厦门大学谢顺吉团队近日实现了用电极化能力描述符设计甲醇中唯一C-H键活化的光催化剂。相关论文于2025年6月19日发表在《美国化学会志》上。

光催化越来越多地被用作绿色合成的有效工具，其中特定化学键的精确活化对于实现高选择性至关重要。基于描述符的标度已成为评估非均相光催化中结构-活性关系的有效方法；然而，与选择性相关的描述符仍然很少。研究组介绍了“电极化能力（δ）”作为一种新的描述符，它考虑了活性位点及其周围微环境的极性，结合了电、结构和轨道的贡献。δ允许量化各种半导体之间的表面-吸附物相互作用。

该描述符在甲醇中C-H或O-H键的光催化活化中进行了评估，其中优先的C-H键活化导致氧化偶联，从而产生乙二醇（EG），这是一种重要的散装化学品。δ捕获了实验报告的具有不同性能的半导体之间的选择性趋势，并有助于碳掺杂六方氮化硼（C-h-BN）的合理设计，实现了98.9%的卓越EG选择性。该工作强调了通过描述符引导的选择性光催化剂设计加速绿色合成创新的巨大潜力。

附：英文原文

Title: Photocatalyst Design with an Electrical-Polarization-Ability Descriptor for Exclusive C–H Bond Activation in Methanol

Author: Leyuan Cui, Jun Feng, Shimiao Wu, Sha Xu, Xuejiao Wu, Shuhong Zhang, Qinghong Zhang, Gang Fu, Ye Wang, Shunji Xie

Issue&Volume: June 19, 2025

Abstract: Photocatalysis is increasingly used as an effective tool for green synthesis, where the precise activation of specific chemical bonds is crucial for achieving high selectivity. Descriptor-based scaling has emerged as an effective method for assessing structure–activity relationships in heterogeneous photocatalysis; however, selectivity-related descriptors remain scarce. Here, we introduce the “electrical-polarization-ability (δ)” as a novel descriptor that considers the polarity of the active site and its surrounding microenvironment, incorporating electrical, structural, and orbital contributions. δ allows for the quantification of surface–adsorbate interactions across various semiconductors. This descriptor is evaluated in the photocatalytic activation of C–H or O–H bonds in methanol, where preferential C–H bond activation leads to oxidative coupling to yield ethylene glycol (EG), an important bulk chemical. δ captures selectivity trends among experimentally reported semiconductors with diverse properties and aids in the rational design of carbon-doped hexagonal boron nitride (C-h-BN), achieving an exceptional EG selectivity of 98.9%. Our work underscores the promising potential to accelerate innovation in green synthesis through descriptor-guided selective photocatalyst design.

DOI: 10.1021/jacs.5c02280

Source: https://pubs.acs.org/doi/abs/10.1021/jacs.5c02280