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

Abstract

Ceria (CeO 2) and sodium-modified ceria (Ce-Na) were prepared through combustion synthesis. Palladium was deposited onto the supports (Pd/CeO 2 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/CeO 2. 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:
 [1];  [1];  [1];  [1];  [1];  [1]
  1. Ames Lab. and Iowa State Univ., Ames, IA (United States)
Publication Date:
Research Org.:
Ames Laboratory (AMES), Ames, IA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
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:
Journal Article: 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.
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. doi:10.1016/j.jcat.2016.12.018.
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. doi:10.1016/j.jcat.2016.12.018. https://www.osti.gov/servlets/purl/1347411.
@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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  • Ceria (CeO 2) and sodium-modified ceria (Ce-Na) were prepared through combustion synthesis. Palladium was deposited onto the supports (Pd/CeO 2 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/CeO 2. 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 supportmore » 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.« less
  • Cited by 1
  • In order to elucidate active sites for selective dehydrogenation of methanol to formaldehyde on sodium-modified silicalite-1, adsorption of methanol on sodium-modified and -unmodified silicalite-1 has been investigated by a temperature-programmed desorption technique, infrared spectroscopy, and ab initio molecular orbital calculations. In sodium-modified silicalite-1, three kinds of the adsorption sites are present, that is, silanol sites, sodium-ion sites, and active oxygen bridge sites. Dissociative adsorption of methanol on the active oxygen bridge probably causes generation of silanol and methoxyl groups on the silicalite surface. by heating a sodium-modified silicalite-1 sample at 970 K, the number of the active oxygen bridges increasedmore » compared with that for the sample preheated at 770 K and its catalytic activity for methanol dehydrogenation also increased. Thus, it is proposed that methanol dehydrogenation is driven by the active oxygen bridges.« less
  • New information about the active sites for the water gas shift (WGS) reaction over Cu-CeO{sub 2} systems was obtained using in-situ, time-resolved X-ray diffraction (TR-XRD), X-ray absorption spectroscopy (TR-XAS, Cu K and Ce L3 edges), and infrared spectroscopy (DRIFTS). Cu-CeO{sub 2} nanoparticles prepared by a novel reversed microemulsion method (doped Ce1-xCuxO2 sample) and an impregnation method (impregnated CuO{sub x}/CeO{sub 2} sample) were studied. The results from all of the samples indicate that both metallic copper and oxygen vacancies in ceria were involved in the generation of active sites for the WGS reaction. Evidence was found for a synergistic Cu-O vacancymore » interaction. This interaction enhances the chemical activity of Cu, and the presence of Cu facilitates the formation of O vacancies in ceria under reaction conditions. Water dissociation occurred on the O vacancy sites or the Cu-O vacancy interface. No significant amounts of formate were formed on the catalysts during the WGS reaction. The presence of strongly bound carbonates is an important factor for the deactivation of the catalysts at high temperatures. This work identifies for the first time the active sites for the WGS reaction on Cu-CeO{sub 2} catalysts and illustrates the importance of in situ structural studies for heterogeneous catalytic reactions.« less
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