Metal Variance in Multivariate Metal–Organic Frameworks for Boosting Catalytic Conversion of CO 2

作者：Xu Chen, Jing‐Yi Song, Ji Zheng, Yumei Wang, Jie Luo, Puxin Weng, Bing‐Chen Cai, Xiao‐Chun Lin, Guo‐Hong Ning, Dan Li · 发表于：Journal of the American Chemical Society · 年份：2024 · DOI：10.1021/jacs.4c04556 · 被引用次数：133 · 研究领域：Metal-Organic Frameworks: Synthesis and Applications、Carbon dioxide utilization in catalysis、Machine Learning in Materials Science

Developing efficient, low-cost, MOF catalysts for CO 2 conversion at low CO 2 concentrations under mild conditions is particularly interesting but remains highly challenging. Herein, we prepared an isostructural series of two-dimensional (2D) multivariate metal–organic frameworks (MTV-MOFs) containing copper- and/or silver-based cyclic trinuclear complexes (Cu-CTC and Ag-CTC). These MTV-MOFs can be used as efficient and reusable heterogeneous catalysts for the cyclization of propargylamine with CO 2 . The catalytic performance of these MTV-MOFs can be engineered by fine-tuning the Ag/Cu ratio in the framework. Interestingly, the induction of 10% Ag remarkably improved the catalytic efficiency with a turnover frequency (TOF) of 243 h –1, which is 20-fold higher than that of 100% Cu-based MOF (i.e., TOF = 10.8 h –1 ). More impressively, such a bimetallic MOF still exhibited high catalytic activity even for simulated flue gas with 10% CO 2 concentration. Furthermore, the reaction mechanism has been examined through the employment of NMR monitoring experiments and DFT calculations.