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Title: Revealing long- and short-range structural modifications within phosphorus-treated HZSM-5 zeolites by atom probe tomography, nuclear magnetic resonance and powder X-ray diffraction

Abstract

In this study, the average and the local structure of phosphorus-treated HZSM-5 zeolites were investigated by means of atom probe tomography, powder X-ray diffraction (at ambient and cryogenic temperatures) and 1H, 29Si, 27Al, and 31P magic angle spinning (MAS) solid state nuclear magnetic resonance (NMR) spectroscopy. Phosphatation to yield a product with P/Al ≤ 1 followed by thermal treatment leads to breaking of the Si–OH–Al bridging groups, and subsequent partial dealumination of the zeolite framework, as shown by the contraction of the orthorhombic unit-cell volume and by the loss of tetrahedral framework Al, as observed in the 27Al Multiple Quantum (MQ) MAS NMR spectrum. Most of the framework Al is present in an electronic environment distorted by the presence of phosphorus and appears not to be involved in classic Si–OH–Al Brønsted acid sites. The 31P MAS NMR signals indicate that phosphorus interacts with the zeolitic framework to locally form silico-aluminophosphate (SAPO) domains and the presence of a new kind of acidic site was confirmed by the resonance at ~8.6 ppm in the 1H MAS NMR spectra, attributed to P–OH groups. Increasing the phosphorus loading (P/Al >> 1) promotes further dealumination of the framework and cross-dehydroxylation between P–OH and Si–OH species,more » leading to the formation of a crystalline silicon orthophosphate phase. With decreasing Al content, the monoclinic HZSM-5 structure becomes preferred, especially at 85 K where the strain relaxation is higher. Nevertheless, the presence of a higher amount of silicophosphate impurities hinders the low-temperature strain release of the framework, indicating that some of these species are localized in the zeolite pores and contribute to the strain build up.« less

Authors:
ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [2]; ORCiD logo [2]; ORCiD logo [3]; ORCiD logo [2]; ORCiD logo [1]; ORCiD logo [4]
  1. Utrecht University (The Netherlands). Inorganic Chemistry and Catalysis
  2. Utrecht University (The Netherlands). NMR Spectroscopy, Bijvoet Center for Biomolecular Research
  3. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Center for Nanophase Materials Science (CNMS)
  4. Utrecht University (The Netherlands). Inorganic Chemistry and Catalysis; Albemarle Catalyst Company BV, Amsterdam (The Netherlands)
Publication Date:
Research Org.:
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Sponsoring Org.:
USDOE Office of Science (SC)
OSTI Identifier:
1482432
Grant/Contract Number:  
[AC05-00OR22725]
Resource Type:
Accepted Manuscript
Journal Name:
Physical Chemistry Chemical Physics. PCCP (Print)
Additional Journal Information:
[Journal Name: Physical Chemistry Chemical Physics. PCCP (Print); Journal Volume: 20; Journal Issue: 44]; Journal ID: ISSN 1463-9076
Publisher:
Royal Society of Chemistry
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 36 MATERIALS SCIENCE

Citation Formats

Danisi, Rosa Micaela, Schmidt, Joel E., Lucini Paioni, Alessandra, Houben, Klaartje, Poplawsky, Jonathan D., Baldus, Marc, Weckhuysen, Bert M., and Vogt, Eelco T. C. Revealing long- and short-range structural modifications within phosphorus-treated HZSM-5 zeolites by atom probe tomography, nuclear magnetic resonance and powder X-ray diffraction. United States: N. p., 2018. Web. doi:10.1039/c8cp03828g.
Danisi, Rosa Micaela, Schmidt, Joel E., Lucini Paioni, Alessandra, Houben, Klaartje, Poplawsky, Jonathan D., Baldus, Marc, Weckhuysen, Bert M., & Vogt, Eelco T. C. Revealing long- and short-range structural modifications within phosphorus-treated HZSM-5 zeolites by atom probe tomography, nuclear magnetic resonance and powder X-ray diffraction. United States. doi:10.1039/c8cp03828g.
Danisi, Rosa Micaela, Schmidt, Joel E., Lucini Paioni, Alessandra, Houben, Klaartje, Poplawsky, Jonathan D., Baldus, Marc, Weckhuysen, Bert M., and Vogt, Eelco T. C. Thu . "Revealing long- and short-range structural modifications within phosphorus-treated HZSM-5 zeolites by atom probe tomography, nuclear magnetic resonance and powder X-ray diffraction". United States. doi:10.1039/c8cp03828g. https://www.osti.gov/servlets/purl/1482432.
@article{osti_1482432,
title = {Revealing long- and short-range structural modifications within phosphorus-treated HZSM-5 zeolites by atom probe tomography, nuclear magnetic resonance and powder X-ray diffraction},
author = {Danisi, Rosa Micaela and Schmidt, Joel E. and Lucini Paioni, Alessandra and Houben, Klaartje and Poplawsky, Jonathan D. and Baldus, Marc and Weckhuysen, Bert M. and Vogt, Eelco T. C.},
abstractNote = {In this study, the average and the local structure of phosphorus-treated HZSM-5 zeolites were investigated by means of atom probe tomography, powder X-ray diffraction (at ambient and cryogenic temperatures) and 1H, 29Si, 27Al, and 31P magic angle spinning (MAS) solid state nuclear magnetic resonance (NMR) spectroscopy. Phosphatation to yield a product with P/Al ≤ 1 followed by thermal treatment leads to breaking of the Si–OH–Al bridging groups, and subsequent partial dealumination of the zeolite framework, as shown by the contraction of the orthorhombic unit-cell volume and by the loss of tetrahedral framework Al, as observed in the 27Al Multiple Quantum (MQ) MAS NMR spectrum. Most of the framework Al is present in an electronic environment distorted by the presence of phosphorus and appears not to be involved in classic Si–OH–Al Brønsted acid sites. The 31P MAS NMR signals indicate that phosphorus interacts with the zeolitic framework to locally form silico-aluminophosphate (SAPO) domains and the presence of a new kind of acidic site was confirmed by the resonance at ~8.6 ppm in the 1H MAS NMR spectra, attributed to P–OH groups. Increasing the phosphorus loading (P/Al >> 1) promotes further dealumination of the framework and cross-dehydroxylation between P–OH and Si–OH species, leading to the formation of a crystalline silicon orthophosphate phase. With decreasing Al content, the monoclinic HZSM-5 structure becomes preferred, especially at 85 K where the strain relaxation is higher. Nevertheless, the presence of a higher amount of silicophosphate impurities hinders the low-temperature strain release of the framework, indicating that some of these species are localized in the zeolite pores and contribute to the strain build up.},
doi = {10.1039/c8cp03828g},
journal = {Physical Chemistry Chemical Physics. PCCP (Print)},
number = [44],
volume = [20],
place = {United States},
year = {2018},
month = {8}
}

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