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Title: Reduction of Propionic Acid over a Pd-Promoted ReO x/SiO 2 Catalyst Probed by X-ray Absorption Spectroscopy and Transient Kinetic Analysis

Abstract

A Pd-promoted Re/SiO 2 catalyst was prepared by sequential impregnation and compared to monometallic Pd/SiO 2 and Re/SiO 2. All samples were characterized by electron microscopy, H 2 and CO chemisorption, H 2 temperature-programmed reduction, and in situ X-ray absorption spectroscopy at the Re L III and Pd K-edges. The samples were also tested in the reduction of propionic acid to 1-propanol and propionaldehyde at 433 K in 0.1–0.2 MPa H 2. Whereas monometallic Pd was inactive for carboxylic acid reduction, monometallic Re catalyzed aldehyde formation but only after high-temperature prereduction that produced metallic Re. When Pd was present with Re in a bimetallic catalyst, Pd facilitated the reduction of Re in H 2 to ~+4 oxidation state at modest temperatures, producing an active catalyst for the conversion of propionic acid to 1-propanol. Under the conditions of this study, the orders of reaction in propionic acid and H 2 were approximately zero and one, respectively. Transient kinetic analysis of the carboxylic acid reduction to alcohols revealed that at least 50% of the Re in the bimetallic catalyst participated in the catalytic reaction. In conclusion, the Pd is proposed to enhance the catalytic activity of the bimetallic catalyst by spilling overmore » hydrogen that can partially reduce Re and react with surface intermediates.« less

Authors:
 [1]; ORCiD logo [1]; ORCiD logo [2]; ORCiD logo [3];  [4];  [4]; ORCiD logo [2]; ORCiD logo [1]
  1. Univ. of Virginia, Charlottesville, VA (United States)
  2. Univ. College London, London (United Kingdom)
  3. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
  4. Brookhaven National Lab. (BNL), Upton, NY (United States)
Publication Date:
Research Org.:
Brookhaven National Lab. (BNL), Upton, NY (United States); Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1477954
Alternate Identifier(s):
OSTI ID: 1495984
Report Number(s):
BNL-209173-2018-JAAM
Journal ID: ISSN 2168-0485
Grant/Contract Number:  
SC0012704; AC05-00OR22725
Resource Type:
Accepted Manuscript
Journal Name:
ACS Sustainable Chemistry & Engineering
Additional Journal Information:
Journal Volume: 6; Journal Issue: 9; Journal ID: ISSN 2168-0485
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; 1-Propanol; Carboxylic acid; Palladium; Propionaldehyde; Propionic acid; Rhenium; Transient kinetics; X-ray absorption spectroscopy

Citation Formats

Kammert, James D., Xie, Jiahan, Godfrey, Ian J., Unocic, Raymond R., Stavitski, Eli, Attenkofer, Klaus, Sankar, Gopinathan, and Davis, Robert J. Reduction of Propionic Acid over a Pd-Promoted ReOx/SiO2 Catalyst Probed by X-ray Absorption Spectroscopy and Transient Kinetic Analysis. United States: N. p., 2018. Web. doi:10.1021/acssuschemeng.8b02820.
Kammert, James D., Xie, Jiahan, Godfrey, Ian J., Unocic, Raymond R., Stavitski, Eli, Attenkofer, Klaus, Sankar, Gopinathan, & Davis, Robert J. Reduction of Propionic Acid over a Pd-Promoted ReOx/SiO2 Catalyst Probed by X-ray Absorption Spectroscopy and Transient Kinetic Analysis. United States. doi:10.1021/acssuschemeng.8b02820.
Kammert, James D., Xie, Jiahan, Godfrey, Ian J., Unocic, Raymond R., Stavitski, Eli, Attenkofer, Klaus, Sankar, Gopinathan, and Davis, Robert J. Thu . "Reduction of Propionic Acid over a Pd-Promoted ReOx/SiO2 Catalyst Probed by X-ray Absorption Spectroscopy and Transient Kinetic Analysis". United States. doi:10.1021/acssuschemeng.8b02820. https://www.osti.gov/servlets/purl/1477954.
@article{osti_1477954,
title = {Reduction of Propionic Acid over a Pd-Promoted ReOx/SiO2 Catalyst Probed by X-ray Absorption Spectroscopy and Transient Kinetic Analysis},
author = {Kammert, James D. and Xie, Jiahan and Godfrey, Ian J. and Unocic, Raymond R. and Stavitski, Eli and Attenkofer, Klaus and Sankar, Gopinathan and Davis, Robert J.},
abstractNote = {A Pd-promoted Re/SiO2 catalyst was prepared by sequential impregnation and compared to monometallic Pd/SiO2 and Re/SiO2. All samples were characterized by electron microscopy, H2 and CO chemisorption, H2 temperature-programmed reduction, and in situ X-ray absorption spectroscopy at the Re LIII and Pd K-edges. The samples were also tested in the reduction of propionic acid to 1-propanol and propionaldehyde at 433 K in 0.1–0.2 MPa H2. Whereas monometallic Pd was inactive for carboxylic acid reduction, monometallic Re catalyzed aldehyde formation but only after high-temperature prereduction that produced metallic Re. When Pd was present with Re in a bimetallic catalyst, Pd facilitated the reduction of Re in H2 to ~+4 oxidation state at modest temperatures, producing an active catalyst for the conversion of propionic acid to 1-propanol. Under the conditions of this study, the orders of reaction in propionic acid and H2 were approximately zero and one, respectively. Transient kinetic analysis of the carboxylic acid reduction to alcohols revealed that at least 50% of the Re in the bimetallic catalyst participated in the catalytic reaction. In conclusion, the Pd is proposed to enhance the catalytic activity of the bimetallic catalyst by spilling over hydrogen that can partially reduce Re and react with surface intermediates.},
doi = {10.1021/acssuschemeng.8b02820},
journal = {ACS Sustainable Chemistry & Engineering},
number = 9,
volume = 6,
place = {United States},
year = {2018},
month = {7}
}

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