Defect Formation, T-Atom Substitution and Adsorption of Guest Molecules in MSE-Type Zeolite Framework—DFT Modeling
We used computational modeling, based on Density Functional Theory, to help understand the preference for the formation of silanol nests and the substitution of Si by Ti or Al in different crystallographic positions of the MSE-type framework. All these processes were found to be energetically favora...
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| Format: | Article |
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MDPI AG
2021-12-01
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| Series: | Molecules |
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| Online Access: | https://www.mdpi.com/1420-3049/26/23/7296 |
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| author | Petko St. Petkov Kristina Simeonova Iskra Z. Koleva Hristiyan A. Aleksandrov Yoshihiro Kubota Satoshi Inagaki Valentin Valtchev Georgi N. Vayssilov |
| author_facet | Petko St. Petkov Kristina Simeonova Iskra Z. Koleva Hristiyan A. Aleksandrov Yoshihiro Kubota Satoshi Inagaki Valentin Valtchev Georgi N. Vayssilov |
| author_sort | Petko St. Petkov |
| collection | DOAJ |
| description | We used computational modeling, based on Density Functional Theory, to help understand the preference for the formation of silanol nests and the substitution of Si by Ti or Al in different crystallographic positions of the MSE-type framework. All these processes were found to be energetically favorable by more than 100 kJ/mol. We suggested an approach for experimental identification of the T atom position in Ti-MCM-68 zeolite via simulation of infrared spectra of pyridine and acetonitrile adsorption at Ti. The modeling of adsorption of hydrogen peroxide at Ti center in the framework has shown that the molecular adsorption was preferred over the dissociative adsorption by 20 to 40 kJ/mol in the presence or absence of neighboring T-atom vacancy, respectively. |
| first_indexed | 2024-03-10T04:47:23Z |
| format | Article |
| id | doaj.art-6cb4cee8e7ae43998c9ad6fe166479c2 |
| institution | Directory Open Access Journal |
| issn | 1420-3049 |
| language | English |
| last_indexed | 2024-03-10T04:47:23Z |
| publishDate | 2021-12-01 |
| publisher | MDPI AG |
| record_format | Article |
| series | Molecules |
| spelling | doaj.art-6cb4cee8e7ae43998c9ad6fe166479c22023-11-23T02:50:22ZengMDPI AGMolecules1420-30492021-12-012623729610.3390/molecules26237296Defect Formation, T-Atom Substitution and Adsorption of Guest Molecules in MSE-Type Zeolite Framework—DFT ModelingPetko St. Petkov0Kristina Simeonova1Iskra Z. Koleva2Hristiyan A. Aleksandrov3Yoshihiro Kubota4Satoshi Inagaki5Valentin Valtchev6Georgi N. Vayssilov7Faculty of Chemistry and Pharmacy, University of Sofia, 1 James Bourchier Blvd., 1164 Sofia, BulgariaFaculty of Chemistry and Pharmacy, University of Sofia, 1 James Bourchier Blvd., 1164 Sofia, BulgariaFaculty of Chemistry and Pharmacy, University of Sofia, 1 James Bourchier Blvd., 1164 Sofia, BulgariaFaculty of Chemistry and Pharmacy, University of Sofia, 1 James Bourchier Blvd., 1164 Sofia, BulgariaDivision of Materials Science and Chemical Engineering, Yokohama National University, 79-5 Tokiwadai, Hodogaya-ku, Yokohama 240-8501, JapanDivision of Materials Science and Chemical Engineering, Yokohama National University, 79-5 Tokiwadai, Hodogaya-ku, Yokohama 240-8501, JapanLaboratoire Catalyse et Spectrochimie, Normandie Université, ENSICAEN, CNRS, 6 Boulevard Maréchal Juin, 14050 Caen, FranceFaculty of Chemistry and Pharmacy, University of Sofia, 1 James Bourchier Blvd., 1164 Sofia, BulgariaWe used computational modeling, based on Density Functional Theory, to help understand the preference for the formation of silanol nests and the substitution of Si by Ti or Al in different crystallographic positions of the MSE-type framework. All these processes were found to be energetically favorable by more than 100 kJ/mol. We suggested an approach for experimental identification of the T atom position in Ti-MCM-68 zeolite via simulation of infrared spectra of pyridine and acetonitrile adsorption at Ti. The modeling of adsorption of hydrogen peroxide at Ti center in the framework has shown that the molecular adsorption was preferred over the dissociative adsorption by 20 to 40 kJ/mol in the presence or absence of neighboring T-atom vacancy, respectively.https://www.mdpi.com/1420-3049/26/23/7296zeolitesilanol vacancyTi incorporationMSE frameworkDFT modeling |
| spellingShingle | Petko St. Petkov Kristina Simeonova Iskra Z. Koleva Hristiyan A. Aleksandrov Yoshihiro Kubota Satoshi Inagaki Valentin Valtchev Georgi N. Vayssilov Defect Formation, T-Atom Substitution and Adsorption of Guest Molecules in MSE-Type Zeolite Framework—DFT Modeling Molecules zeolite silanol vacancy Ti incorporation MSE framework DFT modeling |
| title | Defect Formation, T-Atom Substitution and Adsorption of Guest Molecules in MSE-Type Zeolite Framework—DFT Modeling |
| title_full | Defect Formation, T-Atom Substitution and Adsorption of Guest Molecules in MSE-Type Zeolite Framework—DFT Modeling |
| title_fullStr | Defect Formation, T-Atom Substitution and Adsorption of Guest Molecules in MSE-Type Zeolite Framework—DFT Modeling |
| title_full_unstemmed | Defect Formation, T-Atom Substitution and Adsorption of Guest Molecules in MSE-Type Zeolite Framework—DFT Modeling |
| title_short | Defect Formation, T-Atom Substitution and Adsorption of Guest Molecules in MSE-Type Zeolite Framework—DFT Modeling |
| title_sort | defect formation t atom substitution and adsorption of guest molecules in mse type zeolite framework dft modeling |
| topic | zeolite silanol vacancy Ti incorporation MSE framework DFT modeling |
| url | https://www.mdpi.com/1420-3049/26/23/7296 |
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