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

Journal Article · · Catalysts
DOI:https://doi.org/10.3390/catal8070292· OSTI ID:1504924
 [1];  [1];  [1];  [1];  [1];  [1];  [1]
  1. Univ. of Pennsylvania, Philadelphia, PA (United States)
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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.

Research Organization:
Energy Frontier Research Centers (EFRC) (United States). Catalysis Center for Energy Innovation (CCEI); Univ. of Delaware, Newark, DE (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
Grant/Contract Number:
SC0001004
OSTI ID:
1504924
Journal Information:
Catalysts, Vol. 8, Issue 7; ISSN 2073-4344
Publisher:
MDPICopyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 14 works
Citation information provided by
Web of Science

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Cited By (2)

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

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Related Subjects

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