上海科技大学知识管理系统

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 CO2 to CO, such 2D MOFs demonstrate Faradaic efficiency over 92 %. Surprisingly, the CO2 reduction catalyzed by these MOFs indicates favorable adsorption of CO2 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. © 2024 Wiley-VCH GmbH.