Engineering Single Ni Sites on 3D Cage‐like Cucurbit[n]uril Ligands for Efficient and Selective CO 2 Photocatalytic Reduction

作者：Jingyi Wang, Xiyi Li, Chia‐Hao Chang, Tianyu Zhang, Xuze Guan, Qiong Liu, Liquan Zhang, Ping Wen, Ivan Tang, Yuewen Zhang, Xiaofeng Yang, Junwang Tang, Yang Lan · 发表于：Angewandte Chemie International Edition · 年份：2024 · DOI：10.1002/anie.202417384 · 被引用次数：24 · 研究领域：CO2 Reduction Techniques and Catalysts、Metal-Organic Frameworks: Synthesis and Applications、Covalent Organic Framework Applications

Abstract Solar‐driven CO 2 selective reduction with high conversion is a challenging task yet holds immense promise for both CO 2 neutralization and green fuel production. Enhancing CO 2 adsorption at the catalytic centre can trigger a highly efficient CO 2 capture‐to‐conversion process. Herein, we introduce cucurbit[n]urils (CB[n]), a new family of molecular ligands, as a key component in the creation of a 3D cage‐like metal (nickel, Ni)‐complex molecular co‐catalyst (CB[7]‐Ni) for photocatalysis. It exhibits an unprecedented CO yield rate of 72.1 μmol ⋅ h −1 with a high selectivity of 97.9 % under visible light irradiation. To verify the origin of the carbon source in the products, a straightforward isotopic tracing method is designed based on tandem reactions. The catalytic process commences with photoelectron transfer from Ru(bpy) 3 2+ to the Ni 2+ site, resulting in the reduction of Ni 2+ to Ni + . The locally enriched CO 2 molecules in the cage ligand CB[7] undergo selective reduction by the Ni + nearby to form CO product. This work exemplifies the inspiring potential of ligand structure engineering in advancing the development of efficient unanchored molecular co‐catalysts.