A Triazole-Containing Metal-Organic Framework as a Highly Effective and Substrate Size-Dependent Catalyst for CO2 Conversion
A Triazole-Containing Metal-Organic Framework as a Highly Effective and Substrate Size-Dependent Catalyst for CO2 Conversion
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含三唑的金属有机框架作为高效且底物尺寸依赖性的 CO2 转化催化剂
DOI：
10.1021/jacs.5b13335
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发表时间：
2016-02-24
影响因子：
15
通讯作者：
Zhao, Yanli
中科院分区：
文献类型：
--
作者：
Li, Pei-Zhou;Wang, Xiao-Jun;Zhao, Yanli
一个高度多孔的金属有机框架（MOF），将暴露的金属网站和富氮的三唑基团，成功地构建通过点击octcarboxylate配体和Cu（II）离子的溶剂热组装，它呈现出对CO2分子的高亲和力，通过气体吸附和拉曼光谱检测清楚地验证。所构建的具有CO2吸附性能和暴露的路易斯酸金属位点的MOF可以作为基于CO2的化学固定的优良催化剂。MOF的催化活性通过对CO2与小环氧化物的环加成的显著高效率来证实。当将衬底扩展到更大的衬底时，其。活动急剧减少。这些观察结果表明，MOF催化的小底物的CO2环加成反应在框架内进行，而大的不能容易地进入多孔框架的催化反应。因此，由于孔径的限制，合成的MOF对不同的底物表现出高的催化选择性。高效率和对小的环氧化物的催化CO2环加成的尺寸依赖的选择性，使这种MOF的碳固定的一个有前途的多相催化剂。
A highly porous metal-organic framework (MOF) incorporating both exposed metal sites and nitrogen-rich triazole groups was successfully constructed via solvothermal assembly of a clicked octcarboxylate ligand and Cu(II) ions, which presents a high affinity toward CO2 molecules clearly verified by gas adsorption and Raman spectral detection. The constructed MOF featuring CO2-adsorbing property and exposed Lewis-acid metal sites could serve as an excellent catalyst for CO2-based chemical fixation. Catalytic activity of the MOF was confirmed by remarkably high efficiency on CO2 cycloaddition with small epoxides. When extending the substrates to larger ones, its. activity showed a sharp decrease. These observations reveal that MOF-catalyzed CO2 cycloaddition of small substrates was carried out within the framework, while large ones cannot easily enter into the porous framework for catalytic reactions. Thus, the synthesized MOF exhibits high catalytic selectivity to different substrates on account of the confinement of the pore diameter. The high efficiency and size-dependent selectivity toward small epoxides on catalytic CO2 cycloaddition make this MOF a promising heterogeneous catalyst for carbon fixation.