Huang Zhi-Sang, Wang Yin-Feng, Qi Ming-Yu, Conte Marco, Tang Zi-Rong, Xu Yi-Jun
College of Chemistry, State Key Laboratory of Photocatalysis on Energy and Environment, Fuzhou University, 350116, Fuzhou, China.
Institute of Fundamental and Frontier Sciences, University of Electronic Science and Technology of China, 611731, Chengdu, China.
Angew Chem Int Ed Engl. 2024 Nov 18;63(47):e202412707. doi: 10.1002/anie.202412707. Epub 2024 Oct 14.
Photo-driven cross-coupling of o-arylenediamines and alcohols has emerged as an alternative for the synthesis of bio-active benzimidazoles. However, tackling the key problem related to efficient adsorption and activation of both coupling partners over photocatalysts towards activity enhancement remains a challenge. Here, we demonstrate an efficient interface synergy strategy by coupling exposed oxygen vacancies (V) and Pd Lewis acid sites for benzimidazole and hydrogen (H) coproduction over Pd-loaded TiO nanospheres with the highest photoredox activity compared to previous works so far. The results show that the introduction of V optimizes the energy band structure and supplies coordinatively unsaturated sites for adsorbing and activating ethanol molecules, affording acetaldehyde active intermediates. Pd acts as a Lewis acid site, enhancing the adsorption of alkaline amine molecules via Lewis acid-base pair interactions and driving the condensation process. Furthermore, V and Pd synergistically promote interfacial charge transfer and separation. This work offers new insightful guidance for the rational design of semiconductor-based photocatalysts with interface synergy at the molecular level towards the high-performance coproduction of renewable fuels and value-added feedstocks.
邻苯二胺与醇的光驱动交叉偶联已成为合成生物活性苯并咪唑的一种替代方法。然而，解决与光催化剂上两种偶联伙伴的有效吸附和活化以提高活性相关的关键问题仍然是一项挑战。在此，我们展示了一种有效的界面协同策略，通过将暴露的氧空位（V）和钯路易斯酸位点耦合，在负载钯的TiO纳米球上实现苯并咪唑和氢气（H）的联产，与迄今为止的先前工作相比，具有最高的光氧化还原活性。结果表明，V的引入优化了能带结构，并为吸附和活化乙醇分子提供了配位不饱和位点，生成乙醛活性中间体。钯作为路易斯酸位点，通过路易斯酸碱对相互作用增强碱性胺分子的吸附，并驱动缩合过程。此外，V和钯协同促进界面电荷转移和分离。这项工作为基于半导体的光催化剂的合理设计提供了新的深刻指导，该催化剂在分子水平上具有界面协同作用，以实现可再生燃料和增值原料的高性能联产。
