Reduction of Propionic Acid over a Pd-Promoted ReOx/SiO2 Catalyst Probed by X-ray Absorption Spectroscopy and Transient Kinetic Analysis

doi:10.1021/acssuschemeng.8b02820

Title: Reduction of Propionic Acid over a Pd-Promoted ReO_x/SiO₂ Catalyst Probed by X-ray Absorption Spectroscopy and Transient Kinetic Analysis

Abstract

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. 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.

Authors:

Kammert, James D. ^[1];

^[1];

^[2];

^[3]; Stavitski, Eli ^[4]; Attenkofer, Klaus ^[4];

^[2];

^[1]

Univ. of Virginia, Charlottesville, VA (United States)
Univ. College London, London (United Kingdom)
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Brookhaven National Lab. (BNL), Upton, NY (United States)

Publication Date:: 2018-07-12

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)

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.

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                    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.

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                    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.

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@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. 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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DOI: 10.1021/acssuschemeng.8b02820

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Works referencing / citing this record:

Recent Developments of Heterogeneous Catalysts for Hydrogenation of Carboxylic Acids to their Corresponding Alcohols
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Tamura, Masazumi; Nakagawa, Yoshinao; Tomishige, Keiichi
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DOI: 10.1002/ajoc.201900667

Valorization of Biomass‐derived Small Oxygenates: Kinetics, Mechanisms and Site Requirements of H ₂ ‐involved Hydrogenation and Deoxygenation Pathways over Heterogeneous Catalysts
journal, February 2019

Shi, Hui
ChemCatChem, Vol. 11, Issue 7
DOI: 10.1002/cctc.201801828

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Similar Records

Title: Reduction of Propionic Acid over a Pd-Promoted ReOx/SiO2 Catalyst Probed by X-ray Absorption Spectroscopy and Transient Kinetic Analysis

Abstract

Citation Formats

Recent Developments of Heterogeneous Catalysts for Hydrogenation of Carboxylic Acids to their Corresponding Alcohols journal, January 2020

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Title: Reduction of Propionic Acid over a Pd-Promoted ReO_x/SiO₂ Catalyst Probed by X-ray Absorption Spectroscopy and Transient Kinetic Analysis

Recent Developments of Heterogeneous Catalysts for Hydrogenation of Carboxylic Acids to their Corresponding Alcohols
journal, January 2020

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journal, February 2019