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Title: Thermodynamic complexity of sulfated zirconia catalysts

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 (ΔH SZ) 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 (ΔH f), 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:
 [1] ;  [2] ;  [3] ;  [4] ;  [5]
  1. East China University of Science and Technology, Shanghai (China); Univ. of California, Davis, CA (United States)
  2. Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
  3. Univ. of California, Davis, CA (United States)
  4. East China University of Science and Technology, Shanghai (China)
  5. Washington State Univ., Pullman, WA (United States)
Publication Date:
Report Number(s):
LA-UR-17-24705
Journal ID: ISSN 0021-9517
Grant/Contract Number:
AC52-06NA25396; FG02-05ER15667
Type:
Accepted Manuscript
Journal Name:
Journal of Catalysis
Additional Journal Information:
Journal Volume: 342; Journal Issue: C; Journal ID: ISSN 0021-9517
Publisher:
Elsevier
Research Org:
Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
Sponsoring Org:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
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
OSTI Identifier:
1467326
Alternate Identifier(s):
OSTI ID: 1359263

Liu, Naiwang, Guo, Xiaofeng, Navrotsky, Alexandra, Shi, Li, and Wu, Di. Thermodynamic complexity of sulfated zirconia catalysts. United States: N. p., 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. doi:10.1016/j.jcat.2016.08.001.
Liu, Naiwang, Guo, Xiaofeng, Navrotsky, Alexandra, Shi, Li, and Wu, Di. 2016. "Thermodynamic complexity of sulfated zirconia catalysts". United States. doi: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 = {2016},
month = {8}
}