Tunable catalytic properties of multi-metal-organic frameworks for aerobic styrene oxidation
Tunable catalytic properties of multi-metal-organic frameworks for aerobic styrene oxidation
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多金属有机框架对苯乙烯需氧氧化的可调催化性能
DOI：
10.1016/j.cej.2016.04.102
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发表时间：
2016-09-01
影响因子：
15.1
通讯作者：
Fan, Maohong
中科院分区：
文献类型：
--
作者：
Fu, Yanghe;Xu, Lai;Fan, Maohong
采用一锅法制备了不同Cu/Co比的Cu和Co混合金属有机骨架（MOFs）MOF-74（Cu/Co），并对其进行了表征。无论所合成的MOF中的Cu/Co比是多少，Cu 2+和Co 2+都可以均匀地分布在MOF-74中。在无溶剂、温和的反应条件下，将合成的MOF-74（Cu/Co）材料用于苯乙烯的O-2氧化反应。结果表明，可以通过改变M0 F-74中的Cu/Co比率来调节M0 F-74（Cu/Co）的催化性能。M0 F-74（Cu）具有相当低的催化活性，但对苯甲醛具有绝对选择性，而M0 F-74（Co）具有相对较高的催化活性，导致苯甲醛、环氧苯乙烯和苯乙醛以及聚苯乙烯的形成。令人惊讶的是，在M0 F-74（Co）中掺入Cu 2+可以完全抑制苯乙烯的聚合，而在M0 F-74（Cu）中掺入Co2+可以显著提高苯乙烯向苯甲醛、苯乙烯环氧化物和苯乙醛的转化率。此外，随着Co ~（2+）含量的增加，苯乙烯的转化率、环氧苯乙烯和苯乙醛的选择性增加，而苯甲醛的选择性降低。此外，还比较了MOF-74（Cu/Co）与MOF-74（Cu）和MOF-74（Co）物理混合物的催化性能，证明了MOF-74（Cu/Co）中Co2+和Cu 2+对苯乙烯的催化氧化具有协同效应。目前的工作揭示了一种策略，将多个金属阳离子到MOFs中，以提高特定的催化性能或实现新的催化性能。(C)2016爱思唯尔B. V.保留所有权利。
The Cu and Co mixed metal-organic frameworks (MOFs) MOF-74(Cu/Co) with different Cu/Co ratios were prepared via a facile one-pot synthesis method and then characterized by means of various techniques. Whatever the Cu/Co ratios in the synthesized MOFs were, both Cu2+ and Co2+ could be uniformly distributed in MOF-74. The synthesized MOF-74(Cu/Co) materials were used as catalysts in styrene oxidation with O-2 under solvent-free and mild reaction conditions. The results show that the catalytic properties of MOF-74(Cu/Co) can be tuned by varying the Cu/Co ratio in MOF-74. MOF-74(Cu) has a rather low catalytic activity but an absolute selectivity for benzaldehyde while MOF-74(Co) possesses a relatively higher catalytic activity, leading to the formation of benzaldehyde, styrene epoxide, and phenylacetaldehyde as well as to polystyrene. It is surprising that the incorporation of Cu2+ in MOF-74 (Co) can completely inhibit the polymerization of styrene while the incorporation of Co2+ in MOF-74 (Cu) can significantly enhance the conversion of styrene to benzaldehyde, styrene epoxide, and phenylacetaldehyde. In addition, by increasing the Co2+ amount in MOF-74(Cu/Co), the conversion of styrene and the selectivity for styrene epoxide and phenylacetaldehyde are increased while the selectivity for benzaldehyde is decreased. Moreover, the catalytic properties of MOF-74(Cu/Co) were compared with those of the physical mixtures of MOF-74(Cu) and MOF-74(Co), demonstrating the synergetic effects of Co2+ and Cu2+ in MOF-74(Cu/Co) on the catalytic oxidation of styrene. The current work reveals a strategy to incorporate multiple metal cations into MOFs for enhancing a specific catalytic property or achieving a new catalytic property. (C) 2016 Elsevier B.V. All rights reserved.