Two-Dimensional Silver-Isocyanide Frameworks

Kaiyue Jiang; Pu Yan; Pengfei Shi; Jichao Zhang; Xinyu Chai; Yunfei Wang; Chenhui Zhu; Chongqing Yang; Chenbao Lu; Yi Liu; Kecheng Cao; Xiaodong Zhuang

doi:10.1002/anie.202417658

Two-Dimensional Silver-Isocyanide Frameworks

Angew Chem Int Ed Engl. 2024 Oct 1:e202417658. doi: 10.1002/anie.202417658. Online ahead of print.

Authors

Kaiyue Jiang¹, Pu Yan², Pengfei Shi¹, Jichao Zhang³, Xinyu Chai¹, Yunfei Wang⁴, Chenhui Zhu⁴, Chongqing Yang⁵, Chenbao Lu^{1

6}, Yi Liu⁷, Kecheng Cao², Xiaodong Zhuang^{1

8}

Affiliations

¹ 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.
² School of Physical Science and Technology and Shanghai Key Laboratory of High-resolution Electron Microscopy, ShanghaiTech University, Shanghai, 201210, China.
³ Shanghai Synchrotron Radiation Facility, Shanghai Advanced Research Institute, Chinese Academy of Sciences, 239 Zhangheng Road, Shanghai, 201204, China.
⁴ Advanced Light Source, Lawrence Berkeley National Laboratory, Berkeley, CA 94720, USA.
⁵ Carbon Capture and Utilization Research Center, College of Smart Energy, Shanghai Jiao Tong University, Shanghai, 200240, China.
⁶ College of Chemistry, Zhengzhou University, Zhengzhou, 450001, Henan, China.
⁷ The Molecular Foundry, Lawrence Berkeley National Laboratory, Berkeley, CA 94720, USA.
⁸ Frontiers Science Center for Transformative Molecules, Zhang Jiang Institute for Advanced Study, Shanghai Jiao Tong University, 429 Zhangheng Road, Shanghai, 201203, China.

PMID: 39354679
DOI: 10.1002/anie.202417658

Abstract

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.

Keywords: active carbon site; isocyanide; metal–organic framework; silver; two-dimensional.

Abstract

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