具有波浪形层的卟啉基共价有机框架用于高效光催化CO₂还原，这一成果由北京科技大学姜建壮小组经过不懈努力而取得。相关论文于2025年4月2日发表于国际顶尖学术期刊《科学通报》杂志上。

基于二维（2D）卟啉（Por）的共价有机框架（COFs）为光催化CO₂还原提供了一种有吸引力且有效的策略，但由于π -π堆叠而形成的层状结构对活性位点的暴露、质量转移和光生成载流子具有挑战性。在本研究中，制备了一系列基于卟啉的二维共轭COFs，它们分别具有不同程度的扭曲连接单元卟啉块。实验和理论计算结果表明，由于N-N单键连接的两个咔唑单元之间存在较大的空间位阻，在NN-Por-COF中形成了一个波动较大的层状结构，增强了传质，暴露了更多的催化位点。咔唑的引入也改变了卟啉Co中心的电子结构，降低了反应能垒。通过对结构和电子效应的优化，使得NN-Por-COF具有优异的光催化CO₂还原性能，CO转化率分别高达22.38和3.02 mmol g^-1 h^-1 在纯净和稀释（10%）的CO2气氛下，优于大多数报道的卟啉基光催化剂。

附：英文原文

Title: Porphyrin-based covalent organic frameworks with undulated layers for efficient photocatalytic CO2 reduction

Author: Houhe Pan a, Yongzhong Bian a b, Jianzhuang Jiang a c

Issue&Volume: 2025/04/02

Abstract: Two-dimensional (2D) porphyrin (Por)-based covalent organic frameworks (COFs) provide an attractive and effective strategy for photocatalytic CO2 reduction, but the layered structure due to π–π stacking is challenging for the exposure of active sites and transfer of mass and photogenerated carriers. In this study, a series of 2D conjugated porphyrin-based COFs were prepared using porphyrin blocks with linking units having different degrees of twisting. According to the experimental and theoretical calculation results, owing to the large spatial steric hindrance between the two carbazole units connected by the N–N single bond, a greatly undulating layered structure was formed in NN-Por-COF, which enhanced mass transfer and exposed more catalytic sites. The introduction of carbazole also modulated the electronic structure of the porphyrin Co center, which lowered the reaction energy barrier. The optimization of the structural and electronic effects led to the excellent photocatalytic CO2 reduction performance of NN-Por-COF, with CO conversion rates as high as 22.38 and 3.02 mmol g1 h1 under pure and diluted (10%) CO2 atmosphere, respectively, which are superior to those of most of the reported porphyrin-based photocatalysts.

DOI: 10.1016/j.scib.2025.04.002

Source: https://www.sciencedirect.com/science/article/abs/pii/S2095927325003470