Self-Supporting Metal-Organic Layers as Single-Site Solid Catalysts
Self-Supporting Metal-Organic Layers as Single-Site Solid Catalysts
复制标题
作为单中心固体催化剂的自支撑金属有机层
DOI：
10.1002/anie.201512054
复制
发表时间：
2016-04-11
影响因子：
16.6
通讯作者：
Lin, Wenbin
中科院分区：
文献类型：
--
作者：
Cao, Lingyun;Lin, Zekai;Lin, Wenbin
金属有机层（MOLs）代表了一类新兴的可调谐和功能化的二维材料。本文报道了以[Hf_6O_4（OH）（4）（HCO_2）（6）]为二级结构单元（SBU）和苯-1，3，5-三苯甲酸（BTB）为桥联配体的自支撑MOL的溶剂热合成。通过TEM和AFM直接对MOL结构进行了表征，并在MOL结构上掺杂了4-（4-苯甲酸）-（2，2，2-三联吡啶）-5，5-二羧酸酯（TPY），然后与铁中心配位，得到了高活性和可重复使用的单中心固体催化剂，用于末端烯烃的硅氢加成反应。基于MOL的非均相催化剂不受置于所有已知多孔固体催化剂（包括金属-有机骨架）上的扩散约束。这项工作揭示了一个全新的战略，设计单位点固体催化剂，并打开了大门，一类新的二维配位材料的分子功能。
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.