华南师范大学兰亚乾团队报道了在COF上原位构建单原子电子桥以增强光催化制氢。相关研究成果发表在2024年8月13日出版的《德国应用化学》。

光催化制氢是未来能源系统中最有价值的技术之一。

该文中，研究人员设计了一种具有小尺寸金属簇和富氮配体的金属共价有机框架（MCOFs），名为COF-Cu₃TG。基于该设计，选择了小尺寸的金属团簇来增加活性位点的密度，缩短电子传输到活性位点的距离。

而另一种含有富氮有机配体的构建块充当了一个节点，可以在光催化过程中原位锚定金属原子，形成层间单原子电子桥（SAEB）以加速电子传输。它们共同促进了光催化性能。这代表了Ru原子的进一步利用，是光敏剂的另一种应用。

在层之间原位产生N₂-Ru-N₂电子桥（Ru-SAEB），导致光催化剂的氢气生产率显著提高到10.47mmol g^-1h^-1。通过理论计算和EXAFS，合理推断出Ru-SAEB的存在位置和作用机制，进一步证实了Ru-SAEB构型的合理性。发现小尺寸Cu3团簇和Ru-SAEB之间足够接近时，可以加速电子转移。

该项工作证明了小分子团簇与Ru-SAEB在高效光催化制氢方面的协同作用。

附：英文原文

Title: In situ Construction of Single-Atom Electronic Bridge on COF to Enhance Photocatalytic H2 Production

Author: Jie Li, Jie Zhou, Xiao-Han Wang, Can Guo, Run-Han Li, Huifen Zhuang, Wenhai Feng, Yingjie Hua, Ya-Qian Lan

Issue&Volume: 2024-08-13

Abstract: Photocatalytic hydrogen production is one of the most valuable technologies in the future energy system. Here, we designed a metal-covalent organic frameworks (MCOFs) with both small-sized metal clusters and nitrogen-rich ligands, named COF-Cu3TG. Based on our design, small-sized metal clusters were selected to increase the density of active sites and shorten the distance of electron transport to active sites. While another building block containing nitrogen-rich organic ligands acted as a node that could in situ anchor metal atoms during photocatalysis and form interlayer single-atom electron bridges (SAEB) to accelerate electron transport. Together, they promoted photocatalytic performance. This represented the further utilization of Ru atoms and was an additional application of the photosensitizer. N2-Ru-N2 electron bridge (Ru-SAEB) was created in situ between the layers, resulting in a considerable enhancement in the hydrogen production rate of the photocatalyst to 10.47 mmol g-1 h-1. Through theoretical calculation and EXAFS, the existence position and action mechanism of Ru-SAEB were reasonably inferred, further confirming the rationality of the Ru-SAEB configuration. A sufficiently proximity between the small-sized Cu3 cluster and the Ru-SAEB was found to expedite electron transfer. This work demonstrated the synergistic impact of small molecular clusters with Ru-SAEB for efficient photocatalytic hydrogen production.

DOI: 10.1002/anie.202411721

Source: https://onlinelibrary.wiley.com/doi/10.1002/anie.202411721