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Title: Role of the Support and Reaction Conditions on the Vapor-Phase Deoxygenation of m-Cresol over Pt/C and Pt/TiO2 Catalysts

The catalytic deoxygenation of biomass fast pyrolysis vapors offers a promising route for the sustainable production of liquid transportation fuels. However, a clear understanding of the mechanistic details involved in this process has yet to be achieved, and questions remain regarding the role of the catalyst support and the influence of reaction conditions. In order to gain insight into these questions, the deoxygenation of m-cresol was investigated over Pt/C and Pt/TiO2 catalysts using experimental and computational techniques. The performance of each catalyst was evaluated in a packed-bed reactor under two conditions (523 K, 2.0 MPa and 623 K, 0.5 MPa), and the energetics of the ring hydrogenation, direct deoxygenation, and tautomerization mechanisms were calculated over hydrogen-covered Pt(111) and oxygen vacancies on the surface of TiO2(101). Over Pt(111), ring hydrogenation to 3-methylcyclohexanone and 3-methylcyclohexanol was found to be the most energetically favorable pathway. Over TiO2(101), tautomerization and direct deoxygenation to toluene were identified as additional energetically favorable routes. These calculations are consistent with the experimental data, in which Pt/TiO2 was more active on a metal site basis and exhibited higher selectivity to toluene at 623 K relative to Pt/C. On the basis of these results, it is likely that the reactivitymore » of Pt/TiO2 and Pt/C is driven by the metallic phase at 523 K, while contributions from the TiO2 support enhance deoxygenation at 623 K. These results highlight the synergistic effects between hydrogenation catalysts and reducible metal oxide supports and provide insight into the reaction pathways responsible for their enhanced deoxygenation performance.« less
Authors:
 [1] ;  [1] ;  [1] ;  [1] ;  [1] ;  [1]
  1. National Renewable Energy Lab. (NREL), Golden, CO (United States). National Bioenergy Center
Publication Date:
OSTI Identifier:
1247125
Report Number(s):
NREL/JA-5100-66208
Journal ID: ISSN 2155-5435
Grant/Contract Number:
AC36-08GO28308; MCB-090159
Type:
Accepted Manuscript
Journal Name:
ACS Catalysis
Additional Journal Information:
Journal Volume: 6; Journal Issue: 4; Journal ID: ISSN 2155-5435
Publisher:
American Chemical Society (ACS)
Research Org:
National Renewable Energy Lab. (NREL), Golden, CO (United States)
Sponsoring Org:
USDOE Office of Energy Efficiency and Renewable Energy (EERE)
Country of Publication:
United States
Language:
English
Subject:
09 BIOMASS FUELS; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANAYLYTICAL CHEMISTRY; hydrodeoxygenation; catalytic fast pyrolysis; TiO2; m-cresol; bio-oil; DFT; hydrogen coverage; platinum