The effect of ring size on the selective oxidation of cycloalkenes using supported metal catalysts
The effect of ring size on the selective oxidation of cycloalkenes using supported metal catalysts
复制标题
环尺寸对负载型金属催化剂选择性氧化环烯烃的影响
DOI：
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发表时间：
2013
期刊：
影响因子：
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通讯作者：
G. Hutchings
中科院分区：
文献类型：
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作者：
Hamed M. Alshammari;Peter J. Miedziak;D. Knight;D. Willock;G. Hutchings
在这项工作中，我们扩展了我们以前的研究，使用负载金纳米粒子和催化量的过氧化物氧化环烯烃。我们证明了这种催化剂可以在绿色条件下，无溶剂，以空气为氧化剂气体，氧化各种大小的环烯烃。考察了载体、制备方法和金属的选择对催化剂性能的影响，结果表明，负载金的性能优于钯或金钯合金，氧化物是这些金催化剂的最佳载体，颗粒最小的制备方法活性最高。结果表明，环烯烃的反应活性与环的大小有关，在相同温度下，小环比大环具有更强的活性。对环氧化物的选择性取决于环烯烃环的大小。特别是，对于碳原子少于7个的环来说，环氧化物的选择性很低。我们讨论了这种选择性效应的来源，用密度泛函理论计算研究了环应变对中间体和反应产物的影响。
In this work we expand on our previous studies on the oxidation of cyclic alkenes using supported gold nanoparticles together with catalytic amounts of peroxides. We demonstrate that various sized cyclic alkenes can be oxidised by this catalyst, under green conditions, without solvent and using air as the oxidant gas. The effect of support, preparation method and choice of metal have been investigated, we demonstrate that supported gold is superior to palladium or a gold palladium alloy, we show that oxides provide the best support for these gold catalysts and the preparation methods that afford the smallest particles are the most active. We show that the reactivity of the cyclic alkenes is related to the ring size with the smaller rings more reactive than the larger rings at the same temperature. The selectivity to the epoxide is dependent on the size of the cyclic alkene ring. In particular, the epoxide selectivity is very low for rings containing fewer than seven carbon atoms. We discuss the origins of this selectivity effect, using DFT calculations to investigate the effect of ring strain on the intermediates and reaction products.
影响因子：
16.6
作者：
bin Saiman, Mohd Izham;Brett, Gemma L.;Hutchings, Graham J.
通讯作者：
Hutchings, Graham J.
影响因子：
3.3
作者：
Lopez-Sanchez, Jose Antonio;Dimitratos, Nikolaos;Hutchings, Graham J.
通讯作者：
Hutchings, Graham J.