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Effect of Ge/Si substitutions on the local geometry of Si framework sites in zeolites: A combined high resolutionsup29/supSi MAS NMR and DFT/MM study on zeolite Beta polymorph C (BEC)
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SYSNO ASEP 0488843 Druh ASEP J - Článek v odborném periodiku Zařazení RIV J - Článek v odborném periodiku Poddruh J Článek ve WOS Název Effect of Ge/Si substitutions on the local geometry of Si framework sites in zeolites: A combined high resolutionsup29/supSi MAS NMR and DFT/MM study on zeolite Beta polymorph C (BEC) Tvůrce(i) Whittleton, Sarah R. (UFCH-W)
Vicente, A. (FR)
Fernandez, C. (FR)
Rastegar, Somayeh Faal (UFCH-W) ORCID, RID
Fishchuk, Anna V. (UFCH-W)
Sklenák, Štěpán (UFCH-W) RID, ORCID, SAIZdroj.dok. Microporous and Mesoporous Materials. - : Elsevier - ISSN 1387-1811
Roč. 267, SEP 2018 (2018), s. 124-133Poč.str. 10 s. Jazyk dok. eng - angličtina Země vyd. NL - Nizozemsko Klíč. slova 29 Si MAS NMR ; bec ; Ge-zeolites ; Germanoaluminosilicates ; Zeolite Beta polymorph C Vědní obor RIV CF - Fyzikální chemie a teoretická chemie Obor OECD Physical chemistry CEP GA15-14007S GA ČR - Grantová agentura ČR Institucionální podpora UFCH-W - RVO:61388955 UT WOS 000435060700015 EID SCOPUS 85044509771 DOI 10.1016/j.micromeso.2018.03.021 Anotace We employed density functional theory/molecular mechanics (DFT/MM) calculations and 29 Si magic-angle spinning (MAS) NMR spectroscopy to investigate the effect of single and multiple Ge/Si substitutions on the 29 Si NMR parameters as well as the local geometry of SiO 4 tetrahedra of the nearest (Ge-O-Si) and next-nearest (Ge-O-Si-O-Si) neighboring Si atoms. The influences of the Ge/Si substitutions are compared with the effects of the corresponding Al/Si substitutions (i.e., Al-O-Si and Al-O-Si-O-Si, respectively). Zeolite Beta polymorph C (BEC), containing double four-membered rings (D4Rs) and exhibiting three distinguishable T sites in the framework, was chosen for this study as a model of germanium containing zeolites. Our computations give a systematic downshift of the 29 Si chemical shift of Si by 1–6 ppm for Ge-O-Si sequences. Furthermore, the contributions of two, three, and four Ge atom s as the nearest neighbors to the downshift of Si are not additive and the calculated downshifts lie in the intervals from 2 to 6 ppm, from 1 to 9 ppm, and from 5 to 11 ppm, respectively. Conversely, the contributions of two, three, and four Al atoms as the nearest neighbors are approximately additive. The downshifts caused by Ge nearest neighbors are less than half compared with the corresponding downshifts caused by Al. Moreover, our calculations show that there are no systematic contributions of Ge and Al as next-nearest neighbors (i.e., Ge-O-Si-O-Si and Al-O-Si-O-Si, respectively) to the 29 Si chemical shift of Si, and not even the direction (sign) can be predicted without calculating the corresponding sequence. Pracoviště Ústav fyzikální chemie J.Heyrovského Kontakt Michaela Knapová, michaela.knapova@jh-inst.cas.cz, Tel.: 266 053 196 Rok sběru 2019
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