Dong Jian-Peng, Xu Yue, Zhang Xun-Guang, Zhang Huan, Yao Ling, Wang Rui, Zang Shuang-Quan
Henan Key Laboratory of Crystalline Molecular Functional Materials, Henan International Joint Laboratory of Tumor Theranostical Cluster Materials, Green Catalysis Center, College of Chemistry, Zhengzhou University, Zhengzhou, 450001, China.
Angew Chem Int Ed Engl. 2023 Nov 27;62(48):e202313648. doi: 10.1002/anie.202313648. Epub 2023 Oct 20.
Atomically precise Cu clusters are highly desirable as catalysts for CO reduction reaction (CO RR), and they provide an appropriate model platform for elaborating their structure-activity relationship. However, an efficient overall photocatalytic CO RR with H O using assembled Cu-cluster aggregates as single component photocatalyst has not been reported. Herein, we report a stable crystalline Cu-S-N cluster photocatalyst with local protonated N-H groups (denoted as Cu -NH). The catalyst exhibits suitable photocatalytic redox potentials, high structural stability, active catalytic species, and a narrow band gap, which account for its outstanding photocatalytic CO RR performance under visible light, with ≈100 % selectivity for CO evolution. Remarkably, systematic isostructural Cu-cluster control experiments, in situ infrared spectroscopy, and density functional theory calculations revealed that the protonated pyrimidine N atoms in the Cu -NH cluster act as a proton relay station, providing a local proton during the photocatalytic CO RR. This efficiently lowers the energy barrier for the formation of the *COOH intermediate, which is the rate-limiting step, efficiently enhancing the photocatalytic performance. This work lays the foundation for the development of atomically precise metal-cluster-based photocatalysts.
原子精确的铜簇作为一氧化碳还原反应（CO RR）的催化剂备受青睐，并且它们为阐述其结构-活性关系提供了合适的模型平台。然而，尚未有报道使用组装的铜簇聚集体作为单一组分光催化剂实现高效的光催化CO RR与水反应。在此，我们报道了一种具有局部质子化N-H基团的稳定结晶铜-硫-氮簇光催化剂（表示为Cu -NH）。该催化剂展现出合适的光催化氧化还原电位、高结构稳定性、活性催化物种以及窄带隙，这解释了其在可见光下出色的光催化CO RR性能，对CO析出的选择性约为100%。值得注意的是，系统的同结构铜簇对照实验、原位红外光谱以及密度泛函理论计算表明，Cu -NH簇中质子化的嘧啶N原子充当质子中继站，在光催化CO RR过程中提供局部质子。这有效地降低了形成*COOH中间体这一速率限制步骤的能量势垒，有效提高了光催化性能。这项工作为基于原子精确金属簇的光催化剂的开发奠定了基础。
