conversion of monometallic to bimetallic sites in a Fe-Co nitroprusside (FeCo-NP) to steer the reaction path from H<sub>2</sub> evolution to CO<sub>2</sub> reduction. Monometallic Co sites achieve efficient H<sub>2</sub> production with 28.5 mmol g<sup>-1</sup> activity and 85.4% selectivity. Photoinduced release of nitrosyl groups from Fe sites generates bimetallic Fe-Co sites, which suppress H<sub>2</sub> evolution and enhance CO<sub>2</sub> reduction, yielding 31.5 mmol g<sup>-1</sup> activity and 87.3% selectivity for C1 products. Mechanistic investigations reveal that monometallic Co sites catalyze H<sub>2</sub> evolution via H<sub>2</sub>O adsorption and O-H cleavage while bimetallic Fe-Co sites facilitate both H<sub>2</sub>O and CO<sub>2</sub> adsorption and subsequent O and C hydrogenation for CO and HCOOH. This work uncovers a strategy to manipulate competing reaction pathways via photoinduced conversion of monometallic to bimetallic sites, which provides unique insights into addressing environmental issues and energy crises.