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Title: A Characterization Study of Reactive Sites in ALD-Synthesized WOx/ZrO2 Catalysts

Abstract

A series of ZrO2-supported WOx catalysts were prepared using atomic layer deposition (ALD) with W(CO)6, and were then compared to a WOx/ZrO2 catalyst prepared via conventional impregnation. The types of sites present in these samples were characterized using temperature-programmed desorption/thermogravimetric analysis (TPD-TGA) measurements with 2-propanol and 2-propanamine. Weight changes showed that the WOx catalysts grew at a rate of 8.8 × 1017 W atoms/m2 per cycle. Scanning transmission electron microscopy/energy-dispersive spectroscopy (STEM-EDS) indicated that WOx was deposited uniformly, as did the 2-propanol TPD-TGA results, which showed that ZrO2 was completely covered after five ALD cycles. Furthermore, 2-propanamine TPD-TGA demonstrated the presence of three types of catalytic sites, the concentrations of which changed with the number of ALD cycles: dehydrogenation sites associated with ZrO2, Brønsted-acid sites associated with monolayer WOx clusters, and oxidation sites associated with higher WOx coverages. The Brønsted sites were not formed via ALD of WOx on SiO2. The reaction rates for 2-propanol dehydration were correlated with the concentration of Brønsted sites. While TPD-TGA of 2-propanamine did not differentiate the strength of Brønsted-acid sites, H–D exchange between D2O and either toluene or chlorobenzene indicated that the Brønsted sites in tungstated zirconia were much weaker than those in H-ZSM-5more » zeolites.« less

Authors:
 [1];  [1];  [1];  [1];  [1];  [1];  [1]
  1. Univ. of Pennsylvania, Philadelphia, PA (United States)
Publication Date:
Research Org.:
Energy Frontier Research Centers (EFRC) (United States). Catalysis Center for Energy Innovation (CCEI); Univ. of Delaware, Newark, DE (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1504924
Grant/Contract Number:  
SC0001004
Resource Type:
Accepted Manuscript
Journal Name:
Catalysts
Additional Journal Information:
Journal Volume: 8; Journal Issue: 7; Journal ID: ISSN 2073-4344
Publisher:
MDPI
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; solid acids; metal-oxide catalysts; tungstated zirconia; atomic layer deposition; Brønsted-acid strength; temperature-programmed desorption/thermogravimetric analysis; H–D exchange

Citation Formats

Wang, Cong, Mao, Xinyu, Lee, Jennifer D., Onn, Tzia Ming, Yeh, Yu -Hao, Murray, Christopher B., and Gorte, Raymond J. A Characterization Study of Reactive Sites in ALD-Synthesized WOx/ZrO2 Catalysts. United States: N. p., 2018. Web. doi:10.3390/catal8070292.
Wang, Cong, Mao, Xinyu, Lee, Jennifer D., Onn, Tzia Ming, Yeh, Yu -Hao, Murray, Christopher B., & Gorte, Raymond J. A Characterization Study of Reactive Sites in ALD-Synthesized WOx/ZrO2 Catalysts. United States. https://doi.org/10.3390/catal8070292
Wang, Cong, Mao, Xinyu, Lee, Jennifer D., Onn, Tzia Ming, Yeh, Yu -Hao, Murray, Christopher B., and Gorte, Raymond J. Thu . "A Characterization Study of Reactive Sites in ALD-Synthesized WOx/ZrO2 Catalysts". United States. https://doi.org/10.3390/catal8070292. https://www.osti.gov/servlets/purl/1504924.
@article{osti_1504924,
title = {A Characterization Study of Reactive Sites in ALD-Synthesized WOx/ZrO2 Catalysts},
author = {Wang, Cong and Mao, Xinyu and Lee, Jennifer D. and Onn, Tzia Ming and Yeh, Yu -Hao and Murray, Christopher B. and Gorte, Raymond J.},
abstractNote = {A series of ZrO2-supported WOx catalysts were prepared using atomic layer deposition (ALD) with W(CO)6, and were then compared to a WOx/ZrO2 catalyst prepared via conventional impregnation. The types of sites present in these samples were characterized using temperature-programmed desorption/thermogravimetric analysis (TPD-TGA) measurements with 2-propanol and 2-propanamine. Weight changes showed that the WOx catalysts grew at a rate of 8.8 × 1017 W atoms/m2 per cycle. Scanning transmission electron microscopy/energy-dispersive spectroscopy (STEM-EDS) indicated that WOx was deposited uniformly, as did the 2-propanol TPD-TGA results, which showed that ZrO2 was completely covered after five ALD cycles. Furthermore, 2-propanamine TPD-TGA demonstrated the presence of three types of catalytic sites, the concentrations of which changed with the number of ALD cycles: dehydrogenation sites associated with ZrO2, Brønsted-acid sites associated with monolayer WOx clusters, and oxidation sites associated with higher WOx coverages. The Brønsted sites were not formed via ALD of WOx on SiO2. The reaction rates for 2-propanol dehydration were correlated with the concentration of Brønsted sites. While TPD-TGA of 2-propanamine did not differentiate the strength of Brønsted-acid sites, H–D exchange between D2O and either toluene or chlorobenzene indicated that the Brønsted sites in tungstated zirconia were much weaker than those in H-ZSM-5 zeolites.},
doi = {10.3390/catal8070292},
journal = {Catalysts},
number = 7,
volume = 8,
place = {United States},
year = {Thu Jul 19 00:00:00 EDT 2018},
month = {Thu Jul 19 00:00:00 EDT 2018}
}

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Works referenced in this record:

Stoichiometric adsorption complexes in H-ZSM-5
journal, November 1988


Influence of composition and Cu impregnation method on the performance of Cu/CeO2/YSZ SOFC anodes
journal, March 2006


WOx/ZrO2 catalysts
journal, August 2004


Structural Determination of Bulk and Surface Tungsten Oxides with UV−vis Diffuse Reflectance Spectroscopy and Raman Spectroscopy
journal, September 2007

  • Ross-Medgaarden, Elizabeth I.; Wachs, Israel E.
  • The Journal of Physical Chemistry C, Vol. 111, Issue 41
  • DOI: 10.1021/jp074219c

Proton transfer to toluene in H-ZSM-5: TPD, IR, and NMR studies
journal, January 1988

  • Farneth, W. E.; Roe, D. C.; Kofke, T. J. Gricus
  • Langmuir, Vol. 4, Issue 1
  • DOI: 10.1021/la00079a028

Smart Pd Catalyst with Improved Thermal Stability Supported on High-Surface-Area LaFeO 3 Prepared by Atomic Layer Deposition
journal, January 2018

  • Onn, Tzia Ming; Monai, Matteo; Dai, Sheng
  • Journal of the American Chemical Society, Vol. 140, Issue 14
  • DOI: 10.1021/jacs.7b12900

A Study of Tetrahydrofurfuryl Alcohol to 1,5-Pentanediol Over Pt–WOx/C
journal, February 2018


Structural and Catalytic Characterization of Solid Acids Based on Zirconia Modified by Tungsten Oxide
journal, January 1999

  • Barton, David G.; Soled, Stuart L.; Meitzner, George D.
  • Journal of Catalysis, Vol. 181, Issue 1
  • DOI: 10.1006/jcat.1998.2269

Zn-Promoted H-ZSM-5 for Endothermic Reforming of n -Hexane at High Pressures
journal, March 2016

  • Yeh, Yu-Hao; Zhu, Shiyu; Staiber, Patrick
  • Industrial & Engineering Chemistry Research, Vol. 55, Issue 14
  • DOI: 10.1021/acs.iecr.6b00639

n-Pentane Isomerization over Pt/WOx/ZrO2 Catalysts: A 1H and 13C NMR Study
journal, February 2001

  • Filimonova, S. V.; Nosov, A. V.; Scheithauer, M.
  • Journal of Catalysis, Vol. 198, Issue 1
  • DOI: 10.1006/jcat.2000.3112

Atomic Layer Deposition of Tungsten Oxide for Solar Cell Application
journal, January 2014


New insights into the nature of the acidic catalytic active sites present in ZrO2-supported tungsten oxide catalysts
journal, May 2008


Isotopic and Chemical Titration of Acid Sites in Tungsten Oxide Domains Supported on Zirconia
journal, February 2001

  • Baertsch, Chelsey D.; Soled, Stuart L.; Iglesia, Enrique
  • The Journal of Physical Chemistry B, Vol. 105, Issue 7
  • DOI: 10.1021/jp003073d

Atomic Layer Deposition of WO3 Thin Films using W(CO)6 and O3 Precursors
journal, August 2012

  • Malm, Jari; Sajavaara, Timo; Karppinen, Maarit
  • Chemical Vapor Deposition, Vol. 18, Issue 7-9
  • DOI: 10.1002/cvde.201206986

Mechanism and kinetics of 1-dodecanol etherification over tungstated zirconia
journal, October 2017


High Pressure Cracking of n-Hexane Over H-ZSM-5
journal, February 2013


Studies on the Catalytic Activity of Zirconia Promoted with Sulfate, Iron, and Manganese
journal, January 1996

  • Wan, Kam T.; Khouw, Charles B.; Davis, Mark E.
  • Journal of Catalysis, Vol. 158, Issue 1
  • DOI: 10.1006/jcat.1996.0030

n-Pentane Isomerization Catalyzed by Fe- and Mn-Containing Tungstated Zirconia Characterized by Raman Spectroscopy
journal, April 2000

  • Scheithauer, M.; Jentoft, R. E.; Gates, B. C.
  • Journal of Catalysis, Vol. 191, Issue 2
  • DOI: 10.1006/jcat.1999.2771

Zeolite Catalysis: Water Can Dramatically Increase or Suppress Alkane C–H Bond Activation
journal, August 2014

  • Chen, Kuizhi; Damron, Joshua; Pearson, Carlie
  • ACS Catalysis, Vol. 4, Issue 9
  • DOI: 10.1021/cs500858d

Synthesis of solid superacid of tungsten oxide supported on zirconia and its catalytic action for reactions of butane and pentane
journal, January 1988

  • Hino, Makoto; Arata, Kazushi
  • Journal of the Chemical Society, Chemical Communications, Issue 18
  • DOI: 10.1039/c39880001259

An Examination of Brønsted Acid Sites in H-[Fe]ZSM-5 for Olefin Oligomerization and Adsorption
journal, August 2002


Nature of Catalytically Active Sites in the Supported WO 3 /ZrO 2 Solid Acid System: A Current Perspective
journal, February 2017


A Comparative Study of the Surface Structure, Acidity, and Catalytic Performance of Tungstated Zirconia Prepared from Crystalline Zirconia or Amorphous Zirconium Oxyhydroxide
journal, July 2006

  • Lebarbier, Vanessa; Clet, Guillaume; Houalla, Marwan
  • The Journal of Physical Chemistry B, Vol. 110, Issue 28
  • DOI: 10.1021/jp0571224

An examination of alkali-exchanged BEA zeolites as possible Lewis-acid catalysts
journal, May 2016


The effect of oxide acidity on HMF etherification
journal, January 2014

  • Luo, Jing; Yu, Jingye; Gorte, Raymond J.
  • Catal. Sci. Technol., Vol. 4, Issue 9
  • DOI: 10.1039/C4CY00563E

Adsorption and reaction properties of SnBEA, ZrBEA and H-BEA for the formation of p-xylene from DMF and ethylene
journal, January 2016

  • Yu, Jingye; Zhu, Shiyu; Dauenhauer, Paul J.
  • Catalysis Science & Technology, Vol. 6, Issue 14
  • DOI: 10.1039/C6CY00501B

Evidence for the Formation of W 5+ Centers and OH Groups upon Hydrogen Reduction of Platinum-Promoted Tungstated Zirconia Catalysts
journal, April 2003

  • Kuba, Stefan; Che, Michel; Grasselli, Robert K.
  • The Journal of Physical Chemistry B, Vol. 107, Issue 15
  • DOI: 10.1021/jp022313h

Works referencing / citing this record:

H-D Exchange of Simple Aromatics as a Measure of Brønsted-Acid Site Strengths in Solids
journal, September 2018


Atomic Layer Deposition for Preparing Isolated Co Sites on SiO2 for Ethane Dehydrogenation Catalysis
journal, January 2020