TY - JOUR
T1 - Characterization of MFI and BEA embedded in mesoporous molecular sieve - Thermal stability
AU - Österholm, Heidi
AU - Kumar, Narendra
AU - Lindblad, Marina
AU - Tiitta, Marja
AU - Salmi, Tapio
AU - Murzin, Dmitry
N1 - Funding Information:
This work is in part supported by Grants from TEKES. The authors are grateful to Dr. Andrew Root, MagSOL for MAS NMR measurements, Ms. Helena Leuku, Ms. Riitta Vuorenmaa at Neste Oil for analyses.
Copyright:
Copyright 2012 Elsevier B.V., All rights reserved.
PY - 2012/5/15
Y1 - 2012/5/15
N2 - MFI and BEA zeolite seeds were embedded in MCM-41 gel mixture with or without additional aluminum isopropoxide. These novel meso-microporous molecular sieves, NK-MM-MFI and NK-MM-BEA, contain zeolite crystallites surrounded by a mesoporous ordered phase. A thorough characterization was made utilizing XRF, XRD, N 2-physisorption and 27Al MAS NMR as well as acidity and acid site strength measurements by 1H MAS NMR and NH 3-TPD. Al content was varied from 0.4 to 3.9 wt.% to tailor acidity and porosity. The embedded NK-MM-MFI and NK-MM-BEA materials were compared to pure zeolites and MCM-41. The mesoporous phase had a stronger effect on porosity and number of acid sites, while acid site strength was dominated by the microporous zeolite seeds. Total number of acid sites increased linearly with Al content, which also was true for Brønsted acidity in NK-MM-MFI, while no effect on Brønsted acidity was observed in NK-MM-BEA. The thermal stability of NK-MM-MFI and NK-MM-BEA, as well as of MFI, BEA and MCM-41, was studied by calcination in air at 773, 873 and 1173 K. The exposure to 1173 K caused a decrease in unit cell dimension of the MCM-41 phase. The unit cell shrinkage was the largest in pure MCM-41 and the smallest in NK-MM-MFI. The zeolite addition stabilized the mesoporous structure, effect of MFI was more pronounced than of BEA. Total acidity and Brønsted acidity decreased, while only minor loss of tetrahedral framework Al was observed. The loss in acidity was caused by thermal dehydroxylation and being thus reversible. It was shown that the structure, porosity and framework Al were thermally stable in NK-MM-MFI and NK-MM-BEA.
AB - MFI and BEA zeolite seeds were embedded in MCM-41 gel mixture with or without additional aluminum isopropoxide. These novel meso-microporous molecular sieves, NK-MM-MFI and NK-MM-BEA, contain zeolite crystallites surrounded by a mesoporous ordered phase. A thorough characterization was made utilizing XRF, XRD, N 2-physisorption and 27Al MAS NMR as well as acidity and acid site strength measurements by 1H MAS NMR and NH 3-TPD. Al content was varied from 0.4 to 3.9 wt.% to tailor acidity and porosity. The embedded NK-MM-MFI and NK-MM-BEA materials were compared to pure zeolites and MCM-41. The mesoporous phase had a stronger effect on porosity and number of acid sites, while acid site strength was dominated by the microporous zeolite seeds. Total number of acid sites increased linearly with Al content, which also was true for Brønsted acidity in NK-MM-MFI, while no effect on Brønsted acidity was observed in NK-MM-BEA. The thermal stability of NK-MM-MFI and NK-MM-BEA, as well as of MFI, BEA and MCM-41, was studied by calcination in air at 773, 873 and 1173 K. The exposure to 1173 K caused a decrease in unit cell dimension of the MCM-41 phase. The unit cell shrinkage was the largest in pure MCM-41 and the smallest in NK-MM-MFI. The zeolite addition stabilized the mesoporous structure, effect of MFI was more pronounced than of BEA. Total acidity and Brønsted acidity decreased, while only minor loss of tetrahedral framework Al was observed. The loss in acidity was caused by thermal dehydroxylation and being thus reversible. It was shown that the structure, porosity and framework Al were thermally stable in NK-MM-MFI and NK-MM-BEA.
KW - Characterization
KW - Embedding
KW - Micro-mesoporous molecular sieve
KW - Thermal stability
UR - http://www.scopus.com/inward/record.url?scp=84857918609&partnerID=8YFLogxK
U2 - 10.1016/j.micromeso.2011.10.006
DO - 10.1016/j.micromeso.2011.10.006
M3 - Article
AN - SCOPUS:84857918609
SN - 1387-1811
VL - 154
SP - 124
EP - 132
JO - Microporous and Mesoporous Materials
JF - Microporous and Mesoporous Materials
ER -