Electron Cloud Density Modulation in Three-Dimensional Porphyrin-Based Covalent Organic Frameworks for Enhanced Photocatalytic CO 2 Reduction

作者：Dayang Cheng, Longyi Ding, Chengtao Gong, Liyan Zhang, Lili Ma, Yongwu Peng, Guozan Yuan · 发表于：ACS Materials Letters · 年份：2025 · DOI：10.1021/acsmaterialslett.5c00139 · 被引用次数：6 · 研究领域：Covalent Organic Framework Applications、Advanced Photocatalysis Techniques、CO2 Reduction Techniques and Catalysts

Covalent organic frameworks (COFs), with their tunable structures and defined active sites, hold promise for photocatalytic reduction of CO 2 reduction. Systematic modulation of linker electron cloud density represents a critical strategy for optimizing the catalytic performance of COF-based photocatalysts, yet this approach faces several challenges. In this work, we employed 8-connected porphyrin as a building block to synthesize three distinct three-dimensional (3D) COF materials through the adjustment of the length and functional groups of the biconnected units. The synthesized 3D COFs exhibited varying catalytic activities for photocatalytic CO 2 conversion. Notably, COF-3-Co, which incorporates the benzimidazole unit (BFBie), demonstrated the best CO production yield and selectivity. Combined experimental and theoretical investigations revealed that the high electron cloud density of the BFBie unit effectively facilitated electron transfer, thereby significantly enhancing the photocatalytic activity. The findings presented herein provide valuable insights into the rational design and synthesis of efficient COF-based photocatalysts for the reduction of CO 2 .