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大孔聚(氢甲基硅氧烷)网络作为用于沉积钯催化剂的杂化陶瓷(陶瓷聚合物)的前体。

Macroporous Poly(hydromethylsiloxane) Networks as Precursors to Hybrid Ceramics (Ceramers) for Deposition of Palladium Catalysts.

作者信息

Mrówka Jan, Kosydar Robert, Kornaus Kamil, Partyka Janusz, Hasik Magdalena

机构信息

Faculty of Materials Science and Ceramics, AGH University of Krakow, Al. Mickiewicza 30, 30-059 Krakow, Poland.

Jerzy Haber Institute of Catalysis and Surface Chemistry, Polish Academy of Sciences, ul. Niezapominajek 8, 30-239 Krakow, Poland.

出版信息

Molecules. 2024 Aug 11;29(16):3808. doi: 10.3390/molecules29163808.

Abstract

Poly(hydromethylsiloxane) (PHMS) was cross-linked with 1,3,5,7-tetramethyl-1,3,5,7-tetravinylcyclotetrasiloxane (D) in water-in-oil High Internal Phase Emulsions to form macroporous materials known as polyHIPEs. It was shown that in the process of pyrolysis under Ar atmosphere at 520 °C, the obtained polyHIPEs were converted to ceramers with high yields (82.8-88.0 wt.%). Structurally, the obtained ceramers were hybrid ceramics, i.e., they consisted of Si-O framework and preserved organic moieties. Macropores present in the polyHIPE precursors remained in ceramers. Ceramers contained also micro- and mesopores which resulted from the precursor's mass loss during pyrolysis. Total pore volume and BET specific surface area related to the existence of micro- and mesopores in ceramers depended on the PHMS: D ratio applied in polyHIPE synthesis. The highest total pore volume (0.143 cm/g) and specific surface area (344 m/g) were reached after pyrolysis of the precursor prepared with the lowest amount of D as compared to PHMS. The composite materials obtained after deposition of PdO nanoparticles onto ceramers followed by reduction of PdO by H were active and selective catalysts for phenylacetylene hydrogenation to styrene.

摘要

聚(羟甲基硅氧烷)(PHMS)与1,3,5,7-四甲基-1,3,5,7-四乙烯基环四硅氧烷(D)在油包水高内相乳液中交联,形成了称为聚高内相乳液聚合物(polyHIPEs)的大孔材料。结果表明,在520℃的氩气气氛下热解过程中,所得到的聚高内相乳液聚合物以高收率(82.8 - 88.0 wt.%)转化为陶瓷聚合物。从结构上看,所得到的陶瓷聚合物是杂化陶瓷,即它们由Si - O骨架组成并保留了有机部分。聚高内相乳液聚合物前体中存在的大孔保留在陶瓷聚合物中。陶瓷聚合物中还含有微孔和介孔,这是由于前体在热解过程中的质量损失所致。与陶瓷聚合物中微孔和介孔的存在相关的总孔体积和BET比表面积取决于聚高内相乳液聚合物合成中所使用的PHMS:D比例。与PHMS相比,用最低量的D制备的前体热解后达到了最高的总孔体积(0.143 cm/g)和比表面积(344 m/g)。在陶瓷聚合物上沉积PdO纳米颗粒然后用H还原PdO后得到的复合材料是用于苯乙炔加氢制苯乙烯的活性和选择性催化剂。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/15f5/11356917/955cbe3a40c4/molecules-29-03808-g001.jpg

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