近日，中山大学张利团队研究了用于CO₂光还原的卟啉金属-有机框架中的S配位Ru单原子工程。该项研究成果发表在2025年12月11日出版的《结构化学》杂志上。

在CO₂光还原反应中，单原子催化剂的性能可通过精确调控其配位结构进行优化。

研究组通过在固定于卟啉基金属有机框架（Zn-PCN-222）Zr₆O₈簇上的钌单原子（Ru-SAs）中引入巯基（–SH）进行修饰。所得材料RuS-SAs@Zn-PCN-222在以氨硼烷为H*供体、将CO₂还原为HCOO⁻的光催化反应中表现出高活性，其HCOO⁻生成速率达54.4 mmol·g^–1·h^–1，选择性为99.9%。该速率分别是Zn-PCN-222和未修饰巯基的Ru-SAs@Zn-PCN-222的约20.1倍和4.5倍。

光电化学测试表明，引入的RuS-SAs增强了RuS-SAs@Zn-PCN-222中光生电荷的分离和迁移。进一步的原位实验揭示，RuS-SAs既可接收来自Zn-PCN-222的光生电子，也能接受来自–SH基团的电子，随后将其注入惰性CO₂分子中，从而促进CO₂活化及其与H*的后续偶联形成HCOO⁻。

附：英文原文

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

Author: anonymous

Issue&Volume: 2025-12-11

Abstract: 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.

DOI: 10.1016/j.cjsc.2025.100841

Source: https://cjsc.ac.cn/cms/issues/941