上海交通大学邱惠斌研究团队近日取得一项新成果。经过不懈努力，他们的最新研究开发出用于光催化水析氢的准一维之字形共价有机框架。相关论文于2024年9月10日发表在《美国化学会杂志》上。

该课题组人员开发了一种通用的方法，通过V形双异位连接和X形四异位结的缩合，制备了15种具有之字形排列的一维多孔有机链的高结晶共价有机框架（COFs）。具有不同芳香核、连接和功能的广泛连接子和结的适当几何组合提供了一系列准一维COFs，主要孔径为7-13 Å表面积是116-784 m² g^-1。

其中，具有位点选择性杂原子氮(N)掺杂的1D COFs有利于可调控制带结构和共轭，并且在光催化水裂解中具有高达80 mmol g^-1 h^-1的显着析氢速率。这种在多孔晶体材料中编程功能的一般策略，有可能通过精确的周期性掺杂来调整拓扑上定义良好的电子特性。

研究人员表示，共价有机框架(COFs)具有广泛的应用前景。然而，限制它们在一维方向上的共价扩展仍然是一个关键的挑战。

附：英文原文

Title: Quasi-One-Dimensional Zigzag Covalent Organic Frameworks for Photocatalytic Hydrogen Evolution from Water

Author: Chao Yang, Jiabo Le, Yongbo Kuang, Zheng Meng, Haojie Dai, Yongfeng Zhou, Huibin Qiu

Issue&Volume: September 10, 2024

Abstract: Covalent organic frameworks (COFs) have potential applications in a wide range of fields. However, it remains a critical challenge to constrain their covalent expansions in the one-dimensional (1D) direction. Here, we developed a general approach to fabricate 15 different highly crystalline COFs with zigzag-packed 1D porous organic chains through the condensation of V-shaped ditopic linkers and X-shaped tetratopic knots. Appropriate geometrical combinations of a wide scope of linkers and knots with distinct aromatic cores, linkages, and functionalities offer a series of quasi-1D COFs with dominant pore sizes of 7–13 and surface areas of 116–784 m2 g–1. Among them, nitrogen (N)-doped 1D COFs with site-specific doping of heteroatoms favor a tunable control of band structures and conjugations and thus allow a remarkable hydrogen evolution rate up to 80 mmol g–1 h–1 in photocatalytic water splitting. This general strategy toward programming function in porous crystalline materials has the potential to tune the topologically well-defined electronic properties through precisely periodic doping.

DOI: 10.1021/jacs.4c07780

Source: https://pubs.acs.org/doi/abs/10.1021/jacs.4c07780