{"title":"丙酮在酸性沸石上的吸附和互变异构反应:不同类型沸石的约束效应","authors":"B. Boekfa, P. Pantu, M. Probst, J. Limtrakul","doi":"10.1021/JP1058947","DOIUrl":null,"url":null,"abstract":"The adsorption and tautomerization reaction of acetone in H-FER, H-ZSM-5, and H-MCM-22 zeolites has been studied using full quantum calculations at the M06-2X/6-311+G(2df,2p) level of theory. The combination of a large quantum cluster and this meta-hybrid density functional results in reasonably accurate adsorption energies of −26.9, −28.1, and −23.9 kcal/mol for acetone adsorption in H-FER, H-ZSM-5, and H-MCM-22, respectively. Due to the acidity of the zeolite and the framework confinement effect, the tautomerization of acetone proceeds through a much lower activation barrier than in the isolated gas phase or in the presence of water molecules alone. The activation energies are calculated to be 24.9, 20.5, and 16.6 kcal/mol in H-FER, H-ZSM-5 and H-MCM-22, respectively. The endothermic reaction energy decreases with increasing of the zeolite pore sizes and amounts to 22.7, 17.6, and 15.9 kcal/mol for the reaction in H-FER, H-ZSM-5 and H-MCM-22, respectively. In addition, the adsorbed acetone enol is found...","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"114 1","pages":"15061-15067"},"PeriodicalIF":3.3000,"publicationDate":"2010-08-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://sci-hub-pdf.com/10.1021/JP1058947","citationCount":"67","resultStr":"{\"title\":\"Adsorption and Tautomerization Reaction of Acetone on Acidic Zeolites: The Confinement Effect in Different Types of Zeolites\",\"authors\":\"B. Boekfa, P. Pantu, M. Probst, J. Limtrakul\",\"doi\":\"10.1021/JP1058947\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"The adsorption and tautomerization reaction of acetone in H-FER, H-ZSM-5, and H-MCM-22 zeolites has been studied using full quantum calculations at the M06-2X/6-311+G(2df,2p) level of theory. The combination of a large quantum cluster and this meta-hybrid density functional results in reasonably accurate adsorption energies of −26.9, −28.1, and −23.9 kcal/mol for acetone adsorption in H-FER, H-ZSM-5, and H-MCM-22, respectively. Due to the acidity of the zeolite and the framework confinement effect, the tautomerization of acetone proceeds through a much lower activation barrier than in the isolated gas phase or in the presence of water molecules alone. The activation energies are calculated to be 24.9, 20.5, and 16.6 kcal/mol in H-FER, H-ZSM-5 and H-MCM-22, respectively. The endothermic reaction energy decreases with increasing of the zeolite pore sizes and amounts to 22.7, 17.6, and 15.9 kcal/mol for the reaction in H-FER, H-ZSM-5 and H-MCM-22, respectively. In addition, the adsorbed acetone enol is found...\",\"PeriodicalId\":61,\"journal\":{\"name\":\"The Journal of Physical Chemistry C\",\"volume\":\"114 1\",\"pages\":\"15061-15067\"},\"PeriodicalIF\":3.3000,\"publicationDate\":\"2010-08-19\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"https://sci-hub-pdf.com/10.1021/JP1058947\",\"citationCount\":\"67\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"The Journal of Physical Chemistry C\",\"FirstCategoryId\":\"1\",\"ListUrlMain\":\"https://doi.org/10.1021/JP1058947\",\"RegionNum\":3,\"RegionCategory\":\"化学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q2\",\"JCRName\":\"CHEMISTRY, PHYSICAL\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"The Journal of Physical Chemistry C","FirstCategoryId":"1","ListUrlMain":"https://doi.org/10.1021/JP1058947","RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q2","JCRName":"CHEMISTRY, PHYSICAL","Score":null,"Total":0}
Adsorption and Tautomerization Reaction of Acetone on Acidic Zeolites: The Confinement Effect in Different Types of Zeolites
The adsorption and tautomerization reaction of acetone in H-FER, H-ZSM-5, and H-MCM-22 zeolites has been studied using full quantum calculations at the M06-2X/6-311+G(2df,2p) level of theory. The combination of a large quantum cluster and this meta-hybrid density functional results in reasonably accurate adsorption energies of −26.9, −28.1, and −23.9 kcal/mol for acetone adsorption in H-FER, H-ZSM-5, and H-MCM-22, respectively. Due to the acidity of the zeolite and the framework confinement effect, the tautomerization of acetone proceeds through a much lower activation barrier than in the isolated gas phase or in the presence of water molecules alone. The activation energies are calculated to be 24.9, 20.5, and 16.6 kcal/mol in H-FER, H-ZSM-5 and H-MCM-22, respectively. The endothermic reaction energy decreases with increasing of the zeolite pore sizes and amounts to 22.7, 17.6, and 15.9 kcal/mol for the reaction in H-FER, H-ZSM-5 and H-MCM-22, respectively. In addition, the adsorbed acetone enol is found...
期刊介绍:
The Journal of Physical Chemistry A/B/C is devoted to reporting new and original experimental and theoretical basic research of interest to physical chemists, biophysical chemists, and chemical physicists.