Dual-Spin Centers in a Grid-like Covalent Organic Framework Promote Near-Unity CO 2 Electroreduction

作者：Qianfeng Gu, Yinger Xin, Mingzi Sun, Yuanzhang Zhao, Yaqi Liao, Yuchan Zhang, Zihao Chen, Yifan Cui, Lei Zhang, Yung‐Kang Peng, Qi Liu, Yang Ren, Fu‐Rong Chen, Bolong Huang, R. Ye, Qichun Zhang · 发表于：Journal of the American Chemical Society · 年份：2026 · DOI：10.1021/jacs.5c19281 · 被引用次数：16 · 研究领域：CO2 Reduction Techniques and Catalysts、Covalent Organic Framework Applications、Carbon dioxide utilization in catalysis

Spin manipulation has emerged as a promising strategy for enhancing molecular electrocatalytic performance. However, precisely controlling dual spin centers and delineating their contribution to reaction kinetics remain a considerable challenge. Herein, we demonstrate that incorporating quinone moieties into a grid-like covalent organic framework (COF) enables a dual-spin-center catalysis system, simultaneously stabilizing semiquinone radicals and inducing an electronic reconfiguration with low-spin character at the cobalt center. Spectroscopic and theoretical analyses reveal a synergistic mechanism. The spin-polarized electron density of semiquinone radicals creates an internal potential gradient that promotes electron transfer, while their favorable π–π interactions enhance CO 2 affinity and boost CO 2 activation efficiency. Meanwhile, the cobalt site with a computed e g 1 occupancy (low-spin) leads to more delocalized d-electrons, a downshifted d-band center, and optimized intermediate adsorption. As a result, the dual-spin system achieves reduced barriers for *COOH formation via spin-coupling interactions and facilitated *CO desorption, collectively enabling near-unity selectivity for CO 2 -to-CO conversion. This work establishes the concurrent engineering of organic and metal spin environments as a foundational design principle for advanced molecular electrocatalysts.