A Comparative Ab Initio Study of Anhydrous Dehydrogenation of Linear-Chain Alcohols on Cu(110)

Chen, Wei; Cubuk, Ekin Dogus; Montemore, Matthew M.; Reece, Christian; Madix, Robert J.; Friend, Cynthia M.; Kaxiras, Efthimios

doi:10.1021/acs.jpcc.8b01698

Title: A Comparative Ab Initio Study of Anhydrous Dehydrogenation of Linear-Chain Alcohols on Cu(110)

Journal Article · 27 March 2018 · Journal of Physical Chemistry. C

DOI: https://doi.org/10.1021/acs.jpcc.8b01698 · OSTI ID:1483821

^[1]; Cubuk, Ekin Dogus ^[1];

^[2]; Reece, Christian ^[3]; Madix, Robert J. ^[2];

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

Harvard Univ., Cambridge, MA (United States). Dept. of Physics, and John A. Paulson School of Engineering and Applied Science
Harvard Univ., Cambridge, MA (United States). John A. Paulson School of Engineering and Applied Science, and Dept. of Chemistry and Chemical Biology
Harvard Univ., Cambridge, MA (United States). Applied Science, and Dept. of Chemistry and Chemical Biology

The catalytic behavior of Cu surfaces in the anhydrous production of aldehydes from alcohols, a process of industrial significance, is puzzling: the two simplest alcohols (methanol and ethanol) show dramatically different decomposition behavior on Cu. In this work, we study the thermodynamic and kinetic processes involved in the anhydrous dehydrogenation of linear-chain alcohols including methanol, ethanol, 1-propanol, and 1-butanol on the Cu(110) surface using multiscale approaches. First, we obtain the adsorption structures and energies of the reaction intermediates, in which van der Waals (vdW) interactions play a crucial role. Then, we determine the kinetic barriers for the two dehydrogenation steps, namely, the O–H and the subsequent C–H bond-breaking on Cu. The reaction of methoxy-to-formaldehyde has a rather high-energy transition state, in contrast to that of alkoxide-to-aldehyde in the longer-chain systems. This difference qualitatively explains the lower production efficiency of formaldehyde on Cu. Finally, we simulate the production rates of aldehydes based on which we optimize reaction conditions and propose possible avenues for enhancing the production of anhydrous formaldehyde using Cu-based catalysts.

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Research Organization:: Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States). Oak Ridge Leadership Computing Facility (OLCF); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). National Energy Research Scientific Computing Center (NERSC); Energy Frontier Research Centers (EFRC) (United States). Integrated Mesoscale Architectures for Sustainable Catalysis (IMASC)

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

Grant/Contract Number:: SC0012573

OSTI ID:: 1483821

Journal Information:: Journal of Physical Chemistry. C, Journal Name: Journal of Physical Chemistry. C Journal Issue: 14 Vol. 122; ISSN 1932-7447

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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