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用于高效二氧化碳捕获与转化的超强稳健铟基金属有机框架材料

Exceptionally Robust In-Based Metal-Organic Framework for Highly Efficient Carbon Dioxide Capture and Conversion.

作者信息

Liu Lin, Wang Shi-Ming, Han Zheng-Bo, Ding Meili, Yuan Da-Qiang, Jiang Hai-Long

机构信息

College of Chemistry, Liaoning University , Shenyang 110036, P. R. China.

Hefei National Laboratory for Physical Sciences at the Microscale, Collaborative Innovation Center of Suzhou Nano Science and Technology, Department of Chemistry, University of Science and Technology of China , Hefei, Anhui 230026, P. R. China.

出版信息

Inorg Chem. 2016 Apr 4;55(7):3558-65. doi: 10.1021/acs.inorgchem.6b00050. Epub 2016 Mar 14.

Abstract

An In-based metal-organic framework, with 1D nanotubular open channels, In2(OH)(btc)(Hbtc)0.4(L)0.6·3H2O (1), has been synthesized via an in situ ligand reaction, in which 1,2,4-H3btc is partially transformed into the L ligand. Compound 1 exhibits exceptional thermal and chemical stability, especially in water or acidic media. The activated 1 presents highly selective sorption of carbon dioxide (CO2) over dinitrogen. Interestingly, diffuse-reflectance infrared Fourier transform spectroscopy with a carbon monoxide probe molecule demonstrates that both Lewis and Brønsted acid sites are involved in compound 1. As a result, as a heterogeneous Lewis and Brønsted acid bifunctional catalyst, 1 possesses excellent activity and recyclability for chemical fixation of CO2 coupling with epoxides into cyclic carbonates under mild conditions. In addition, the mechanism for the CO2 cycloaddition reaction has also been discussed.

摘要

一种具有一维纳米管状开放通道的铟基金属有机框架化合物In₂(OH)(btc)(Hbtc)₀.₄(L)₀.₆·3H₂O (1),通过原位配体反应合成,其中1,2,4-H₃btc部分转化为L配体。化合物1表现出优异的热稳定性和化学稳定性,尤其是在水或酸性介质中。活化后的1对二氧化碳(CO₂)具有比氮气更高的选择性吸附。有趣的是,用一氧化碳探针分子进行的漫反射红外傅里叶变换光谱表明,路易斯酸位点和布朗斯特酸位点都存在于化合物1中。因此,作为一种多相路易斯酸和布朗斯特酸双功能催化剂,1在温和条件下将CO₂与环氧化物化学固定为环状碳酸酯具有优异的活性和可循环性。此外,还讨论了CO₂环加成反应的机理。

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