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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. doi: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. doi: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 = {2018},
month = {7}
}

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    Works referencing / citing this record:

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