Fateme Poorsharbaf Ghavi, Petr Golis, Martin Kubů, Jan Přech, Maksym Opanasenko
{"title":"沸石的酸度和孔隙率特性影响其在百里酚合成中的催化性能","authors":"Fateme Poorsharbaf Ghavi, Petr Golis, Martin Kubů, Jan Přech, Maksym Opanasenko","doi":"10.1016/j.micromeso.2024.113198","DOIUrl":null,"url":null,"abstract":"<div><p>Thymol is synthesized from m-cresol alkylation reaction with 2-propanol. A few commercial zeolites have been tested in this reaction, but the influence of acidity and porosity of a zeolite on the m-cresol conversion and thymol yield is scarcely studied. Isomorphously-substituted Al-, Ga-, Fe-, B-, and In-UTL with different heteroelements and thus different ratio between strong and weak sites give insight into the effect of acidity. Isoreticular zeolites Al-UTL, Al-IPC-7, and Al-IPC-2 with different pore sizes reveal the effect of porosity. In this study, m-cresol conversion was far from comparable over Al-UTL or Ga-UTL (X = 18–19 %) and Fe-UTL, B-UTL, or In-UTL (X = 2–3 %) having different concentration of strong Brønsted acid sites. Thymol yield was also higher over Al- and Ga-UTL (Y = 11–13 %) than over Fe-, B-, and In-UTL (Y = 1–2 %). The easier accessibility to the strong Brønsted acid sites in Al-UTL, provided by bigger pore sizes, resulted in higher m-cresol conversion and thymol yield compared to Al-IPC-7 (X = 15 % and Y = 8 %) and Al-IPC-2 (X = 6 % and Y = 2 %). In addition, the stronger Brønsted acidity and large and extra-large porosity in Al-UTL and Ga-UTL facilitated the rearrangement of isopropyl-3-methylphenyl ether - the product of the O-alkylation pathway - to thymol. Thus, Al-UTL and Ga-UTL (along with Al-FAU reference material) confirmed the optimum structural properties for a high selectivity to thymol.</p></div>","PeriodicalId":392,"journal":{"name":"Microporous and Mesoporous Materials","volume":null,"pages":null},"PeriodicalIF":4.8000,"publicationDate":"2024-05-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.sciencedirect.com/science/article/pii/S1387181124002208/pdfft?md5=a204653b1a24fdc202e65e0486394257&pid=1-s2.0-S1387181124002208-main.pdf","citationCount":"0","resultStr":"{\"title\":\"Acidity and porosity properties of zeolites affect their catalytic performance in thymol synthesis\",\"authors\":\"Fateme Poorsharbaf Ghavi, Petr Golis, Martin Kubů, Jan Přech, Maksym Opanasenko\",\"doi\":\"10.1016/j.micromeso.2024.113198\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<div><p>Thymol is synthesized from m-cresol alkylation reaction with 2-propanol. A few commercial zeolites have been tested in this reaction, but the influence of acidity and porosity of a zeolite on the m-cresol conversion and thymol yield is scarcely studied. Isomorphously-substituted Al-, Ga-, Fe-, B-, and In-UTL with different heteroelements and thus different ratio between strong and weak sites give insight into the effect of acidity. Isoreticular zeolites Al-UTL, Al-IPC-7, and Al-IPC-2 with different pore sizes reveal the effect of porosity. In this study, m-cresol conversion was far from comparable over Al-UTL or Ga-UTL (X = 18–19 %) and Fe-UTL, B-UTL, or In-UTL (X = 2–3 %) having different concentration of strong Brønsted acid sites. Thymol yield was also higher over Al- and Ga-UTL (Y = 11–13 %) than over Fe-, B-, and In-UTL (Y = 1–2 %). The easier accessibility to the strong Brønsted acid sites in Al-UTL, provided by bigger pore sizes, resulted in higher m-cresol conversion and thymol yield compared to Al-IPC-7 (X = 15 % and Y = 8 %) and Al-IPC-2 (X = 6 % and Y = 2 %). In addition, the stronger Brønsted acidity and large and extra-large porosity in Al-UTL and Ga-UTL facilitated the rearrangement of isopropyl-3-methylphenyl ether - the product of the O-alkylation pathway - to thymol. Thus, Al-UTL and Ga-UTL (along with Al-FAU reference material) confirmed the optimum structural properties for a high selectivity to thymol.</p></div>\",\"PeriodicalId\":392,\"journal\":{\"name\":\"Microporous and Mesoporous Materials\",\"volume\":null,\"pages\":null},\"PeriodicalIF\":4.8000,\"publicationDate\":\"2024-05-27\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"https://www.sciencedirect.com/science/article/pii/S1387181124002208/pdfft?md5=a204653b1a24fdc202e65e0486394257&pid=1-s2.0-S1387181124002208-main.pdf\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Microporous and Mesoporous Materials\",\"FirstCategoryId\":\"88\",\"ListUrlMain\":\"https://www.sciencedirect.com/science/article/pii/S1387181124002208\",\"RegionNum\":3,\"RegionCategory\":\"材料科学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q1\",\"JCRName\":\"CHEMISTRY, APPLIED\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Microporous and Mesoporous Materials","FirstCategoryId":"88","ListUrlMain":"https://www.sciencedirect.com/science/article/pii/S1387181124002208","RegionNum":3,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q1","JCRName":"CHEMISTRY, APPLIED","Score":null,"Total":0}
Acidity and porosity properties of zeolites affect their catalytic performance in thymol synthesis
Thymol is synthesized from m-cresol alkylation reaction with 2-propanol. A few commercial zeolites have been tested in this reaction, but the influence of acidity and porosity of a zeolite on the m-cresol conversion and thymol yield is scarcely studied. Isomorphously-substituted Al-, Ga-, Fe-, B-, and In-UTL with different heteroelements and thus different ratio between strong and weak sites give insight into the effect of acidity. Isoreticular zeolites Al-UTL, Al-IPC-7, and Al-IPC-2 with different pore sizes reveal the effect of porosity. In this study, m-cresol conversion was far from comparable over Al-UTL or Ga-UTL (X = 18–19 %) and Fe-UTL, B-UTL, or In-UTL (X = 2–3 %) having different concentration of strong Brønsted acid sites. Thymol yield was also higher over Al- and Ga-UTL (Y = 11–13 %) than over Fe-, B-, and In-UTL (Y = 1–2 %). The easier accessibility to the strong Brønsted acid sites in Al-UTL, provided by bigger pore sizes, resulted in higher m-cresol conversion and thymol yield compared to Al-IPC-7 (X = 15 % and Y = 8 %) and Al-IPC-2 (X = 6 % and Y = 2 %). In addition, the stronger Brønsted acidity and large and extra-large porosity in Al-UTL and Ga-UTL facilitated the rearrangement of isopropyl-3-methylphenyl ether - the product of the O-alkylation pathway - to thymol. Thus, Al-UTL and Ga-UTL (along with Al-FAU reference material) confirmed the optimum structural properties for a high selectivity to thymol.
期刊介绍:
Microporous and Mesoporous Materials covers novel and significant aspects of porous solids classified as either microporous (pore size up to 2 nm) or mesoporous (pore size 2 to 50 nm). The porosity should have a specific impact on the material properties or application. Typical examples are zeolites and zeolite-like materials, pillared materials, clathrasils and clathrates, carbon molecular sieves, ordered mesoporous materials, organic/inorganic porous hybrid materials, or porous metal oxides. Both natural and synthetic porous materials are within the scope of the journal.
Topics which are particularly of interest include:
All aspects of natural microporous and mesoporous solids
The synthesis of crystalline or amorphous porous materials
The physico-chemical characterization of microporous and mesoporous solids, especially spectroscopic and microscopic
The modification of microporous and mesoporous solids, for example by ion exchange or solid-state reactions
All topics related to diffusion of mobile species in the pores of microporous and mesoporous materials
Adsorption (and other separation techniques) using microporous or mesoporous adsorbents
Catalysis by microporous and mesoporous materials
Host/guest interactions
Theoretical chemistry and modelling of host/guest interactions
All topics related to the application of microporous and mesoporous materials in industrial catalysis, separation technology, environmental protection, electrochemistry, membranes, sensors, optical devices, etc.