A DFT and MD study of aqueous-phase dehydrogenation of glycerol on Pt(1 1 1): comparing chemical accuracy versus computational expense in different methods for calculating aqueous-phase system energies

Tianjun Xie, Sapna Sarupria, Rachel B. Getman

Research output: Contribution to journalArticlepeer-review

19 Scopus citations

Abstract

Glycerol, which is one of the most abundant by-products in biodiesel production, can be converted into H2 through aqueous-phase reforming (APR). Dehydrogenation is one of the main processes in glycerol APR. In this work, we use computational methods to study Pt(1 1 1)-catalysed glycerol dehydrogenation under aqueous conditions. There are 84 intermediates and 250 possible reactions in the dehydrogenation network. Inclusion of the liquid environment adds computational expense, especially if we are to study all the reaction intermediates and reactions under explicit water solvation using quantum methods. In this work, we present a method that can be used to efficiently estimate reaction energies under explicit solvation with reasonable accuracy and computational expense. The method couples a linear scaling relationship for obtaining adsorbate binding energies with Lennard-Jones + Coulomb potentials for obtaining water–adsorbate interaction energies. Comparing reaction energies calculated with this approach to reaction energies obtained from a more extensive approach that attains quantum-level accuracy (published previously by our group), we find good correlation (R2 = 0.84) and reasonable accuracy (the mean absolute error, MAE = 0.28 eV).

Original languageEnglish (US)
Pages (from-to)370-378
Number of pages9
JournalMolecular Simulation
Volume43
Issue number5-6
DOIs
StatePublished - Apr 13 2017
Externally publishedYes

Bibliographical note

Funding Information:
This research was funded by the National Science Foundation [grant number CBET-1438325]; the Chemical and Biomolecular Engineering Department at Clemson University. Simulations were performed on the Palmetto Supercomputer Cluster, which is maintained by the Cyberinfrastructure Technology Integration Group at Clemson University. We thank Dr Steven Louis Pellizzeri, who is a postdoctoral associate in our group, for his help in applying the extended linear scaling relationship used in this work. We also thank undergraduate research assistants Grant Hummel and Andrew Bingham, who helped calculate energies for some of the adsorbates studied in this work. Grant and Andrew worked in our group as part of Clemson University?s EURKEA! program, which is funded through the Clemson University Calhoun Honors College.

Publisher Copyright:
© 2017 Informa UK Limited, trading as Taylor & Francis Group.

Keywords

  • Aqueous-phase reforming
  • catalysis
  • glycerol
  • hierarchical modelling
  • linear scaling relationship

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