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Metal organic frameworks as catalysts in solvent-free or ionic liquid assisted conditions
Green Chemistry ( IF 9.3 ) Pub Date : 2017-10-09 00:00:00 , DOI: 10.1039/c7gc02260c Amarajothi Dhakshinamoorthy 1, 2, 3, 4, 5 , Abdullah M. Asiri 6, 7, 8, 9 , Mercedes Alvaro 5, 10, 11, 12 , Hermenegildo Garcia 5, 6, 10, 11, 12
Green Chemistry ( IF 9.3 ) Pub Date : 2017-10-09 00:00:00 , DOI: 10.1039/c7gc02260c Amarajothi Dhakshinamoorthy 1, 2, 3, 4, 5 , Abdullah M. Asiri 6, 7, 8, 9 , Mercedes Alvaro 5, 10, 11, 12 , Hermenegildo Garcia 5, 6, 10, 11, 12
Affiliation
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Metal organic frameworks (MOFs) are being intensively studied as solid catalysts for organic reactions in liquid media. This review focuses on those reports in which these materials have been used as catalysts in the absence of solvents or embedding ionic liquids (ILs). One of the major roles of solvents in liquid phase reactions is to desorb reagents and products from the active sites, facilitating the turnover of the active sites. For this reason, it is a general observation that most solid catalysts undergo strong deactivation and poisoning in the absence of solvents. In the present review, examples are presented showing that, due to their large porosity and framework flexibility, MOFs can be used as catalysts in the absence of solvents for several reaction types including cyanosilylations, condensations, cyloadditions and CO2 insertions, among others, and that they show even better performance than in the presence of conventional organic solvents. This review also describes the synergy that arises from the combination of ILs, frequently with suitable task-specific chains, and MOFs due to the cooperation with the catalysis when two centres in MOF and ionic liquid are present and due to the change in the microenvironment of the active sites. By embedding an ionic liquid in the MOF pores or by synthesising the ionic liquid covalently attached to the ligand in satellite positions, reusable and efficient catalysts requiring the minimum amount of ionic liquid can be obtained. Both complementary strategies increase the greenness of MOFs as heterogeneous catalysts and have advantages from the environmental point of view. Finally, the last section describes the catalytic activity of hierarchical porous MOFs in some selected reactions.
中文翻译：
金属有机骨架在无溶剂或离子液体辅助条件下作为催化剂
金属有机骨架（MOFs）作为液体介质中有机反应的固体催化剂正在被深入研究。本文的重点是那些在没有溶剂或没有离子液体（ILs）的情况下将这些材料用作催化剂的报告。液相反应中溶剂的主要作用之一是从活性位点解吸试剂和产物，从而促进活性位点的周转。因此，通常观察到，大多数固体催化剂在不存在溶剂的情况下会发生强烈的失活和中毒现象。在本综述中，实例表明，由于其大的孔隙率和骨架的柔韧性，MOF可以在不存在溶剂的情况下用作催化剂，用于多种反应类型，包括氰基甲硅烷基化，缩合，环取代和CO2个插入，以及与常规有机溶剂相比，它们表现出更好的性能。这篇综述还描述了由于ILs（经常与合适的任务特定链结合）和MOF的结合所产生的协同作用，这是由于当存在MOF和离子液体中的两个中心时，与催化的合作以及由于Mos的微环境的变化而引起的。活动站点。通过将离子液体嵌入MOF孔中或通过合成共价键合在配体上的配体上的离子液体，可以获得需要最少离子液体量的可重复使用且有效的催化剂。两种互补策略均提高了MOF作为非均相催化剂的绿色度，并从环境角度来看具有优势。最后，
更新日期：2018-01-02
中文翻译：
金属有机骨架在无溶剂或离子液体辅助条件下作为催化剂
金属有机骨架（MOFs）作为液体介质中有机反应的固体催化剂正在被深入研究。本文的重点是那些在没有溶剂或没有离子液体（ILs）的情况下将这些材料用作催化剂的报告。液相反应中溶剂的主要作用之一是从活性位点解吸试剂和产物，从而促进活性位点的周转。因此，通常观察到，大多数固体催化剂在不存在溶剂的情况下会发生强烈的失活和中毒现象。在本综述中，实例表明，由于其大的孔隙率和骨架的柔韧性，MOF可以在不存在溶剂的情况下用作催化剂，用于多种反应类型，包括氰基甲硅烷基化，缩合，环取代和CO2个插入，以及与常规有机溶剂相比，它们表现出更好的性能。这篇综述还描述了由于ILs（经常与合适的任务特定链结合）和MOF的结合所产生的协同作用，这是由于当存在MOF和离子液体中的两个中心时，与催化的合作以及由于Mos的微环境的变化而引起的。活动站点。通过将离子液体嵌入MOF孔中或通过合成共价键合在配体上的配体上的离子液体，可以获得需要最少离子液体量的可重复使用且有效的催化剂。两种互补策略均提高了MOF作为非均相催化剂的绿色度，并从环境角度来看具有优势。最后，
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