Jiang Kaiyue, Yan Pu, Shi Pengfei, Zhang Jichao, Chai Xinyu, Wang Yunfei, Zhu Chenhui, Yang Chongqing, Lu Chenbao, Liu Yi, Cao Kecheng, Zhuang Xiaodong
The Soft2D Lab, State Key Laboratory of Metal Matrix Composites, Shanghai Key Laboratory of Electrical Insulation and Thermal Ageing, School of Chemistry and Chemical Engineering, Shanghai Jiao Tong University, 130 Dongchuan Road, Shanghai, 200240, China.
School of Physical Science and Technology and Shanghai Key Laboratory of High-resolution Electron Microscopy, ShanghaiTech University, Shanghai, 201210, China.
Angew Chem Int Ed Engl. 2025 Jan 27;64(5):e202417658. doi: 10.1002/anie.202417658. Epub 2024 Nov 6.
Metal-organic frameworks (MOFs) have been widely studied due to their versatile applications and easily tunable structures. However, heteroatom-metal coordination dominates the MOFs community, and the rational synthesis of carbon-metal coordination-based MOFs remains a significant challenge. Herein, two-dimensional (2D) MOFs based on silver-carbon linkages are synthesized through the coordination between silver(I) salt and isocyanide-based monomers at ambient condition. The as-synthesized 2D MOFs possess well-defined crystalline structures and a staggered AB stacking mode. Most interestingly, these 2D MOFs, without π-π stacking between layers, exhibit narrow band gaps down to 1.42 eV. As electrochemical catalysts for converting CO to CO, such 2D MOFs demonstrate Faradaic efficiency over 92 %. Surprisingly, the CO reduction catalyzed by these MOFs indicates favorable adsorption of CO and *COOH on the active carbon sites of the isocyanide groups rather than on silver sites. This is attributed to the critical σ donor role of isocyanides and the corresponding ligand-to-metal charge-transfer effect. This work not only paves the way toward a new family of MOFs based on metal-isocyanide coordination but also offers a rare platform for understanding the electrocatalysis processes on strongly polarized carbon species.
金属有机框架材料（MOFs）因其广泛的应用和易于调控的结构而受到广泛研究。然而，杂原子-金属配位在MOFs领域占据主导地位，基于碳-金属配位的MOFs的合理合成仍然是一项重大挑战。在此，通过银（I）盐与异腈基单体在环境条件下的配位反应，合成了基于银-碳键的二维（2D）MOFs。所合成的二维MOFs具有明确的晶体结构和交错的AB堆积模式。最有趣的是，这些二维MOFs层间不存在π-π堆积，其带隙窄至1.42 eV。作为将CO转化为CO₂的电化学催化剂，此类二维MOFs的法拉第效率超过92%。令人惊讶的是，这些MOFs催化的CO₂还原表明，CO和*COOH在异腈基团的活性碳位点上具有良好的吸附性，而非在银位点上。这归因于异腈的关键σ供体作用以及相应的配体-金属电荷转移效应。这项工作不仅为基于金属-异腈配位的新型MOFs家族铺平了道路，也为理解强极化碳物种上的电催化过程提供了一个难得的平台。
