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Title: Revealing the Mechanistic Details for the Selective Deoxygenation of Carboxylic Acids over Dynamic MoO 3 Catalysts
The selective activation of renewable carboxylic acids could enable the formation of a variety of highly valuable renewable products, including surfactants, valuable dienes, and renewable hydrogen carriers. A kinetic study is performed to enhance understanding of the selective deoxygenation of carboxylic acid on promoted MoO3 at mild temperatures. Although several studies indicate that deoxygenation of oxygenated biomass-derived compounds on MoO3 occurs via a reverse Mars−van Krevelen mechanism, this study suggests that the deoxygenation of pentanoic acid (PA) on an oxygen vacancy can also be explained by a Langmuir−Hinshelwood mechanism. A detailed analysis of the experimental data indicates that the incorporation of Pt on MoO3 shifts the reaction order with respect to hydrogen from 1 to 0.5 at a low partial pressure of PA. We reveal that the rate-determining step (RDS) shifts upon the incorporation of Pt from H2 dissociation to H addition to adsorbed acid molecules. We further illustrate how the RDS can shift as a function of PA coverage. The inhibition effect of PA and its possible causes are discussed for both MoO3 and 0.05 wt % Pt/MoO3 catalysts. Here, we decouple promoter effects from the creation of highly active sites located at the Pt/MoO3 interface. The nature of the active site involved upon Pt incorporation is also studied by separating Pt from MoO3 at a controlled distance using carbon nanotubes as hydrogen bridges, confirming that the kinetically relevant role of Pt is to serve as a promoter of the MoO3.  more » « less
Award ID(s):
1653935
PAR ID:
10428880
Author(s) / Creator(s):
; ; ; ;
Date Published:
Journal Name:
ACS Catalysis
ISSN:
2155-5435
Page Range / eLocation ID:
8455 to 8466
Format(s):
Medium: X
Sponsoring Org:
National Science Foundation
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