Theoretical Studies of Activation Energies and Pre-Exponential Factors of Alcohol Dehydrogenation on Cu
ORAL
Abstract
We study the thermodynamic and kinetic processes involved in the anhydrous dehydrogenation of linear-chain alcohols on the Cu(110) surface using multiscale approaches. 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. We also use a Monte Carlo sampling to calculate the entropies of initial and transition states. The estimated pre-exponential factors, beyond the harmonic approximation, are found to have a molecular size dependence.
*This work was supported by the Integrated Mesoscale Architectures for Sustainable Catalysis, an Energy Frontier Research Center funded by the U.S. Department of Energy, Office of Science, Basic Energy Sciences under Award #DE-SC0012573.
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Presenters
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Wei Chen
- Harvard University