化工新型材料

化工新型材料 ›› 2020, Vol. 48 ›› Issue (10) : 201-205. DOI: 10.19817/j.cnki.issn 1006-3536.2020.10.043

科学研究

二氧化硅负载铂催化剂的制备及性能研究

^1,2,3

^4*

^1,2,3*

⁴

^1,2,3

作者信息 +

Preparation and property of SiO₂ supported Pt catalyst

Cai Cheng^1,2,3, Zhang Zhijie⁴, Hu Tao^1,2,3, Dai Lina⁴, Wang Haoyu^1,2,3, Wu Chonggang^1,2,3, Gong Xinghou^1,2,3

Author information +

文章历史 +

PDF

摘要

将乙烯基三乙氧基硅烷(VTES)改性的纳米SiO₂与氯铂酸(H₂PtCl₆·6H₂O)反应,通过乙烯基与Pt的络合作用制备SiO₂负载Pt催化剂。对催化剂的Pt负载量和结构进行表征,探究了VTES与纳米SiO₂质量比对催化剂Pt负载量的影响,并通过硅氢加成反应考察了催化剂的催化活性和重复利用性。结果表明,通过VTES改性的SiO₂可以负载更多、更稳定的Pt催化剂。所制备的Pt/SiO₂-Vi₅催化剂Pt负载量为0.504%。将其用于二氯甲基硅烷与1-辛烯的硅氢加成反应中,当反应温度为80℃、反应5h时,转化率可达95.22%,β-加成产物的产率为95.11%,且催化剂至少可进行4次循环反应而催化活性无明显损失。

Abstract

SiO₂ supported Pt catalysts were prepared via the reaction of nano-SiO₂ modified by vinyltriethoxysilane(VTES) and chloroplatinic acid hexahydrate(H₂PtCl₆·6H₂O) through the complexation between the vinyl groups and Pt.Pt content and structure of the catalysts were characterized.Effect of the mass ratio of VTES to SiO₂ on Pt content were investigated,and the catalytic activity and recyclability of the catalyst were examined by a hydrosilylation reaction.Results showed that SiO₂ modified by VTES could support more amount and stable Pt catalyst,with Pt content of the Pt/SiO₂-Vi₅ catalyst reached 0.504%.The Pt/SiO₂-Vi₅ catalyst displayed high activity in the hydrosilylation of dichloromethylsilane with 1-octene.When the reaction was conducted at 80℃ for 5h,the conversion of the reactant and yield of β-adduct reached 95.22% and 95.11%,respectively.Furthermore,the recovered catalyst could be recycled and reused for at least four times without any significant loss in activity.

关键词

二氧化硅 / 乙烯基三乙氧基硅烷 / 硅氢加成反应 / 铂催化剂

Key words

SiO₂ / vinyltriethoxysilane / hydrosilylation / Pt catalyst

引用本文

引用格式 ▾

二氧化硅负载铂催化剂的制备及性能研究[J]. 化工新型材料, 2020, 48(10): 201-205 DOI:10.19817/j.cnki.issn 1006-3536.2020.10.043

登录浏览全文

4963

注册一个新账户忘记密码

参考文献

原文顺序 | 出版日期 | 本文引用

[1] 李光亮.有机硅高分子化学[M].北京:科学出版社, 1998:3-27.
[2] Hofmann R, VlatkoviAc＇5 M, Wiesbrock F.Fifty years of hydrosilylation in polymer science:a review of current trends of low-cost transition-metal and metal-free catalysts, non-thermally triggered hydrosilylation reactions, and industrial applications[J].Polymers, 2017, 9(10):534.
[3] Nakajima Y, Shimada S.Hydrosilylation reaction of olefins:recent advances and perspectives[J].RSC Advances, 2015, 5(26):20603-20616.
[4] 马国维, 翁剑秀, 范宏.硅氢加成反应在功能有机硅化合物及材料中的应用[J].科技通报, 2012, 28(11):140-147.
[5] 萧斌, 李凤仪, 戴延凤.硅氢加成反应高选择性合成甲基苯乙基二氯硅烷[J].分子催化, 2006, 20(2):153-157.
[6] Speier J L.Homogeneous catalysis of hydrosilation by transition metals[J].Advances in Organometallic Chemistry, 1979, 17:407-447.
[7] Karstedt B.Platinum complexes of unsaturated siloxanes and platinum containing organopolysiloxanes:US, 3814730[P].1974-06-04.https://patents.google.com/patent/US3814730A/en.
[8] Pagliaro M, Ciriminna R, Pandarus V, et al.Platinum-based heterogeneously catalyzed hydrosilylation[J].European Journal of Organic Chemistry, 2013, 2013(28):6227-6235.
[9] Dioumaev V K, Bullock R M.A recyclable catalyst that precipitates at the end of the reaction[J].Nature, 2003, 424(6948):530.
[10] Xiao J, Qiu Z, He W, et al.Progress in platinum catalysts supported by inorganic carriers for hydrosilylation[J].Chinese Journal of Organic Chemistry, 2016, 36(5):987-999.
[11] 储诚灿, 苏朝晖.聚合物负载纳米材料及其在催化领域的应用[J].应用化学, 2016, 33(4):379-390.
[12] Rao F, Deng S, Chen C, et al.Graphite oxide-supported Karstedt catalyst for the hydrosilylation of olefins with triethoxysilane[J].Catalysis Communications, 2014, 46(5):1-5.
[13] Alonso F, Buitrago R, Moglie Y, et al.Hydrosilylation of alkynes catalysed by platinum on titania[J].Journal of Organometallic Chemistry, 2011, 696(1):368-372.
[14] Li F, Li Y.Preparation of efficient and environment-friendly silica-supported EDTA platinum catalyst and its applications in hydrosilylation of olefins and methyldichlorosilane[J].Journal of Molecular Catalysis A:Chemical, 2016, 420:254-263.
[15] Bai Y, Zhang S, Deng Y, et al.Use of functionalized PEG with 4-aminobenzoic acid stabilized platinum nanoparticles as an efficient catalyst for the hydrosilylation of alkenes[J].Journal of Colloid and Interface Science, 2013, 394:428-433.
[16] Zai H, Zhao Y, Chen S, et al.Heterogeneously supported pseudo-single atom Pt as sustainable hydrosilylation catalyst[J].Nano Research, 2018:1-9.
[17] Burneau A, Barres O, Gallas J P, et al.Comparative study of the surface hydroxyl groups of fumed and precipitated silicas[J].Langmuir, 1990, 6(8):1364-1372.
[18] Koch Carl C.Nanostructured materials:processing, properties, and applications[M].New York:Noyes Publications, 2002.
[19] Abad A, Corma A, García H.Catalyst parameters determining activity and selectivity of supported gold nanoparticles for the aerobic oxidation of alcohols:the molecular reaction mechanism[J].Chem A Eur J, 2008, 14(1):212-222.
[20] 杨辉, 陈飞.乙烯基三甲氧基硅烷对二氧化硅的超疏水改性研究[J].人工晶体学报, 2015, 44(9):2597-2605.
[21] Naumkin A V, Kraut-Vass A, Gaarenstroom S W, et al.NIST X-ray photoelectron spectroscopy database, NIST standard reference database 20, version 4.1[DB].Washington:US Department of Commerce, 2012.http://srdata.nist.gov/xps.
[22] Li J, Yang C, Zhang L, et al.A novel fumed silica-supported nitrogenous platinum complex as a highly efficient catalyst for the hydrosilylation of olefins with triethoxysilane[J].Journal of Organometallic Chemistry, 2011, 696(9):1845-1849.