Citation: Sihong Li, Weiping Deng, Qijie Mo, Haili Song, Chunying Chen, Li Zhang. Engineering S-coordinated Ru single-atoms in a porphyrinic metal-organic framework for CO2 photoreduction[J]. Chinese Journal of Structural Chemistry, ;2026, 45(3): 100841. doi: 10.1016/j.cjsc.2025.100841 shu

Engineering S-coordinated Ru single-atoms in a porphyrinic metal-organic framework for CO2 photoreduction

The catalytic performance of single-atom catalysts in CO2 photoreduction can be optimized through precise modulation of the coordination structures of single-atoms. In this study, Ru single-atoms (Ru-SAs) immobilized on the Zr6O8 clusters of a porphyrinic metal–organic framework (Zn-PCN-222) were modified with sulfhydryl groups (–SH). The resulting RuS-SAs@Zn-PCN-222 exhibited high photocatalytic activity for CO2 reduction to HCOO− using ammonia borane as the H* donor, giving rise to a HCOO− production rate of 54.4 mmol·g–1·h–1 with 99.9% selectivity, which was approximately 20.1 and 4.5 times higher than that of Zn-PCN-222 and –SH-free Ru-SAs@Zn-PCN-222, respectively. Photoelectrochemical measurements demonstrated that the incorporated RuS-SAs enhanced the separation and migration of photogenerated charges in RuS-SAs@Zn-PCN-222. Further in situ experiments revealed that the RuS-SAs could accept photogenerated electrons from Zn-PCN-222 as well as electrons from the –SH groups, and then inject to inert CO2 molecules, thereby facilitating CO2 activation and its subsequent coupling with H* to form HCOO−.
- CO2 reduction,
- Single-atom,
- Metal-organic frameworks,
- Prphyrin,
- Precise chemistry
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