Efficient Reduction of CO 2 via Modified Bimetallic Metal–Organic Frameworks‐Based Cycloaddition under Mild Conditions

作者：Peng Qin, Zhenxing Shen, Xinyu Mo, Tian Chang, Bo Song, Hao Fan, Zhenchuan Niu · 发表于：Advanced Sustainable Systems · 年份：2025 · DOI：10.1002/adsu.202500657 · 被引用次数：4 · 研究领域：CO2 Reduction Techniques and Catalysts、Carbon dioxide utilization in catalysis、Metal-Organic Frameworks: Synthesis and Applications

Abstract The incorporation of functionalized secondary metal nodes into bimetallic metal–organic frameworks (MOFs) enhances their performance and application potential. This study investigates Cu/Zn‐MOF‐74 catalysts with varying metal ratios for carbon dioxide (CO₂)‐epoxide cycloaddition. Compared to monometallic Cu‐MOF‐74 and Zn‐MOF‐74, the bimetallic system shows superior catalytic activity for epoxides conversion. Vim─COOH@Cu/Zn‐MOF‐74 is developed by introducing hydrogen bond donors (HBD) and nitrogen‐containing linkers. The optimal Vim─COOH@Cu₀.₆₇Zn₀.₃₃‐MOF‐74 demonstrates outstanding performance in CO₂‐epichlorohydrin cycloaddition, achieving 96.4% conversion and 98.5% selectivity under mild conditions (80 °C, 1.0 MPa, 24 h) without co‐catalysts, while maintaining excellent recyclability. Using a one‐pot synthesis, bimetallic MOFs with controlled Cu/Zn ratios are prepared. The framework is further modified by incorporating 1,4‐butanediyl‐3,3′‐bis‐1‐vinylimidazolium bromide and HBD‐functionalized imidazole bromide monomers. The resulting composites achieve over 80% conversion under solvent‐free, co‐catalyst‐free conditions due to synergistic effects between Lewis acid sites, carboxyl groups, and nucleophilic Br⁻ ions. This work presents an effective strategy for developing efficient MOF catalysts for CO₂ conversion. The Vim─COOH@Cu/Zn‐MOF‐74 system demonstrates significant potential for sustainable CO₂ utilization in cyclic carbonate synthesis, combining high activity, s...