Zhou Min, Wang Haozhi, Liu Rong, Liu Zheyang, Xiao Xinyan, Li Weilin, Gao Chao, Lu Zhou, Jiang Zhifeng, Shi Weidong, Xiong Yujie
Institute for Energy Research, School of Chemistry and Chemical Engineering, Jiangsu University, 212013, Zhenjiang, Jiangsu, P. R. China.
School of Materials Science and Engineering, Key Laboratory of Pico Electron Microscopy of Hainan Province, Hainan University, 570228, Haikou, Hainan, P. R. China.
Angew Chem Int Ed Engl. 2024 Sep 2;63(36):e202407468. doi: 10.1002/anie.202407468. Epub 2024 Aug 2.
The creation of frustrated Lewis pairs on catalyst surface is an effective strategy for tuning CO activation. The critical step in the formation of frustrated Lewis pairs is the spatial effect of proximal Lewis acid-Lewis base pairs. Here, we demonstrate a facile surface functionalization methodology that enables hydrogen bonding between N and H atoms to mediate the construction of frustrated Lewis pairs in poly(heptazine imide), thereby increasing the propensity to activate CO molecules. Experimental and theoretical results show that the construction of active hydrogen bonding regions can facilitate the bending of CO molecules. Furthermore, the delocalization of electron clouds induced by the hydrogen bonding-mediated frustrated Lewis pairs can promote the heterolytic cleavage and photocatalytic conversion of CO. This work highlights the potential of utilizing hydrogen bonding-mediated strategy in heterogeneously photocatalytic activation of CO over polymer materials.
在催化剂表面创建受阻路易斯对是调节CO活化的有效策略。受阻路易斯对形成的关键步骤是近端路易斯酸-路易斯碱对的空间效应。在此，我们展示了一种简便的表面功能化方法，该方法能使N和H原子之间形成氢键，从而介导聚（七嗪酰亚胺）中受阻路易斯对的构建，进而提高活化CO分子的倾向。实验和理论结果表明，活性氢键区域的构建能够促进CO分子的弯曲。此外，氢键介导的受阻路易斯对所诱导的电子云离域能够促进CO的异裂裂解和光催化转化。这项工作突出了在聚合物材料上通过氢键介导策略进行CO多相光催化活化的潜力。
