Quantification of Brønsted Acid Sites in Zeolites by Water Desorption Thermogravimetry
Abstract
The many studies that have been conducted on water adsorption on zeolites were carried out in “adsorption” mode, from adsorption isotherms or single-point measurements, with the samples being first degassed at high temperature, and then exposed to water vapor at variable partial pressure. Here, we report Thermogravimetric Analysis (TGA) studies of HZSM-5 saturated with water at room temperature, thus studying water adsorption in “desorption” mode. In this work, TGA was used to ascertain the amount of water remaining as a function of the pretreatment temperature, and to identify the temperature at which one water molecule per framework Al atom persists. Solid-state 1H NMR spectroscopy, combined with molecular modeling, provided evidence for water molecules hydrogen bonded to Brønsted acid sites and formation of oxonium species for distinct water per framework Al atom. TGA is shown to be a simple and expeditious technique to measure the number of Brønsted acid sites in aluminosilicate zeolites, with advantages over the traditional methods of IR or TPD of dangerous adsorbed ammonia or pyridine. TGA of adsorbed water also provides information on the water clusters formed at the acid sites of HZSM-5, which are proportional to the number of acid sites.
- Authors:
-
[1];
[2];
[4];
[5];
[1];
[1]
- University of Aveiro (Portugal)
- University of Aveiro (Portugal); BP Amoco Chemical Company Petrochemicals Technology, Naperville, IL (United States)
- BP Petrochemicals Technology, Hull (United Kingdom)
- Argonne National Lab. (ANL), Lemont, IL (United States)
- University of Coimbra (Portugal); Instituto de Ciências Nucleares Aplicadas à Saúde, Pólo das Ciâncias da Saúde, Coimbra (Portugal)
- Publication Date:
- Research Org.:
- Argonne National Lab. (ANL), Argonne, IL (United States)
- Sponsoring Org.:
- BP America; CICECO Aveiro Institute of Materials; Midwest Integrated Center for Computational Materials (MICCoM); European Regional Development Fund (FEDER); Fundação para a Ciência e a Tecnologia (FCT); USDOE Office of Science (SC), Basic Energy Sciences (BES). Materials Sciences & Engineering Division; USDOE Office of Energy Efficiency and Renewable Energy (EERE), Transportation Office. Fuel Cell Technologies Office
- OSTI Identifier:
- 1774788
- Grant/Contract Number:
- AC02-06CH11357
- Resource Type:
- Accepted Manuscript
- Journal Name:
- European Journal of Inorganic Chemistry
- Additional Journal Information:
- Journal Volume: 2020; Journal Issue: 19; Journal ID: ISSN 1434-1948
- Publisher:
- ChemPubSoc Europe
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; acidity; ZSM-5; thermogravimetry; water clusters; zeolites
Citation Formats
Bornes, Carlos, Amelse, Jeffrey A., Peacock, Mark, Marshall, Christopher L., Schwartz, Michael M., Geraldes, Carlos F. G. C., Rocha, João, and Mafra, Luis. Quantification of Brønsted Acid Sites in Zeolites by Water Desorption Thermogravimetry. United States: N. p., 2020.
Web. doi:10.1002/ejic.202000050.
Bornes, Carlos, Amelse, Jeffrey A., Peacock, Mark, Marshall, Christopher L., Schwartz, Michael M., Geraldes, Carlos F. G. C., Rocha, João, & Mafra, Luis. Quantification of Brønsted Acid Sites in Zeolites by Water Desorption Thermogravimetry. United States. https://doi.org/10.1002/ejic.202000050
Bornes, Carlos, Amelse, Jeffrey A., Peacock, Mark, Marshall, Christopher L., Schwartz, Michael M., Geraldes, Carlos F. G. C., Rocha, João, and Mafra, Luis. Tue .
"Quantification of Brønsted Acid Sites in Zeolites by Water Desorption Thermogravimetry". United States. https://doi.org/10.1002/ejic.202000050. https://www.osti.gov/servlets/purl/1774788.
@article{osti_1774788,
title = {Quantification of Brønsted Acid Sites in Zeolites by Water Desorption Thermogravimetry},
author = {Bornes, Carlos and Amelse, Jeffrey A. and Peacock, Mark and Marshall, Christopher L. and Schwartz, Michael M. and Geraldes, Carlos F. G. C. and Rocha, João and Mafra, Luis},
abstractNote = {The many studies that have been conducted on water adsorption on zeolites were carried out in “adsorption” mode, from adsorption isotherms or single-point measurements, with the samples being first degassed at high temperature, and then exposed to water vapor at variable partial pressure. Here, we report Thermogravimetric Analysis (TGA) studies of HZSM-5 saturated with water at room temperature, thus studying water adsorption in “desorption” mode. In this work, TGA was used to ascertain the amount of water remaining as a function of the pretreatment temperature, and to identify the temperature at which one water molecule per framework Al atom persists. Solid-state 1H NMR spectroscopy, combined with molecular modeling, provided evidence for water molecules hydrogen bonded to Brønsted acid sites and formation of oxonium species for distinct water per framework Al atom. TGA is shown to be a simple and expeditious technique to measure the number of Brønsted acid sites in aluminosilicate zeolites, with advantages over the traditional methods of IR or TPD of dangerous adsorbed ammonia or pyridine. TGA of adsorbed water also provides information on the water clusters formed at the acid sites of HZSM-5, which are proportional to the number of acid sites.},
doi = {10.1002/ejic.202000050},
journal = {European Journal of Inorganic Chemistry},
number = 19,
volume = 2020,
place = {United States},
year = {Tue Apr 07 00:00:00 EDT 2020},
month = {Tue Apr 07 00:00:00 EDT 2020}
}
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