Highly porous hybrid metallosilicate materials prepared by
non-hydrolytic sol-gel: Hydrothermal stability and catalytic
properties in ethanol dehydration

J 2020

Highly porous hybrid metallosilicate materials prepared by non-hydrolytic sol-gel: Hydrothermal stability and catalytic properties in ethanol dehydration

STÝSKALÍK, Aleš, Imene KORDOGHLI, Claude POLEUNIS, Arnaud DELCORTE, Carmela APRILE et. al.

Basic information

Original name

Highly porous hybrid metallosilicate materials prepared by non-hydrolytic sol-gel: Hydrothermal stability and catalytic properties in ethanol dehydration

Authors

STÝSKALÍK, Aleš (203 Czech Republic, guarantor, belonging to the institution), Imene KORDOGHLI, Claude POLEUNIS, Arnaud DELCORTE, Carmela APRILE, Luca FUSARO and Damien P. DEBECKER

Edition

Microporous and Mesoporous Materials, Amsterdam, Elsevier, 2020, 1387-1811

Other information

Language

English

Type of outcome

Článek v odborném periodiku

Field of Study

10402 Inorganic and nuclear chemistry

Country of publisher

Netherlands

Confidentiality degree

není předmětem státního či obchodního tajemství

References:

URL

Impact factor

Impact factor: 5.455

RIV identification code

RIV/00216224:14310/20:00116885

Organization unit

Faculty of Science

DOI

http://dx.doi.org/10.1016/j.micromeso.2020.110028

UT WoS

000517854500005

Keywords in English

Non-hydrolytic sol-gel; Hybrid metallosilicate; Hydrothermal stability; Heterogeneous catalysis; Ethanol dehydration

Abstract

V originále

Herein, we present novel phenylene- and xylylene-bridged silica and metallosilicate materials prepared by non-hydrolytic sol-gel. The hybrid silica are highly porous, chemically similar to periodic mesoporous organosilica (PMO), but amorphous without any pore ordering. Analogous hybrid metallosilicates are obtained by directly incorporating Al, Nb, or Sn in the hybrid silica framework. Exhibiting open texture, surface acidity and tunable hydrophobicity, these materials are excellent candidates for catalytic alcohol dehydration reactions. The gas-phase hydrothermal and thermal stability of these materials is examined. While the hybrid silica is expectedly stable, a stark decrease in stability is observed for phenylene bridged silsesquioxanes upon metal introduction. The extent of the hydrolytic Si-C(sp(2)) bond cleavage is quantitatively followed by Si-29 MAS NMR, TG analysis, and GC-FID analysis of effluent coming from samples exposed to water vapor. Two important features affecting the hydrothermal and thermal stability are identified: (i) the homogeneity of metal dispersion within the silica matrix, and (ii) the electronegativity of the incorporated metal. The stability of hybrid metallosilicates is significantly improved by replacing the phenylene bridges with xylylene bridges, due to the presence of more stable Si-C(sp(3)) bonds. Interestingly, the latter hybrid metallosilicate proves to be an active catalyst for the dehydration of ethanol to ethylene. Unlike the other hybrid materials presented here, it reaches high ethylene yields without undergoing degradation and deactivation.

Links

LQ1601, research and development project

Name: CEITEC 2020 (Acronym: CEITEC2020)

Investor: Ministry of Education, Youth and Sports of the CR

90043, large research infrastructures

Name: CIISB

Citovat

STÝSKALÍK, Aleš, Imene KORDOGHLI, Claude POLEUNIS, Arnaud DELCORTE, Carmela APRILE, Luca FUSARO and Damien P. DEBECKER. Highly porous hybrid metallosilicate materials prepared by non-hydrolytic sol-gel: Hydrothermal stability and catalytic properties in ethanol dehydration. Microporous and Mesoporous Materials. Amsterdam: Elsevier, 2020, vol. 297, MAY 1 2020, p. 1-13. ISSN 1387-1811. Available from: https://dx.doi.org/10.1016/j.micromeso.2020.110028.

@article{1691036,
   author = {Stýskalík, Aleš and Kordoghli, Imene and Poleunis, Claude and Delcorte, Arnaud and Aprile, Carmela and Fusaro, Luca and Debecker, Damien P.},
   article_location = {Amsterdam},
   article_number = {MAY 1 2020},
   doi = {http://dx.doi.org/10.1016/j.micromeso.2020.110028},
   keywords = {Non-hydrolytic sol-gel; Hybrid metallosilicate; Hydrothermal stability; Heterogeneous catalysis; Ethanol dehydration},
   language = {eng},
   issn = {1387-1811},
   journal = {Microporous and Mesoporous Materials},
   title = {Highly porous hybrid metallosilicate materials prepared by non-hydrolytic sol-gel: Hydrothermal stability and catalytic properties in ethanol dehydration},
   url = {https://doi.org/10.1016/j.micromeso.2020.110028},
   volume = {297},
   year = {2020}
}

TY  - JOUR
ID  - 1691036
AU  - Stýskalík, Aleš - Kordoghli, Imene - Poleunis, Claude - Delcorte, Arnaud - Aprile, Carmela - Fusaro, Luca - Debecker, Damien P.
PY  - 2020
TI  - Highly porous hybrid metallosilicate materials prepared by non-hydrolytic sol-gel: Hydrothermal stability and catalytic properties in ethanol dehydration
JF  - Microporous and Mesoporous Materials
VL  - 297
IS  - MAY 1 2020
SP  - 1-13
EP  - 1-13
PB  - Elsevier
SN  - 13871811
KW  - Non-hydrolytic sol-gel
KW  - Hybrid metallosilicate
KW  - Hydrothermal stability
KW  - Heterogeneous catalysis
KW  - Ethanol dehydration
UR  - https://doi.org/10.1016/j.micromeso.2020.110028
L2  - https://doi.org/10.1016/j.micromeso.2020.110028
N2  - Herein, we present novel phenylene- and xylylene-bridged silica and metallosilicate materials prepared by non-hydrolytic sol-gel. The hybrid silica are highly porous, chemically similar to periodic mesoporous organosilica (PMO), but amorphous without any pore ordering. Analogous hybrid metallosilicates are obtained by directly incorporating Al, Nb, or Sn in the hybrid silica framework. Exhibiting open texture, surface acidity and tunable hydrophobicity, these materials are excellent candidates for catalytic alcohol dehydration reactions. The gas-phase hydrothermal and thermal stability of these materials is examined. While the hybrid silica is expectedly stable, a stark decrease in stability is observed for phenylene bridged silsesquioxanes upon metal introduction. The extent of the hydrolytic Si-C(sp(2)) bond cleavage is quantitatively followed by Si-29 MAS NMR, TG analysis, and GC-FID analysis of effluent coming from samples exposed to water vapor. Two important features affecting the hydrothermal and thermal stability are identified: (i) the homogeneity of metal dispersion within the silica matrix, and (ii) the electronegativity of the incorporated metal. The stability of hybrid metallosilicates is significantly improved by replacing the phenylene bridges with xylylene bridges, due to the presence of more stable Si-C(sp(3)) bonds. Interestingly, the latter hybrid metallosilicate proves to be an active catalyst for the dehydration of ethanol to ethylene. Unlike the other hybrid materials presented here, it reaches high ethylene yields without undergoing degradation and deactivation.
ER  -

STÝSKALÍK, Aleš, Imene KORDOGHLI, Claude POLEUNIS, Arnaud DELCORTE, Carmela APRILE, Luca FUSARO and Damien P. DEBECKER. Highly porous hybrid metallosilicate materials prepared by non-hydrolytic sol-gel: Hydrothermal stability and catalytic properties in ethanol dehydration. \textit{Microporous and Mesoporous Materials}. Amsterdam: Elsevier, 2020, vol.~297, MAY 1 2020, p.~1-13. ISSN~1387-1811. Available from: https://dx.doi.org/10.1016/j.micromeso.2020.110028.

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