Armin Liepold , Klaus Roos , Wladimir Reschetilowski , Zhi Lin , Joao Rocha , Andreas Philippou , Michael W. Anderson
{"title":"用于处理大分子的新型微孔含铝分子筛ETS-10的表征研究","authors":"Armin Liepold , Klaus Roos , Wladimir Reschetilowski , Zhi Lin , Joao Rocha , Andreas Philippou , Michael W. Anderson","doi":"10.1016/S0927-6513(97)00011-4","DOIUrl":null,"url":null,"abstract":"<div><p>This study reports on the physico-chemical characterisation of an aluminium-containing microporous titanosilicate ETS-10 material in its protonic form in connection with catalytic testing. <sup>27</sup>Al MAS NMR spectra reveal the successful incorporation of aluminium into the lattice structure. XRD patterns indicate that the investigated ETAS-10 material in its protonic form is relatively stable thermally, an indispensable requirement for the application as an industrial catalyst material. Nevertheless, for all samples, except parent ETAS-10, XRD and <sup>29</sup>Si MAS NMR measurements indicate that an increasing amount of amorphous silica is present. Acidity investigations with combined FT-IR spectroscopy and temperature-programmed ammonia desorption and with <sup>1</sup>H MAS NMR revealed that dehydroxylation of bridging hydroxyl groups, which are assumed to be of the type Ti-(OH)-Si, occur between 350 and 550°C. An increase in both the number and strength of catalytically active bridging hydroxyl groups seems to be limited by a conventional protonic ion-exchange. The acid properties corroborate excellently with the catalytic activity and selectivity in <em>n</em>-hexadecane and 1,3,5-triisopropylbenzene cracking. The results show that electron acceptor sites, which may originate from titaniumoxide impurities or defect sites especially in titanium octahedra, could be involved in the catalytic reactions forming radical precursors.</p></div>","PeriodicalId":100926,"journal":{"name":"Microporous Materials","volume":"10 4","pages":"Pages 211-224"},"PeriodicalIF":0.0000,"publicationDate":"1997-07-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://sci-hub-pdf.com/10.1016/S0927-6513(97)00011-4","citationCount":"21","resultStr":"{\"title\":\"Characterisation studies on the new microporous aluminium-containing ETS-10 molecular sieve used for processing larger molecules\",\"authors\":\"Armin Liepold , Klaus Roos , Wladimir Reschetilowski , Zhi Lin , Joao Rocha , Andreas Philippou , Michael W. Anderson\",\"doi\":\"10.1016/S0927-6513(97)00011-4\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<div><p>This study reports on the physico-chemical characterisation of an aluminium-containing microporous titanosilicate ETS-10 material in its protonic form in connection with catalytic testing. <sup>27</sup>Al MAS NMR spectra reveal the successful incorporation of aluminium into the lattice structure. XRD patterns indicate that the investigated ETAS-10 material in its protonic form is relatively stable thermally, an indispensable requirement for the application as an industrial catalyst material. Nevertheless, for all samples, except parent ETAS-10, XRD and <sup>29</sup>Si MAS NMR measurements indicate that an increasing amount of amorphous silica is present. Acidity investigations with combined FT-IR spectroscopy and temperature-programmed ammonia desorption and with <sup>1</sup>H MAS NMR revealed that dehydroxylation of bridging hydroxyl groups, which are assumed to be of the type Ti-(OH)-Si, occur between 350 and 550°C. An increase in both the number and strength of catalytically active bridging hydroxyl groups seems to be limited by a conventional protonic ion-exchange. The acid properties corroborate excellently with the catalytic activity and selectivity in <em>n</em>-hexadecane and 1,3,5-triisopropylbenzene cracking. The results show that electron acceptor sites, which may originate from titaniumoxide impurities or defect sites especially in titanium octahedra, could be involved in the catalytic reactions forming radical precursors.</p></div>\",\"PeriodicalId\":100926,\"journal\":{\"name\":\"Microporous Materials\",\"volume\":\"10 4\",\"pages\":\"Pages 211-224\"},\"PeriodicalIF\":0.0000,\"publicationDate\":\"1997-07-01\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"https://sci-hub-pdf.com/10.1016/S0927-6513(97)00011-4\",\"citationCount\":\"21\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Microporous Materials\",\"FirstCategoryId\":\"1085\",\"ListUrlMain\":\"https://www.sciencedirect.com/science/article/pii/S0927651397000114\",\"RegionNum\":0,\"RegionCategory\":null,\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"\",\"JCRName\":\"\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Microporous Materials","FirstCategoryId":"1085","ListUrlMain":"https://www.sciencedirect.com/science/article/pii/S0927651397000114","RegionNum":0,"RegionCategory":null,"ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"","JCRName":"","Score":null,"Total":0}
引用次数: 21
摘要
本研究报告了一种质子形式的含铝微孔钛硅酸盐ETS-10材料的物理化学特征,并与催化测试相联系。27Al的MAS NMR谱显示铝成功地结合到晶格结构中。XRD图谱表明,所研究的质子态ETAS-10材料具有相对稳定的热稳定性,这是作为工业催化剂材料应用的必要条件。然而,对于所有样品,除了母体ETAS-10, XRD和29Si MAS NMR测量表明,无定形二氧化硅的数量增加。结合FT-IR光谱和程序升温氨解吸以及1H MAS NMR对酸度的研究表明,桥接羟基(假定为Ti-(OH)- si型)的去羟基化发生在350至550°C之间。催化活性桥接羟基的数量和强度的增加似乎受到传统质子离子交换的限制。其酸性质与正十六烷和1,3,5-三异丙苯裂解的催化活性和选择性相吻合。结果表明,电子受体位点可能来源于氧化钛杂质或缺陷位点,特别是钛八面体中的缺陷位点,可能参与了自由基前体形成的催化反应。
Characterisation studies on the new microporous aluminium-containing ETS-10 molecular sieve used for processing larger molecules
This study reports on the physico-chemical characterisation of an aluminium-containing microporous titanosilicate ETS-10 material in its protonic form in connection with catalytic testing. 27Al MAS NMR spectra reveal the successful incorporation of aluminium into the lattice structure. XRD patterns indicate that the investigated ETAS-10 material in its protonic form is relatively stable thermally, an indispensable requirement for the application as an industrial catalyst material. Nevertheless, for all samples, except parent ETAS-10, XRD and 29Si MAS NMR measurements indicate that an increasing amount of amorphous silica is present. Acidity investigations with combined FT-IR spectroscopy and temperature-programmed ammonia desorption and with 1H MAS NMR revealed that dehydroxylation of bridging hydroxyl groups, which are assumed to be of the type Ti-(OH)-Si, occur between 350 and 550°C. An increase in both the number and strength of catalytically active bridging hydroxyl groups seems to be limited by a conventional protonic ion-exchange. The acid properties corroborate excellently with the catalytic activity and selectivity in n-hexadecane and 1,3,5-triisopropylbenzene cracking. The results show that electron acceptor sites, which may originate from titaniumoxide impurities or defect sites especially in titanium octahedra, could be involved in the catalytic reactions forming radical precursors.