Transfer hydrogenation over sodium-modified ceria: Enrichment of redox sites active for alcohol dehydrogenation

Nelson, Nicholas C.; Boote, Brett W.; Naik, Pranjali; Rossini, Aaron J.; Smith, Emily A.; Slowing, Igor I.

doi:10.1016/j.jcat.2016.12.018

Title: Transfer hydrogenation over sodium-modified ceria: Enrichment of redox sites active for alcohol dehydrogenation

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Abstract

Ceria (CeO₂) and sodium-modified ceria (Ce-Na) were prepared through combustion synthesis. Palladium was deposited onto the supports (Pd/CeO₂ and Pd/Ce-Na) and their activity for the aqueous-phase transfer hydrogenation of phenol using 2-propanol under liquid flow conditions was studied. Pd/Ce-Na showed a marked increase (6×) in transfer hydrogenation activity over Pd/CeO₂. Material characterization indicated that water-stable sodium species were not doped into the ceria lattice, but rather existed as subsurface carbonates. Modification of ceria by sodium provided more adsorption and redox active sites (i.e. defects) for 2-propanol dehydrogenation. This effect was an intrinsic property of the Ce-Na support and independent of Pd. The redox sites active for 2-propanol dehydrogenation were thermodynamically equivalent on both supports/catalysts. At high phenol concentrations, the reaction was limited by 2-propanol adsorption. Furthermore, the difference in catalytic activity was attributed to the different numbers of 2-propanol adsorption and redox active sites on each catalyst.

Authors:

Nelson, Nicholas C. ^[1]; Boote, Brett W. ^[1]; Naik, Pranjali ^[1]; Rossini, Aaron J. ^[1]; Smith, Emily A. ^[1]; Slowing, Igor I. ^[1]

Ames Lab. and Iowa State Univ., Ames, IA (United States)

Publication Date:: Tue Jan 17 00:00:00 EST 2017

Research Org.:: Ames Lab., Ames, IA (United States)

Sponsoring Org.:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

OSTI Identifier:: 1347411

Alternate Identifier(s):: OSTI ID: 1350060; OSTI ID: 1420008

Report Number(s):: IS-J-9166; IS-J-9026
Journal ID: ISSN 0021-9517; PII: S0021951716303323

Grant/Contract Number:: AC02-07CH11358

Resource Type:: Accepted Manuscript

Journal Name:: Journal of Catalysis

Additional Journal Information:: Journal Volume: 346; Journal Issue: C; Journal ID: ISSN 0021-9517

Publisher:: Elsevier

Country of Publication:: United States

Language:: English

Subject:: 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; transfer hydrogenation; ceria; sodium; alcohol dehydrogenation; redox; defect sites; oxidation; flow chemistry

Citation Formats


                    Nelson, Nicholas C., Boote, Brett W., Naik, Pranjali, Rossini, Aaron J., Smith, Emily A., and Slowing, Igor I. Transfer hydrogenation over sodium-modified ceria: Enrichment of redox sites active for alcohol dehydrogenation.  United States: N. p., 2017. 
Web.  doi:10.1016/j.jcat.2016.12.018.

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                    Nelson, Nicholas C., Boote, Brett W., Naik, Pranjali, Rossini, Aaron J., Smith, Emily A., & Slowing, Igor I. Transfer hydrogenation over sodium-modified ceria: Enrichment of redox sites active for alcohol dehydrogenation.  United States.  https://doi.org/10.1016/j.jcat.2016.12.018

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                    Nelson, Nicholas C., Boote, Brett W., Naik, Pranjali, Rossini, Aaron J., Smith, Emily A., and Slowing, Igor I. Tue .  
"Transfer hydrogenation over sodium-modified ceria: Enrichment of redox sites active for alcohol dehydrogenation".  United States.  https://doi.org/10.1016/j.jcat.2016.12.018.  https://www.osti.gov/servlets/purl/1347411.

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@article{osti_1347411,

  title        = {Transfer hydrogenation over sodium-modified ceria: Enrichment of redox sites active for alcohol dehydrogenation},

  author       = {Nelson, Nicholas C. and Boote, Brett W. and Naik, Pranjali and Rossini, Aaron J. and Smith, Emily A. and Slowing, Igor I.},

  abstractNote = {Ceria (CeO2) and sodium-modified ceria (Ce-Na) were prepared through combustion synthesis. Palladium was deposited onto the supports (Pd/CeO2 and Pd/Ce-Na) and their activity for the aqueous-phase transfer hydrogenation of phenol using 2-propanol under liquid flow conditions was studied. Pd/Ce-Na showed a marked increase (6×) in transfer hydrogenation activity over Pd/CeO2. Material characterization indicated that water-stable sodium species were not doped into the ceria lattice, but rather existed as subsurface carbonates. Modification of ceria by sodium provided more adsorption and redox active sites (i.e. defects) for 2-propanol dehydrogenation. This effect was an intrinsic property of the Ce-Na support and independent of Pd. The redox sites active for 2-propanol dehydrogenation were thermodynamically equivalent on both supports/catalysts. At high phenol concentrations, the reaction was limited by 2-propanol adsorption. Furthermore, the difference in catalytic activity was attributed to the different numbers of 2-propanol adsorption and redox active sites on each catalyst.},

  doi          = {10.1016/j.jcat.2016.12.018},

  journal      = {Journal of Catalysis},

  number       = C,

  volume       = 346,

  place        = {United States},

  year         = {Tue Jan 17 00:00:00 EST 2017},

  month        = {Tue Jan 17 00:00:00 EST 2017}

}

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