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Adsorption of highly functional oxygenates on metal surfaces


EMSL Project ID
44590

Abstract

This proposal is aimed at conducting computational studies to investigate the surface chemistry of functional alcohols on Pd(111) and related surfaces. Such alcohols are key intermediates in the refining of biomass to valuable fuels and chemicals, and understanding reactivity of functional alcohols on metal surfaces will aid in improvement of supported metal catalysts. The density functional theory (DFT) software code VASP version 5.2 will be employed to investigate the complete decomposition pathways for two relatively simple probe molecules, 1-propanol (CH3CH2CH2OH) and allyl alcohol (CH2=CHCH2OH), to understand how the added C=C functional group of the latter molecule changes surface reaction pathways. These investigations will complement ongoing experimental work in the PI's group, which has found that highly functionalized alcohols and other oxygenates undergo significantly different reactivity even at the alcohol functional position relative to their simple alcohol counterparts. By investigating in a systematic way the role of the C=C functional group in moderating intermediate structures, the reaction energies of elementary steps, and transition state structures and energies, it will be possible to begin to develop structure-property relations that may enable design of improved metal catalysts for reactions of biomass-derived alcohols.

In the proposed work, the decomposition pathways for 1-propanol and allyl alcohol will be mapped out in detail. Experimentally, it has been shown that whereas propanol decomposes exclusively via oxidation to an aldehyde followed by decarbonylation, an additional C-O scission pathway is observed for allyl alcohol. Thus, this investigation will focus on identifying factors that make C-O scission more favorable, and understanding possible ways to manipulate alcohol oxidation versus hydrogenolysis selectivity. Initial calculations will be conducted on Pd(111), and will include computations of both stable adsorbed states and transition states as a function of coverage. Subsequent calculations will explore extension of this chemistry to other metal surfaces to explore general trends. Comparisons to observations from experimental studies of the PI's group and other groups will help in developing a more complete understanding of alcohol reactions on metal surfaces.

Project Details

Project type
Large-Scale EMSL Research
Start Date
2011-10-01
End Date
2014-09-30
Status
Closed

Team

Principal Investigator

James Medlin
Institution
University of Colorado at Boulder

Team Members

Allison Robinson
Institution
University of Colorado at Boulder

Tania Tauer
Institution
University of Colorado at Boulder

Matthew Montemore
Institution
University of Colorado at Boulder

Simon Pang
Institution
University of Colorado at Boulder

Related Publications

Gould TD, MM Montemore, AM Lubers, LD Ellis, A Weimer, JL Falconer, and JW Medlin. 2015. "Enhanced Dry Reforming of Methane on Ni and Ni-Pt Catalysts Synthesized by Atomic Layer Deposition." Applied Catalysis. A, General 492:107–116. doi:10.1016/j.apcata.2014.11.037
Montemore, MM. 2014. Designing Transition Metal Surfaces for their Adsorption Properties and Chemical Reactivity. PhD Thesis, University of Colorado Boulder. 212 p.
Montemore MM, and JW Medlin. 2013. "A Simple, Accurate Model for Alkyl Adsorption on Late Transition Metals." Journal of Physical Chemistry C 117:2835-2843. doi:10.1021/jp310533e
Montemore MM, and JW Medlin. 2013. "A Simple, Accurate Model for Alkyl Adsorption on Late Transition Metals." Journal of Physical Chemistry C 117(6):2835-2843. doi:10.1021/jp310533e
Montemore MM, and JW Medlin. 2013. "Site-Specific Scaling Relations for Hydrocarbon Adsorption on Hexagonal Transition Metal Surfaces." Journal of Physical Chemistry C 117(39):20078–20088. doi:10.1021/jp4076405
Montemore MM, and JW Medlin. 2014. "A Unified Picture of Adsorption on Transition Metals through Different Atoms." Journal of the American Chemical Society 136(26):9272?9275. doi:10.1021/ja504193w
Montemore M M,Andreussi O ,Medlin J W 2016. "Hydrocarbon Adsorption in an Aqueous Environment: A Computational Study of Alkyls on Cu(111)" Journal of Chemical Physics 145():074702. 10.1063/1.4961027