Thermodynamic complexity of sulfated zirconia catalysts
Abstract
Here, a series of sulfated zirconia (SZ) catalysts were synthesized by immersion of amorphous zirconium hydroxide in sulfuric acid of various concentrations (1–5 N). Additionally, these samples were fully characterized by X-ray diffraction (XRD), thermogravimetric analysis and mass spectrometry (TGA-MS), and aqueous sulfuric acid immersion and high temperature oxide melt solution calorimetry. We investigated the enthalpies of the complex interactions between sulfur species and the zirconia surface (ΔHSZ) for the sulfated zirconia precursor (SZP), ranging from -109.46 ± 7.33 (1 N) to -42.50 ± 0.89 (4 N) kJ/mol S. ΔHSZ appears to be a roughly exponential function of sulfuric acid concentration. On the other hand, the enthalpy of SZ formation (ΔHf), becomes more exothermic linearly as sulfur surface coverage increases, from -147.90 ± 4.16 (2.14 nm-2) to -317.03 ± 4.20 (2.29 nm-2) kJ/mol S, indicating formation of energetically more stable polysulfate species.
- Authors:
-
- East China University of Science and Technology, Shanghai (China); Univ. of California, Davis, CA (United States)
- Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
- Univ. of California, Davis, CA (United States)
- East China University of Science and Technology, Shanghai (China)
- Washington State Univ., Pullman, WA (United States)
- Publication Date:
- Research Org.:
- Los Alamos National Laboratory (LANL), Los Alamos, NM (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES)
- OSTI Identifier:
- 1467326
- Alternate Identifier(s):
- OSTI ID: 1359263
- Report Number(s):
- LA-UR-17-24705
Journal ID: ISSN 0021-9517
- Grant/Contract Number:
- AC52-06NA25396; FG02-05ER15667
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Journal of Catalysis
- Additional Journal Information:
- Journal Volume: 342; Journal Issue: C; Journal ID: ISSN 0021-9517
- Publisher:
- Elsevier
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Sulfated zirconia; Enthalpy of formation; Heterogeneous catalysis; Thermodynamics; Calorimetry; Olefins conversion; Stability and activity
Citation Formats
Liu, Naiwang, Guo, Xiaofeng, Navrotsky, Alexandra, Shi, Li, and Wu, Di. Thermodynamic complexity of sulfated zirconia catalysts. United States: N. p., 2016.
Web. doi:10.1016/j.jcat.2016.08.001.
Liu, Naiwang, Guo, Xiaofeng, Navrotsky, Alexandra, Shi, Li, & Wu, Di. Thermodynamic complexity of sulfated zirconia catalysts. United States. https://doi.org/10.1016/j.jcat.2016.08.001
Liu, Naiwang, Guo, Xiaofeng, Navrotsky, Alexandra, Shi, Li, and Wu, Di. Fri .
"Thermodynamic complexity of sulfated zirconia catalysts". United States. https://doi.org/10.1016/j.jcat.2016.08.001. https://www.osti.gov/servlets/purl/1467326.
@article{osti_1467326,
title = {Thermodynamic complexity of sulfated zirconia catalysts},
author = {Liu, Naiwang and Guo, Xiaofeng and Navrotsky, Alexandra and Shi, Li and Wu, Di},
abstractNote = {Here, a series of sulfated zirconia (SZ) catalysts were synthesized by immersion of amorphous zirconium hydroxide in sulfuric acid of various concentrations (1–5 N). Additionally, these samples were fully characterized by X-ray diffraction (XRD), thermogravimetric analysis and mass spectrometry (TGA-MS), and aqueous sulfuric acid immersion and high temperature oxide melt solution calorimetry. We investigated the enthalpies of the complex interactions between sulfur species and the zirconia surface (ΔHSZ) for the sulfated zirconia precursor (SZP), ranging from -109.46 ± 7.33 (1 N) to -42.50 ± 0.89 (4 N) kJ/mol S. ΔHSZ appears to be a roughly exponential function of sulfuric acid concentration. On the other hand, the enthalpy of SZ formation (ΔHf), becomes more exothermic linearly as sulfur surface coverage increases, from -147.90 ± 4.16 (2.14 nm-2) to -317.03 ± 4.20 (2.29 nm-2) kJ/mol S, indicating formation of energetically more stable polysulfate species.},
doi = {10.1016/j.jcat.2016.08.001},
journal = {Journal of Catalysis},
number = C,
volume = 342,
place = {United States},
year = {Fri Aug 26 00:00:00 EDT 2016},
month = {Fri Aug 26 00:00:00 EDT 2016}
}
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