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Title: Molecular structure and sour gas surface chemistry of supported K2O/WO3/Al2O3 catalysts

Abstract

Molecular structures of the unpromoted and K2O-promoted supported WO3/Al2O3 catalysts were studied with in situ Raman and UV–vis spectroscopy. In situ Raman spectra revealed that supported 20% WO3/Al2O3 corresponds to near monolayer coverage of isolated and oligomeric surface WOx species on Al2O3. Above monolayer surface WOx coverage (21% WO3/Al2O3), crystalline WO3 nanoparticles are also present. The addition of K2O to the supported WO3/Al2O3 catalyst increased the concentration of isolated surface WOx species and did not form K2WO4 nanoparticles. The reducibility of the tungsten oxide structures depends on their structures (2D or 3D) and the K2O promoter. Their interaction with acidic CO2 and SO2 gases was also investigated. Adsorption of CO2 creates several surface carbonate species of varying acidity that were detected using a combination of in situ IR and mass spectroscopy. Adsorbed bicarbonate form on weakly basic surface sites on tungsten oxide monolayer WO3/Al2O3 catalyst as well as in the presence of low 2.5% K2O loading. At high 5% K2O loading, the presence of the strong surface basic sites yields adsorbed carbonates. After SO2 pretreatment, however, new strongly adsorbed sulfate appears on the surface that inhibits CO2 adsorption.

Authors:
 [1];  [1];  [1];  [1];  [1];  [2];  [3];  [1]; ORCiD logo [4];  [1]
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  1. Lehigh Univ., Bethlehem, PA (United States). Dept. of Chemical and Biomolecular Engineering
  2. Brookhaven National Lab. (BNL), Upton, NY (United States). Center for Functional Nanomaterials (CFN)
  3. Brookhaven National Lab. (BNL), Upton, NY (United States). Center for Functional Nanomaterials (CFN); Univ. of Pennsylvania, Philadelphia, PA (United States). Materials Science and Engineering
  4. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Chemical Sciences Division; Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Center for Nanophase Materials Science (CNMS)
Publication Date:
Research Org.:
Brookhaven National Lab. (BNL), Upton, NY (United States); Energy Frontier Research Centers (EFRC) (United States). Center for Understanding and Control of Acid Gas-induced Evolution of Materials for Energy (UNCAGE-ME); Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1466585
Alternate Identifier(s):
OSTI ID: 1468086
Report Number(s):
BNL-207989-2018-JAAM
Journal ID: ISSN 0926-3373
Grant/Contract Number:  
SC0012704; AC05-00OR22725
Resource Type:
Accepted Manuscript
Journal Name:
Applied Catalysis B: Environmental
Additional Journal Information:
Journal Volume: 232; Journal Issue: C; Journal ID: ISSN 0926-3373
Publisher:
Elsevier
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; K2O WO3 Al2O3 catalysts; IR; Raman; UV-vis; TPR; DRIFT; CO2; SO2; in situ

Citation Formats

Zhu, Minghui, Li, Bin, Jehng, Jih-Mirn, Sharma, Lohit, Taborda, Julian, Zhang, Lihua, Stach, Eric, Wachs, Israel E., Wu, Zili, and Baltrusaitis, Jonas. Molecular structure and sour gas surface chemistry of supported K2O/WO3/Al2O3 catalysts. United States: N. p., 2018. Web. doi:10.1016/j.apcatb.2018.03.044.
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Zhu, Minghui, Li, Bin, Jehng, Jih-Mirn, Sharma, Lohit, Taborda, Julian, Zhang, Lihua, Stach, Eric, Wachs, Israel E., Wu, Zili, & Baltrusaitis, Jonas. Molecular structure and sour gas surface chemistry of supported K2O/WO3/Al2O3 catalysts. United States. https://doi.org/10.1016/j.apcatb.2018.03.044
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Zhu, Minghui, Li, Bin, Jehng, Jih-Mirn, Sharma, Lohit, Taborda, Julian, Zhang, Lihua, Stach, Eric, Wachs, Israel E., Wu, Zili, and Baltrusaitis, Jonas. Fri . "Molecular structure and sour gas surface chemistry of supported K2O/WO3/Al2O3 catalysts". United States. https://doi.org/10.1016/j.apcatb.2018.03.044. https://www.osti.gov/servlets/purl/1466585.
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@article{osti_1466585,
title = {Molecular structure and sour gas surface chemistry of supported K2O/WO3/Al2O3 catalysts},
author = {Zhu, Minghui and Li, Bin and Jehng, Jih-Mirn and Sharma, Lohit and Taborda, Julian and Zhang, Lihua and Stach, Eric and Wachs, Israel E. and Wu, Zili and Baltrusaitis, Jonas},
abstractNote = {Molecular structures of the unpromoted and K2O-promoted supported WO3/Al2O3 catalysts were studied with in situ Raman and UV–vis spectroscopy. In situ Raman spectra revealed that supported 20% WO3/Al2O3 corresponds to near monolayer coverage of isolated and oligomeric surface WOx species on Al2O3. Above monolayer surface WOx coverage (21% WO3/Al2O3), crystalline WO3 nanoparticles are also present. The addition of K2O to the supported WO3/Al2O3 catalyst increased the concentration of isolated surface WOx species and did not form K2WO4 nanoparticles. The reducibility of the tungsten oxide structures depends on their structures (2D or 3D) and the K2O promoter. Their interaction with acidic CO2 and SO2 gases was also investigated. Adsorption of CO2 creates several surface carbonate species of varying acidity that were detected using a combination of in situ IR and mass spectroscopy. Adsorbed bicarbonate form on weakly basic surface sites on tungsten oxide monolayer WO3/Al2O3 catalyst as well as in the presence of low 2.5% K2O loading. At high 5% K2O loading, the presence of the strong surface basic sites yields adsorbed carbonates. After SO2 pretreatment, however, new strongly adsorbed sulfate appears on the surface that inhibits CO2 adsorption.},
doi = {10.1016/j.apcatb.2018.03.044},
journal = {Applied Catalysis B: Environmental},
number = C,
volume = 232,
place = {United States},
year = {Fri Mar 16 00:00:00 EDT 2018},
month = {Fri Mar 16 00:00:00 EDT 2018}
}
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Journal Article:
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Publisher's Version of Record
https://doi.org/10.1016/j.apcatb.2018.03.044
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Cited by: 17 works
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Figures / Tables:

Figure 1 Figure 1: In situ UV-vis spectra of dehydrated 20% WO3/Al2O3, 21% WO3/Al2O3, 2.5% K2O/19.5% WO3/Al2O3 and 5% K2O/19% WO3/Al2O3 catalysts.
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    Works referencing / citing this record:

    Mesoporous amorphous Al 2 O 3 /crystalline WO 3 heterophase hybrids for electrocatalysis and gas sensing applications
    journal, January 2019

    • Zou, Yidong; Xi, Shibo; Bo, Tao
    • Journal of Materials Chemistry A, Vol. 7, Issue 38
    • DOI: 10.1039/c9ta08633a
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      Figures / Tables found in this record:

      Figure 1 (p. 8)figure
      Table 1 (p. 8)table
      Figure 2 (p. 10)figure
      Table 2 (p. 10)table
      Figure 3 (p. 11)figure
      Figure 4 (p. 13)figure
      Figure 5 (p. 14)figure
      Figure 6 (p. 15)figure
      Figure 7 (p. 17)figure
      Figure 8 (p. 18)figure
      Table 3 (p. 19)table
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