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Title: An Efficient Reaction Pathway Search Method Applied to the Decomposition of Glycerol on Platinum

Abstract

First-principles-calculation-based understanding of the reaction mechanisms of processing biomass derivatives is currently lacking due to the cost involved in performing computations of multireaction mechanisms of large molecules. We combine semiempirical methods (group additivity and Brønsted–Evans–Polanyi (BEP) linear free energy relationships) and density function theory (DFT) calculations to provide an efficient search method of key intermediates and reactions and point out the most likely reaction pathways for conversion of glycerol to synthesis gas on Pt(111). The following pathway, C₃H₈O₃ → CHOHCHOHCH₂OH → CHOHCHOHCHOH → CHOHCOHCHOH → COHCOHCHOH → COCOHCHOH → CO + COHCHOH, is identified as the most favorable one and a highly dehydrogenated species (COCOHCHOH) is a key intermediate for C–C bond cleavage. The (over-)functionalization of biomass changes the nature of the rate-controlling step to dehydrogenation compared to C–C scission in hydrocarbons and monols. Our results indicate that for biomass reforming, catalysts with high initial-step dehydrogenation activity should be developed.

Authors:
 [1];  [1];  [1]
  1. Center for Catalytic Science and Technology, Univ. of Delaware, Newark, DE (United States)
Publication Date:
Research Org.:
Energy Frontier Research Centers (EFRC); Catalysis Center for Energy Innovation (CCEI)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
Contributing Org.:
National Center for Supercomputing Applications (NCSA), Univ. of Illinois, Urbana, IL (United States)
OSTI Identifier:
1065626
DOE Contract Number:  
SC0001004
Resource Type:
Journal Article
Journal Name:
Journal of Physical Chemistry. C
Additional Journal Information:
Journal Volume: 115(38); Journal Issue: 38; Related Information: CCEI partners with the University of Delaware (lead); Brookhaven National Laboratory; California Institute of Technology; Columbia University; University of Delaware; Lehigh University; University of Massachusetts, Amherst; Massachusetts Institute of Technology; University of Minnesota; Pacific Northwest National Laboratory; University of Pennsylvania; Princeton University; Rutgers University; Journal ID: ISSN 1932-7447
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; catalysis (homogeneous), catalysis (heterogeneous), biofuels (including algae and biomass), bio-inspired, hydrogen and fuel cells, materials and chemistry by design, synthesis (novel materials), synthesis (self-assembly), synthesis (scalable processing)

Citation Formats

Chen, Y., Salciccioli, M., and Vlachos, D. G. An Efficient Reaction Pathway Search Method Applied to the Decomposition of Glycerol on Platinum. United States: N. p., 2011. Web. doi:10.1021/jp205483m.
Chen, Y., Salciccioli, M., & Vlachos, D. G. An Efficient Reaction Pathway Search Method Applied to the Decomposition of Glycerol on Platinum. United States. doi:10.1021/jp205483m.
Chen, Y., Salciccioli, M., and Vlachos, D. G. Thu . "An Efficient Reaction Pathway Search Method Applied to the Decomposition of Glycerol on Platinum". United States. doi:10.1021/jp205483m.
@article{osti_1065626,
title = {An Efficient Reaction Pathway Search Method Applied to the Decomposition of Glycerol on Platinum},
author = {Chen, Y. and Salciccioli, M. and Vlachos, D. G.},
abstractNote = {First-principles-calculation-based understanding of the reaction mechanisms of processing biomass derivatives is currently lacking due to the cost involved in performing computations of multireaction mechanisms of large molecules. We combine semiempirical methods (group additivity and Brønsted–Evans–Polanyi (BEP) linear free energy relationships) and density function theory (DFT) calculations to provide an efficient search method of key intermediates and reactions and point out the most likely reaction pathways for conversion of glycerol to synthesis gas on Pt(111). The following pathway, C₃H₈O₃ → CHOHCHOHCH₂OH → CHOHCHOHCHOH → CHOHCOHCHOH → COHCOHCHOH → COCOHCHOH → CO + COHCHOH, is identified as the most favorable one and a highly dehydrogenated species (COCOHCHOH) is a key intermediate for C–C bond cleavage. The (over-)functionalization of biomass changes the nature of the rate-controlling step to dehydrogenation compared to C–C scission in hydrocarbons and monols. Our results indicate that for biomass reforming, catalysts with high initial-step dehydrogenation activity should be developed.},
doi = {10.1021/jp205483m},
journal = {Journal of Physical Chemistry. C},
issn = {1932-7447},
number = 38,
volume = 115(38),
place = {United States},
year = {2011},
month = {9}
}