Selective Aerobic Oxidation of Cumene to Cumene Hydroperoxide over Mono- and Bimetallic Trimesate Metal–Organic Frameworks Prepared by a Facile “Green” Aqueous Synthesis,ACS Sustainable Chemistry & Engineering

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Selective Aerobic Oxidation of Cumene to Cumene Hydroperoxide over Mono- and Bimetallic Trimesate Metal–Organic Frameworks Prepared by a Facile “Green” Aqueous Synthesis
ACS Sustainable Chemistry & Engineering ( IF 7.1 ) Pub Date : 2019-03-22 00:00:00 , DOI: 10.1021/acssuschemeng.8b06472
Anna Nowacka ₁ , Pol Briantais ₂ , Carmelo Prestipino ₂ , Francesc X. Llabrés i Xamena ₁

Affiliation

Co–Ni and Mn–Ni bimetallic trimesate MOFs prepared by a fast aqueous synthesis method are excellent and reusable catalysts for the selective aerobic oxidation of cumene to cumene hydroperoxide (CHP). Isolation of Co²⁺ (or Mn²⁺) in an inert Ni-BTC framework is a good strategy to optimize CHP selectivity above 90%: since only Co²⁺ sites catalyze CHP decomposition, a drop of the CHP selectivity is observed as the cobalt content in the bimetallic MOF increases. The statistical probability of having isolated Co²⁺ sites is calculated as a function of the total cobalt content of the bimetallic compound, assuming homogeneous distribution of Co²⁺ ions in the Ni-BTC framework and preferential occupation of terminal sites. Thus, in our best sample, with a Co:Ni ratio of 5:95, 73% of the total Co²⁺ ions are isolated so that CHP decomposition/overoxidation processes at the surface of the catalyst are not likely to occur before CHP desorption. This can explain the excellent CHP selectivity (91%) attained over this material. This “site isolation” effect is further supported by similar findings on Mn–Ni bimetallic compounds.

中文翻译：

通过简便的“绿色”水合成制备的单金属和双金属三酸酯金属-有机骨架上的异丙苯选择性好氧氧化为氢过氧化异丙苯

通过快速水合成方法制备的Co-Ni和Mn-Ni双金属偏苯三酸酯MOF是出色的可重复使用的催化剂，可用于将异丙苯好氧氧化为氢过氧化枯烯（CHP）。在惰性Ni-BTC框架中分离Co ²⁺（或Mn ²⁺）是优化CHP选择性高于90％的好策略：由于仅Co ²⁺位点催化CHP分解，因此随着CHP选择性的降低，CHP选择性下降。双金属MOF中的钴含量增加。假设Co ²⁺分布均匀，则计算出具有孤立Co ²⁺位点的统计概率是双金属化合物总钴含量的函数Ni-BTC框架中的离子和优先占用终端站点。因此，在我们最好的样品中，Co：Ni比率为5:95，可分离出总Co ²⁺离子的73％，因此在CHP脱附之前不太可能在催化剂表面发生CHP分解/过氧化过程。。这可以解释在该材料上获得的出色的CHP选择性（91％）。锰镍双金属化合物的类似发现进一步支持了这种“位隔离”效应。

更新日期：2019-03-22

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