不同厚度TS-1空心球分子筛的制备及表征
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摘要
以四丙基氢氧化铵(TPAOH)为模板剂,正硅酸乙酯(TEOS)为硅源,低成本硫酸钛(Ti(SO4)2)为钛源,在传统碱处理的基础上通过溶解-再结晶的后处理方法,制备得到了形貌规整且大小均匀的球形TS-1空心纳米颗粒,其颗粒尺寸约为200 nm。采用X射线衍射(XRD),N2吸脱附测试,扫描电镜(SEM),透射电镜(TEM)以及红外可见光谱(FTIR)等手段对不同后处理条件所得空心材料进行表征,结果表明,再结晶时间对空心材料的壁厚有明显的影响,且所得样品中Ti物种主要是以骨架内四配位形式存在的。同母体分子筛相比,空心材料在丙烯环氧化反应中体现出更好的催化活性。
Highly uniform hollow TS-1 zeolites were successfully prepared by a simple dissolutionrecrystallization strategy which based on the traditional alkaline treatment. Using TPAOH as the template,TEOS as the silicon source,low-priced Ti(SO4)2 as the titanium source,the obtained samples have regular morphology with the particle diameter of about 200 nm. The hollow structure was investigated by X-ray diffraction(XRD), N2 adsoprtion-desorption measurements, scanning electron microscopy(SEM),transmission electron microscope(TEM) and Fourier-transform infrared spectroscopy(FTIR)method. The results show that the recrystallization time has great influence on the thickness of the particle,and it is noteworthy that Ti species are exclusively tetrahedrally coordinate in all samples.Compared with the parent TS-1 zeolite, hollow samples exhibited higher catalytic activities in the epoxidation of propylene.
Highly uniform hollow TS-1 zeolites were successfully prepared by a simple dissolutionrecrystallization strategy which based on the traditional alkaline treatment. Using TPAOH as the template,TEOS as the silicon source,low-priced Ti(SO4)2 as the titanium source,the obtained samples have regular morphology with the particle diameter of about 200 nm. The hollow structure was investigated by X-ray diffraction(XRD), N2 adsoprtion-desorption measurements, scanning electron microscopy(SEM),transmission electron microscope(TEM) and Fourier-transform infrared spectroscopy(FTIR)method. The results show that the recrystallization time has great influence on the thickness of the particle,and it is noteworthy that Ti species are exclusively tetrahedrally coordinate in all samples.Compared with the parent TS-1 zeolite, hollow samples exhibited higher catalytic activities in the epoxidation of propylene.
引文
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[2]周继承,王祥生.无机钛硅原料体系合成TS-1催化丙烯环氧化反应[J].分子催化,2000,23(5):363-368.
[3]顾晓利,乔旭,崔咪芬,等.TS-1钛硅分子筛的制备研究新进展[J].现代化工,2005,25:23-29.
[4]左轶,宋万仓,王梦丽,等.固定床反应器上挤条小晶粒TS-1催化丙烯环氧化反应[J].物理化学学报,2013,29(01),183-190.
[5]沈本贤,赵基刚,肖卫国,等.丙烯环氧化反应中TS-1催化剂失活研究[J].燃料化学学报,2007,35(5):609-614.
[6]王丽琴,王祥生,郭新闻,等.合成TS-1分子筛的结晶动力学及催化性能研究[J].催化学报,2003,24(2):132-136.
[7]赵琦,韩秀文,刘秀梅,等.以四丙基溴化铵为模板剂合成TS-1分子筛的研究[J].物理化学学报,1998,14(10),906-912.
[8]张海娇,姚明恺,谢伟,等.TS-1分子筛的无机法合成及其催化苯酚羟基化性能[J].催化学报,2007,28(10):895-899.
[9]左轶,刘民,郭新闻.钛硅分子筛的合成及其催化氧化反应研究进展[J].石油学报(石油加工),2015,31(2):343-359.
[10]夏长久,林民,彭欣欣,等.多尺度孔道分布钛硅分子筛材料制备策略的探讨[J].石油学报(石油加工),2016,32(2):407-417.
[11]吴保军,张明森,梁泽生,等.水热合成条件对TS-1分子筛苯酚羟基化反应性能的影响[J].石油化工,2001,30(10):744-748.
[12]Choi M,Cho H S,Srivastava R,et al.Amphiphilic organosilane-directed synthesis of crystalline zeolite with tunable mesoporosity[J].Nat.Mater.,2006,5(9):718-723.
[13]Na K,Kim C Jo J,Cho K,et al.Directing zeolite structures into hierarchically nanoporous architectures[J].Science,2011,333(6040):328-332.
[14]Rhodes K H,Davis S A,Caruso F,et al.Hierarchical assembly of zeolite nanoparticles into ordered macroporous monoliths using core-shell building blocks[J].Chem.Mater.,2000,12(10):2832-2834.
[15]Wang X D,Yang W L,Tang Y,et al.Fabrication of hollow zeolite spheres[J].Chem.Commun.,2000,21(21):2161-2162.
[16]Valtchev V,Mintova S.Layer-by-layer preparation of zeolite coatings of nanosized crystals[J].Microporous Mesoporous Mater.,2001,43(1):41-49.
[17]Groen J C,Bach T,Ziese U,et al.Creation of hollow zeolite architectures by controlled desilication of Al-zoned ZSM-5 crystals[J].J.Am.Chem.Soc.,2005,127(31):10792-10793.
[18]Mei C S,Liu Z C,Wen P Y,et al.Regular HZSM-5 microboxes prepared via a mild alkaline treatment[J].J.Mater.Chem.,2008,18(29):3496-3500.
[19]Wang Y R,Tuel A.Nanoporous zeolite single crystals:ZSM-5 nanoboxes with uniform intracrystalline hollow structures[J].Microporous Mesoporous Mater.,2008,113(1):286-295.
[20]Pirutko L V,Uriarte A K,Chernyavsky V S,et al.Preparation and catalytic study of metal modified TS-1 in the oxidation of benzene to phenol by N2O[J].Microporous Mesoporous Mater.,2001,48(1):345-353.
[21]Bengoa J F,Gallegos N G,Marchetti S G,et al.A Influence of TS-1 structural properties and operation conditions on benzene catalytic oxidation with H2O2[J].Microporous Mesoporous Mater.,1998,24(4):163-172.