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Title: Ethylene glycol reforming on Pt(111): first-principles microkinetic modeling in vapor and aqueous phases

Abstract

First-principles, periodic density functional theory (DFT) calculations and mean-field microkinetic modeling have been used to investigate the decomposition of ethylene glycol for hydrogen production on Pt(111) in vapor and aqueous phases. All dehydrogenated species derived from ethylene glycol (C2HxO2, x = 0–6) and methanol (CHyO, y = 0–4), and all elementary C–C, C–H, and O–H bond breaking steps are included in the microkinetic model. Reaction path analysis in vapor phase indicates that both initial C–H and O–H dehydrogenation steps are kinetically relevant at all temperatures (470–530 K). Initial O–H bond cleavage is reversible at low temperatures but accounts for an increasingly dominant fraction of the total reaction flux at higher temperatures. C–C bond scission is observed only after significant dehydrogenation (x ≤ 3) and is more likely to happen in surface intermediates where one of the cleavage products is CO. Here, the process is highly selective to the production of H2 compared to methanol. For aqueous-phase model development, free energies of solvation were computed for all surface intermediates and transition states using a continuum solvation approach. Our aqueous-phase microkinetic model predicts a 0.4 eV lower apparent activation energy and an order of magnitude larger turnover frequencies. Initial C–H bond cleavagemore » becomes more important but the general trends are similar to the vapor phase, suggesting that the reaction chemistry is similar in both vapor and aqueous phases.« less

Authors:
 [1];  [2];  [3];  [2]
+ Show Author Affiliations
  1. University of South Carolina, Columbia, SC (United States); University of Engineering & Technology, Lahore (Pakistan)
  2. University of South Carolina, Columbia, SC (United States)
  3. University of South Carolina, Columbia, SC (United States); Chinese Academy of Sciences, Liaoning (China)
Publication Date:
Research Org.:
Univ. of South Carolina, Columbia, SC (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division
OSTI Identifier:
1656907
Grant/Contract Number:  
SC0007167
Resource Type:
Accepted Manuscript
Journal Name:
Catalysis Science and Technology
Additional Journal Information:
Journal Volume: 6; Journal Issue: 23; Journal ID: ISSN 2044-4753
Publisher:
Royal Society of Chemistry
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; DFT; Ethylene glycol; Microkinetic modeling; Aqueous-phase reforming; Implicit solvation; Solvent effects

Citation Formats

Faheem, Muhammad, Saleheen, Mohammad, Lu, Jianmin, and Heyden, Andreas. Ethylene glycol reforming on Pt(111): first-principles microkinetic modeling in vapor and aqueous phases. United States: N. p., 2016. Web. doi:10.1039/c6cy02111e.
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Faheem, Muhammad, Saleheen, Mohammad, Lu, Jianmin, & Heyden, Andreas. Ethylene glycol reforming on Pt(111): first-principles microkinetic modeling in vapor and aqueous phases. United States. https://doi.org/10.1039/c6cy02111e
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Faheem, Muhammad, Saleheen, Mohammad, Lu, Jianmin, and Heyden, Andreas. Fri . "Ethylene glycol reforming on Pt(111): first-principles microkinetic modeling in vapor and aqueous phases". United States. https://doi.org/10.1039/c6cy02111e. https://www.osti.gov/servlets/purl/1656907.
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@article{osti_1656907,
title = {Ethylene glycol reforming on Pt(111): first-principles microkinetic modeling in vapor and aqueous phases},
author = {Faheem, Muhammad and Saleheen, Mohammad and Lu, Jianmin and Heyden, Andreas},
abstractNote = {First-principles, periodic density functional theory (DFT) calculations and mean-field microkinetic modeling have been used to investigate the decomposition of ethylene glycol for hydrogen production on Pt(111) in vapor and aqueous phases. All dehydrogenated species derived from ethylene glycol (C2HxO2, x = 0–6) and methanol (CHyO, y = 0–4), and all elementary C–C, C–H, and O–H bond breaking steps are included in the microkinetic model. Reaction path analysis in vapor phase indicates that both initial C–H and O–H dehydrogenation steps are kinetically relevant at all temperatures (470–530 K). Initial O–H bond cleavage is reversible at low temperatures but accounts for an increasingly dominant fraction of the total reaction flux at higher temperatures. C–C bond scission is observed only after significant dehydrogenation (x ≤ 3) and is more likely to happen in surface intermediates where one of the cleavage products is CO. Here, the process is highly selective to the production of H2 compared to methanol. For aqueous-phase model development, free energies of solvation were computed for all surface intermediates and transition states using a continuum solvation approach. Our aqueous-phase microkinetic model predicts a 0.4 eV lower apparent activation energy and an order of magnitude larger turnover frequencies. Initial C–H bond cleavage becomes more important but the general trends are similar to the vapor phase, suggesting that the reaction chemistry is similar in both vapor and aqueous phases.},
doi = {10.1039/c6cy02111e},
journal = {Catalysis Science and Technology},
number = 23,
volume = 6,
place = {United States},
year = {Fri Oct 28 00:00:00 EDT 2016},
month = {Fri Oct 28 00:00:00 EDT 2016}
}
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https://doi.org/10.1039/c6cy02111e
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