Anhydrous Methanol and Ethanol Dehydrogenation at Cu(111) Step Edges

Hoyt, Robert A.; Montemore, Matthew M.; Sykes, E. Charles H.; Kaxiras, Efthimios

doi:10.1021/acs.jpcc.8b06730

Anhydrous Methanol and Ethanol Dehydrogenation at Cu(111) Step Edges

Journal Article · Wed Sep 05 00:00:00 EDT 2018 · Journal of Physical Chemistry. C

DOI:https://doi.org/10.1021/acs.jpcc.8b06730· OSTI ID:1597699

^[1]; ^[2]; ^[3]; Kaxiras, Efthimios ^[2]

Harvard Univ., Cambridge, MA (United States); Harvard University
Harvard Univ., Cambridge, MA (United States)
Tufts Univ., Medford, MA (United States)

Oxidative methanol dehydrogenation is a significant industrial reaction with global formaldehyde production exceeding 30 million tonnes per year. Unfortunately, oxidative dehydrogenation produces water-aldehyde mixtures that require subsequent distillation. Anhydrous alcohol dehydrogenation is a potential alternative that produces H2 instead of water. Pursuant to recent experimental work showing that highly stepped Cu(111) surfaces exhibit anhydrous dehydrogenation activity, we present firstprinciples density functional theory calculations for methanol and ethanol dehydrogenation at Cu(111) step edges to provide an atomistic understanding of the catalytic mechanism; these sites stabilize all intermediates while reducing activation energies. We find that van der Waals contributions to the energy account for more than 50% of adsorption energies, and their inclusion is essential in achieving good agreement with experimental desorption temperatures. Furthermore, vibrational zero-point energy corrections significantly reduce the activation energy for all reaction steps considered here. Hydrogen bonding among ethanol intermediates at step edges is weakened by geometric frustration. These insights lead us to propose several suggestions for further research on undercoordinated Cu sites as anhydrous alcohol dehydrogenation catalysts.

View Accepted Manuscript (DOE)

Research Organization:: Energy Frontier Research Centers (EFRC) (United States). Integrated Mesoscale Architectures for Sustainable Catalysis (IMASC); Harvard Univ., Cambridge, MA (United States); Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States); Univ. of California, Berkeley, CA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)

Contributing Organization:: National Energy Research Scientific Computing Center (NERSC)

Grant/Contract Number:: SC0012573; AC05-00OR22725; AC02-05CH11231

OSTI ID:: 1597699

Alternate ID(s):: OSTI ID: 1539291

Journal Information:: Journal of Physical Chemistry. C, Journal Name: Journal of Physical Chemistry. C Journal Issue: 38 Vol. 122; ISSN 1932-7447

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Activation energy
Adsorption Ethanol
Alcohols
Aldehydes

Anhydrous Methanol and Ethanol Dehydrogenation at Cu(111) Step Edges

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References (45)

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