Engineering and Sizing Nanoreactors To Confine Metal Complexes for Enhanced Catalytic Performance
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- 作者：Mozaffar Shakeri ; Lucian Roiban ; Vital Yazerski ; Gonzalo Prieto ; Robertus J. M. Klein Gebbink ; Petra E. de Jongh ; Krijn P. de Jong
- 刊名：ACS Catalysis
- 出版年：2014
- 出版时间：October 3, 2014
- 年：2014
- 卷：4
- 期：10
- 页码：3791-3796
- 全文大小：319K
- ISSN：2155-5435
文摘
Homogeneous metal complexes often display superior activity and selectivity in catalysis of chemical transformations. Heterogenization of these complexes by immobilization on solid supports has been used to facilitate recovery, but this is often associated with a decrease in catalytic performance. We here describe a novel approach of sizing and engineering the cavity structure of nanoporous materials as 鈥渘anoreactors鈥?to assemble metal complexes by the 鈥渟hip-in-the-bottle鈥?synthesis to combine the best of homogeneous and heterogeneous catalysts. Catalysis occurred by free metal complexes in confined liquid in these nanoreactors, while the catalysts were recyclable as being heterogeneous at the macroscopic scale. Subnanometer tailoring of window sizes (0.5鈥?.7 nm) of the cavities (16鈥?2 nm) allowed control over loading (6鈥?0 mg-metal complex/g-support) and a high turnover frequency (40鈥?00 hp>鈥? p>) for the hydrolytic kinetic resolution of 1,2-epoxyhexane. Most importantly, the 鈥榟eterogeneous homogeneous catalysts鈥?showed enhanced thermal stability and were stable upon reuse approaching excellent turnover numbers of 100,000. We showed that engineering and sizing of nanoreactors is a powerful approach to control performance of confined catalysts, and this method is generally applicable in host鈥揼uest catalysis.