Self-Supporting Metal-Organic Layers as Single-Site Solid Catalysts

• Published in: Angewandte Chemie (International ed.) 2016-04, Vol.55 (16), p.4962-4966
• Main Authors: Cao, Lingyun, Lin, Zekai, Peng, Fei, Wang, Weiwei, Huang, Ruiyun, Wang, Cheng, Yan, Jiawei, Liang, Jie, Zhang, Zhiming, Zhang, Teng, Long, Lasheng, Sun, Junliang, Lin, Wenbin
• Format: Article
• Language: English
• Subjects: alkenes; Catalytic oxidation; hafnium; heterogeneous catalysis; hydrosilylation; Inorganic Chemistry; INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; metal-organic layers; oorganisk kemi
• ISSN: 1433-7851; 1521-3773; 1521-3773
• DOI: 10.1002/anie.201512054

Metal–organic layers (MOLs) represent an emerging class of tunable and functionalizable two‐dimensional materials. In this work, the scalable solvothermal synthesis of self‐supporting MOLs composed of [Hf6O4(OH)4(HCO2)6] secondary building units (SBUs) and benzene‐1,3,5‐tribenzoate (BTB) bridging ligands is reported. The MOL structures were directly imaged by TEM and AFM, and doped with 4′‐(4‐benzoate)‐(2,2′,2′′‐terpyridine)‐5,5′′‐dicarboxylate (TPY) before being coordinated with iron centers to afford highly active and reusable single‐site solid catalysts for the hydrosilylation of terminal olefins. MOL‐based heterogeneous catalysts are free from the diffusional constraints placed on all known porous solid catalysts, including metal–organic frameworks. This work uncovers an entirely new strategy for designing single‐site solid catalysts and opens the door to a new class of two‐dimensional coordination materials with molecular functionalities. A very thin catalyst: Two‐dimensional metal–organic layers with the thinness of a single monolayer act as highly efficient single‐site solid catalysts for alkene hydrosilylation. They outperform traditional metal–organic frameworks in terms of their activity as diffusional constraints on the substrates and products are removed.