中国科学院福建物质结构研究所刘天赋团队报道了金属化催化卟啉基氢键有机骨架用于光催化CO₂还原。相关研究成果于2021年12月7日发表在《德国应用化学》。

在拓扑引导下，基于四面体卟啉合成子的自组装过程产生了具有预测的方层拓扑（sql）但不满足稳定性的HOF。引人注目的是，简单地在卟啉中心引入过渡金属不会改变网络拓扑结构，但会显著改变非共价相互作用、轨道重叠和分子几何结构，因此最终产生一系列具有高比表面积和优异稳定性的金属卟啉HOF（在沸水、浓HCl中浸泡并在270℃下加热后完好无损）。

通过将光敏剂和催化位点整合到坚固的骨架中，该系列HOF能够有效催化CO₂光还原为CO，其催化性能在很大程度上取决于卟啉中心的螯合金属物种。

研究工作丰富了稳定功能HOF的文库并扩展了其在光催化CO₂还原中的应用。

附：英文原文

Title: Metallization-Prompted Robust Porphyrin-Based Hydrogen-Bonded Organic Frameworks for Photocatalytic CO2 Reduction

Author: Qi Yin, Eugeny V. Alexandrov, Duan-Hui Si, Qian-Qian Huang, Zhi-Bin Fang, Yuan Zhang, An-An Zhang, Wei-Kang Qin, Yu-Lin Li, Tian-Fu Liu, Davide M. Proserpio

Issue&Volume: 2021-12-07

Abstract: Under the topological guidance, the self-assembly process based on tetratopic porphyrin synthon results in a HOF with the predicted square layers topology (sql) but unsatisfied stability. Strikingly, simply introducing transition metal in porphyrin center does not change the network topology but drastically causes noticeable change on noncovalent interaction, orbital overlap, and molecular geometry, therefore ultimately giving rise to a series of metalloporphyrinic HOFs with high surface area, and excellent stability (intact after being soaked in boiling water, concentrated HCl, and heated in 270 oC). With integrating both photosensitizers and catalytic sites into robust backbones, this series of HOFs can effectively catalyze the photoreduction of CO2 to CO, and their catalytic performances greatly depend on the chelated metal species in porphyrin centers. This work enriches the library of stable functional HOFs and expands their applications in photocatalytic CO2 reduction.

DOI: 10.1002/anie.202115854

Source: https://onlinelibrary.wiley.com/doi/10.1002/anie.202115854