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一种通过多羧基连接体实现磁可回收的超顺磁性二氧化硅负载铂纳米催化剂:合成、表征及其在烯烃硅氢化反应中的应用

A magnetically recyclable superparamagnetic silica supported Pt nanocatalyst through a multi-carboxyl linker: synthesis, characterization, and applications in alkene hydrosilylation.

作者信息

Li Laiming, Li Youxin, Yan Jincong, Cao Hang, Shao Dongyun, Bao James J

机构信息

Tianjin Key Laboratory for Modern Drug Delivery and High-Efficiency, Collaborative Innovation Center of Chemical Science and Engineering, School of Pharmaceutical Science and Technology, Tianjin University Room 412-8, Building No. 24, 92 Weijin Road, Nankai District Tianjin 300037 China

出版信息

RSC Adv. 2019 Apr 24;9(22):12696-12709. doi: 10.1039/c9ra00375d. eCollection 2019 Apr 17.

Abstract

To simplify separation procedures, improve the reusability and decrease the loss of Pt, two Pt catalysts anchored on superparamagnetic silica (FeO@SiO-EDTA@Pt and FeO@SiO-DTPA@Pt) were prepared for the first time. The stable magnetic properties made them easily recyclable using a magnet rather than filtration, decantation or centrifugation. After 12 catalytic runs for both 30-50 nm Pt catalysts, the yield of 1-heptylmethyldichlorosilane was still up to 90%. The average loss of Pt in each reaction was only 0.87% for FeO@SiO-EDTA@Pt and 0.66% for FeO@SiO-DTPA@Pt owing to the strong interaction between Pt and carboxyl. The unprecedented activity and selectivity of the two Pt nanoparticle catalysts were observed in the hydrosilylation of alkenes. The turnover number in the reaction between 1-hexene and methyldichlorosilane using 5 × 10 mol of the Pt approached 662 733 for FeO@SiO-EDTA@Pt and 579 947 for FeO@SiO-DTPA@Pt over 12 h. The corresponding hydrosilylation products in excellent yields were obtained when we employed a broad range of alkenes as substrates, including 5 isomerous hexenes and 14 important industry raw materials. FeO@SiO-DTPA@Pt showed a better activity. They have potential for catalyzing more reactions and replacing the current homogeneous Pt catalysts in industry.

摘要

为了简化分离程序、提高可重复使用性并减少铂的损失,首次制备了两种负载在超顺磁性二氧化硅上的铂催化剂(FeO@SiO-EDTA@Pt和FeO@SiO-DTPA@Pt)。其稳定的磁性使得它们易于通过磁铁回收利用,而无需过滤、倾析或离心。对于两种30 - 50 nm的铂催化剂,经过12次催化循环后,1-庚基甲基二氯硅烷的产率仍高达90%。由于铂与羧基之间的强相互作用,FeO@SiO-EDTA@Pt每次反应中铂的平均损失仅为0.87%,FeO@SiO-DTPA@Pt为0.66%。在烯烃的硅氢加成反应中观察到了这两种铂纳米颗粒催化剂前所未有的活性和选择性。在1-己烯与甲基二氯硅烷的反应中,使用5×10⁻⁵ mol的铂,FeO@SiO-EDTA@Pt在12小时内的转换数接近662733,FeO@SiO-DTPA@Pt为579947。当我们使用包括5种异构己烯和14种重要工业原料在内的多种烯烃作为底物时,得到了相应产率优异的硅氢加成产物。FeO@SiO-DTPA@Pt表现出更好的活性。它们具有催化更多反应并在工业中替代当前均相铂催化剂的潜力。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/c5ad/9063652/4d98a18cca77/c9ra00375d-f1.jpg

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