Acidity-reactivity relationships in catalytic esterification over ammonium sulfate-derived sulfated zirconia

Abdallah I.M. Rabee, Gamal A.H. Mekhemer, Amin Osatiashtiani, Mark A. Isaacs, Adam F. Lee, Karen Wilson*, Mohamed I. Zaki

*Corresponding author for this work

Research output: Contribution to journalSpecial issue

Abstract

New insight was gained into the acidity-reactivity relationships of sulfated zirconia (SZ) catalysts prepared via (NH4)2SO4 impregnation of Zr(OH)4 for propanoic acid esterification with methanol. A family of systematically related SZs was characterized by bulk and surface analyses including XRD, XPS, TGA-MS, N2 porosimetry, temperature-programmed propylamine decomposition, and FTIR of adsorbed pyridine, as well as methylbutynol (MBOH) as a reactive probe molecule. Increasing surface sulfation induces a transition from amphoteric character for the parent zirconia and low S loadings <1.7 wt %, evidenced by MBOH conversion to 3-hydroxy-3-methyl-2-butanone, methylbutyne and acetone, with higher S loadings resulting in strong Brønsted-Lewis acid pairs upon completion of the sulfate monolayer, which favored MBOH conversion to prenal. Catalytic activity for propanoic acid esterification directly correlated with acid strength determined from propylamine decomposition, coincident with the formation of Brønsted-Lewis acid pairs identified by MBOH reactive titration. Monodispersed bisulfate species are likely responsible for superacidity at intermediate sulfur loadings.

Original languageEnglish
Article number204
JournalCatalysts
Volume7
Issue number7
DOIs
Publication statusPublished - 5 Jul 2017

Fingerprint

Propylamines
Lewis Acids
ammonium sulfates
Esterification
Ammonium Sulfate
zirconium oxides
Acidity
acidity
Zirconia
reactivity
Decomposition
acids
Acids
Acetone
Titration
Sulfur
Impregnation
Sulfates
Methanol
Monolayers

Bibliographical note

© 2017 by the authors. Licensee MDPI, Basel, Switzerland. This article is an open access article distributed under the terms and conditions of the Creative Commons Attribution (CC BY) license (http://creativecommons.org/licenses/by/4.0/).

Funding: Alexander von Humboldt foundation (Bonn); EPSRC (EP/K000616/2, EP/G007594/4, EP/G007594/2 and EP/K036548/2); Royal Society (Industry Fellowship).

Keywords

  • esterification
  • IR
  • solid acid
  • sulfated zirconia
  • XPS
  • zirconia

Cite this

Rabee, A. I. M., Mekhemer, G. A. H., Osatiashtiani, A., Isaacs, M. A., Lee, A. F., Wilson, K., & Zaki, M. I. (2017). Acidity-reactivity relationships in catalytic esterification over ammonium sulfate-derived sulfated zirconia. Catalysts, 7(7), [204]. https://doi.org/10.3390/catal7070204
Rabee, Abdallah I.M. ; Mekhemer, Gamal A.H. ; Osatiashtiani, Amin ; Isaacs, Mark A. ; Lee, Adam F. ; Wilson, Karen ; Zaki, Mohamed I. / Acidity-reactivity relationships in catalytic esterification over ammonium sulfate-derived sulfated zirconia. In: Catalysts. 2017 ; Vol. 7, No. 7.
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Acidity-reactivity relationships in catalytic esterification over ammonium sulfate-derived sulfated zirconia. / Rabee, Abdallah I.M.; Mekhemer, Gamal A.H.; Osatiashtiani, Amin; Isaacs, Mark A.; Lee, Adam F.; Wilson, Karen; Zaki, Mohamed I.

In: Catalysts, Vol. 7, No. 7, 204, 05.07.2017.

Research output: Contribution to journalSpecial issue

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AU - Osatiashtiani, Amin

AU - Isaacs, Mark A.

AU - Lee, Adam F.

AU - Wilson, Karen

AU - Zaki, Mohamed I.

N1 - © 2017 by the authors. Licensee MDPI, Basel, Switzerland. This article is an open access article distributed under the terms and conditions of the Creative Commons Attribution (CC BY) license (http://creativecommons.org/licenses/by/4.0/). Funding: Alexander von Humboldt foundation (Bonn); EPSRC (EP/K000616/2, EP/G007594/4, EP/G007594/2 and EP/K036548/2); Royal Society (Industry Fellowship).

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N2 - New insight was gained into the acidity-reactivity relationships of sulfated zirconia (SZ) catalysts prepared via (NH4)2SO4 impregnation of Zr(OH)4 for propanoic acid esterification with methanol. A family of systematically related SZs was characterized by bulk and surface analyses including XRD, XPS, TGA-MS, N2 porosimetry, temperature-programmed propylamine decomposition, and FTIR of adsorbed pyridine, as well as methylbutynol (MBOH) as a reactive probe molecule. Increasing surface sulfation induces a transition from amphoteric character for the parent zirconia and low S loadings <1.7 wt %, evidenced by MBOH conversion to 3-hydroxy-3-methyl-2-butanone, methylbutyne and acetone, with higher S loadings resulting in strong Brønsted-Lewis acid pairs upon completion of the sulfate monolayer, which favored MBOH conversion to prenal. Catalytic activity for propanoic acid esterification directly correlated with acid strength determined from propylamine decomposition, coincident with the formation of Brønsted-Lewis acid pairs identified by MBOH reactive titration. Monodispersed bisulfate species are likely responsible for superacidity at intermediate sulfur loadings.

AB - New insight was gained into the acidity-reactivity relationships of sulfated zirconia (SZ) catalysts prepared via (NH4)2SO4 impregnation of Zr(OH)4 for propanoic acid esterification with methanol. A family of systematically related SZs was characterized by bulk and surface analyses including XRD, XPS, TGA-MS, N2 porosimetry, temperature-programmed propylamine decomposition, and FTIR of adsorbed pyridine, as well as methylbutynol (MBOH) as a reactive probe molecule. Increasing surface sulfation induces a transition from amphoteric character for the parent zirconia and low S loadings <1.7 wt %, evidenced by MBOH conversion to 3-hydroxy-3-methyl-2-butanone, methylbutyne and acetone, with higher S loadings resulting in strong Brønsted-Lewis acid pairs upon completion of the sulfate monolayer, which favored MBOH conversion to prenal. Catalytic activity for propanoic acid esterification directly correlated with acid strength determined from propylamine decomposition, coincident with the formation of Brønsted-Lewis acid pairs identified by MBOH reactive titration. Monodispersed bisulfate species are likely responsible for superacidity at intermediate sulfur loadings.

KW - esterification

KW - IR

KW - solid acid

KW - sulfated zirconia

KW - XPS

KW - zirconia

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