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

Faheem, Muhammad; Saleheen, Mohammad; Lu, Jianmin; Heyden, Andreas

doi:10.1039/c6cy02111e

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

Journal Article · Fri Oct 28 04:00:00 EDT 2016 · Catalysis Science and Technology

DOI:https://doi.org/10.1039/c6cy02111e· OSTI ID:1656907

Faheem, Muhammad ^[1]; Saleheen, Mohammad ^[2]; Lu, Jianmin ^[3]; Heyden, Andreas ^[2]

University of South Carolina, Columbia, SC (United States); University of Engineering & Technology, Lahore (Pakistan)
University of South Carolina, Columbia, SC (United States)
University of South Carolina, Columbia, SC (United States); Chinese Academy of Sciences, Liaoning (China)

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 (C₂H_xO₂, x = 0–6) and methanol (CH_yO, 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.

View Accepted Manuscript (DOE)

Research Organization:: University of South Carolina, Columbia, SC (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: SC0007167

OSTI ID:: 1656907

Alternate ID(s):: OSTI ID: 3001216

Journal Information:: Catalysis Science and Technology, Journal Name: Catalysis Science and Technology Journal Issue: 23 Vol. 6; ISSN 2044-4753

Publisher:: Royal Society of ChemistryCopyright Statement

Country of Publication:: United States

Language:: English

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

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