Liu Ning, Jiang Jialong, Chen Zhonghang, Wu Boyuan, Zhang Shiqi, Zhang Yi-Quan, Cheng Peng, Shi Wei
Department of Chemistry, Key Laboratory of Advanced Energy Materials Chemistry (MOE), Frontiers Science Center for New Organic Matter and Renewable Energy Conversion and Storage Center (RECAST), College of Chemistry, Nankai University, Tianjin, 300071, China.
School of Physical Science and Technology, Nanjing Normal University, Nanjing, 210023, P. R. China.
Angew Chem Int Ed Engl. 2023 Nov 20;62(47):e202312306. doi: 10.1002/anie.202312306. Epub 2023 Oct 17.
The electronic state in terms of charge and spin of metal sites is fundamental to govern the catalytic activity of a photocatalyst. Herein, we show that modulation of the electronic states of Cu sites, without changing the coordination environments, of two metal-organic supramolecular assemblies based on π⋅⋅⋅π stacking can significantly improve photocatalytic activity. The use of these heterogeneous photocatalysts, without using noble metal cocatalysts, resulted in an increase of the hydrogen production rate from 522 to 3620 μmol h g . A systematical analysis revealed that the charge density and spin density of the metal centers are efficiently modulated via the modulation of the coordination fields around active copper (II) centers by the variation of the non-coordination groups of terminal ligands, leading to the significant enhancement of photocatalytic activity. This work provides an insight into the electronic state of active metal centers for designing high-performance photocatalysts.
就金属位点的电荷和自旋而言，其电子态对于控制光催化剂的催化活性至关重要。在此，我们表明，基于π⋅⋅⋅π堆积的两种金属有机超分子组装体在不改变配位环境的情况下，对铜位点电子态的调制可显著提高光催化活性。使用这些非均相光催化剂，无需使用贵金属助催化剂，产氢速率从522 μmol h⁻¹ g⁻¹提高到了3620 μmol h⁻¹ g⁻¹。系统分析表明，通过改变末端配体的非配位基团来调制活性铜（II）中心周围的配位场，可有效调制金属中心的电荷密度和自旋密度，从而显著提高光催化活性。这项工作为设计高性能光催化剂时深入了解活性金属中心的电子态提供了思路。
