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Title: Direct spectroscopic evidence for isolated silanols in SiOx/Al2O3 and their formation mechanism

Abstract

The preparation and unambiguous characterization of isolated Brønsted-acidic silanol species on silica–alumina catalysts presents a key challenge in the rational design of solid acid catalysts. In this report, atomic layer deposition (ALD) and liquid-phase preparation (chemical liquid deposition, CLD) are used to install the SiOx sites on Al2O3 catalysts using the same Si source (tetraethylorthosilicate, TEOS). The ALD-derived and CLD-derived SiOx sites are probed with dynamic nuclear polarization (DNP)-enhanced 29Si–29Si double-quantum/single-quantum (DQ/SQ) correlation NMR spectroscopy. The investigation reveals conclusively that the SiOx/Al2O3 material prepared by ALD and CLD, followed by calcination under an O2 stream, contains fully spatially isolated Si species, in contrast with those resulting from the calcination under static air, which is widely accepted as a postgrafting treatment for CLD. Insight into the formation mechanism of these sites is obtained via in situ monitoring of the TEOS + γ-Al2O3 reaction in an environmental diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) cell. Upon calcination, the DRIFTS spectra of SiOx/Al2O3 reveal a signature unambiguously assignable to isolated Brønsted-acidic silanol species. Surprisingly, the results of this study indicate that the method of preparing SiOx/Al2O3 catalysts is less important to the final structure of the silanol sites than the post-treatment conditions. Thismore » finding should greatly simplify the methods for synthesizing site-isolated, Brønsted-acidic SiOx/Al2O3 catalysts.« less

Authors:
 [1];  [2];  [3];  [1];  [1]
+ Show Author Affiliations
  1. Northwestern Univ., Evanston, IL (United States)
  2. Ames Lab., Ames, IA (United States)
  3. Ames Lab. and Iowa State Univ., Ames, IA (United States)
Publication Date:
Research Org.:
Ames Laboratory (AMES), Ames, IA (United States); Northwestern Univ., Evanston, IL (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1355896
Alternate Identifier(s):
OSTI ID: 1871001
Report Number(s):
IS-J-9316
Journal ID: ISSN 1932-7447
Grant/Contract Number:  
FG02-03ER154757; AC02-07CH11358; FG02-03ER15457
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Physical Chemistry. C
Additional Journal Information:
Journal Volume: 121; Journal Issue: 11; Journal ID: ISSN 1932-7447
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; atomic layer deposition; chemical liquid deposition; silica-alumina catalyst; DRIFTS; DNP-SENS

Citation Formats

Mouat, Aidan R., Kobayashi, Takeshi, Pruski, Marek, Marks, Tobin J., and Stair, Peter C. Direct spectroscopic evidence for isolated silanols in SiOx/Al2O3 and their formation mechanism. United States: N. p., 2017. Web. doi:10.1021/acs.jpcc.6b11196.
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Mouat, Aidan R., Kobayashi, Takeshi, Pruski, Marek, Marks, Tobin J., & Stair, Peter C. Direct spectroscopic evidence for isolated silanols in SiOx/Al2O3 and their formation mechanism. United States. https://doi.org/10.1021/acs.jpcc.6b11196
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Mouat, Aidan R., Kobayashi, Takeshi, Pruski, Marek, Marks, Tobin J., and Stair, Peter C. Mon . "Direct spectroscopic evidence for isolated silanols in SiOx/Al2O3 and their formation mechanism". United States. https://doi.org/10.1021/acs.jpcc.6b11196. https://www.osti.gov/servlets/purl/1355896.
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@article{osti_1355896,
title = {Direct spectroscopic evidence for isolated silanols in SiOx/Al2O3 and their formation mechanism},
author = {Mouat, Aidan R. and Kobayashi, Takeshi and Pruski, Marek and Marks, Tobin J. and Stair, Peter C.},
abstractNote = {The preparation and unambiguous characterization of isolated Brønsted-acidic silanol species on silica–alumina catalysts presents a key challenge in the rational design of solid acid catalysts. In this report, atomic layer deposition (ALD) and liquid-phase preparation (chemical liquid deposition, CLD) are used to install the SiOx sites on Al2O3 catalysts using the same Si source (tetraethylorthosilicate, TEOS). The ALD-derived and CLD-derived SiOx sites are probed with dynamic nuclear polarization (DNP)-enhanced 29Si–29Si double-quantum/single-quantum (DQ/SQ) correlation NMR spectroscopy. The investigation reveals conclusively that the SiOx/Al2O3 material prepared by ALD and CLD, followed by calcination under an O2 stream, contains fully spatially isolated Si species, in contrast with those resulting from the calcination under static air, which is widely accepted as a postgrafting treatment for CLD. Insight into the formation mechanism of these sites is obtained via in situ monitoring of the TEOS + γ-Al2O3 reaction in an environmental diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) cell. Upon calcination, the DRIFTS spectra of SiOx/Al2O3 reveal a signature unambiguously assignable to isolated Brønsted-acidic silanol species. Surprisingly, the results of this study indicate that the method of preparing SiOx/Al2O3 catalysts is less important to the final structure of the silanol sites than the post-treatment conditions. This finding should greatly simplify the methods for synthesizing site-isolated, Brønsted-acidic SiOx/Al2O3 catalysts.},
doi = {10.1021/acs.jpcc.6b11196},
journal = {Journal of Physical Chemistry. C},
number = 11,
volume = 121,
place = {United States},
year = {Mon Feb 27 00:00:00 EST 2017},
month = {Mon Feb 27 00:00:00 EST 2017}
}
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https://doi.org/10.1021/acs.jpcc.6b11196
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    Works referencing / citing this record:

    Shedding light on the atomic-scale structure of amorphous silica-alumina and its Brønsted acid sites
    text, January 2019

    Shedding light on the atomic-scale structure of amorphous silica–alumina and its Brønsted acid sites
    journal, January 2019

    • Perras, Frédéric A.; Wang, Zichun; Kobayashi, Takeshi
    • Physical Chemistry Chemical Physics, Vol. 21, Issue 35
    • DOI: 10.1039/c9cp04099d

    Acidity enhancement through synergy of penta- and tetra-coordinated aluminum species in amorphous silica networks
    journal, January 2020

    Determining the Surface Structure of Silicated Alumina Catalysts via Isotopic Enrichment and Dynamic Nuclear Polarization Surface-Enhanced NMR Spectroscopy
    journal, October 2017

    • Rankin, Andrew G. M.; Webb, Paul B.; Dawson, Daniel M.
    • The Journal of Physical Chemistry C, Vol. 121, Issue 41
    • DOI: 10.1021/acs.jpcc.7b08137

    Acidity enhancement through synergy of penta- and tetra-coordinated aluminum species in amorphous silica networks
    journal, January 2020

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