Thermochemistry and micro-kinetic analysis of methanol synthesis on ZnO (0001)

Authors
Andrew J. Medford,
Jens Sehested,
Jan Rossmeisl,
Ib Chorkendorff,
Felix Studt,
Jens K. Nørskov,
Poul Georg Moses
Year of publication
2014
Journal
Journal of Catalysis
Volume
309
Starting page
397
Ending page
407
In this work, we examine the thermochemistry of methanol synthesis intermediates using density func- tional theory (DFT) and analyze the methanol synthesis reaction network using a steady-state micro- kinetic model. The energetics for methanol synthesis over Zn-terminated ZnO (0001) are obtained from DFT calculations using the RPBE and BEEF-vdW functionals. The energies obtained from the two function- als are compared and it is determined that the BEEF-vdW functional is more appropriate for the reaction. The BEEF-vdW energetics are used to construct surface phase diagrams as a function of CO, H2O, and H2 chemical potentials. The computed binding energies along with activation barriers from literature are used as inputs for a mean-field micro-kinetic model for methanol synthesis including the CO and CO2 hydrogenation routes and the water–gas shift reaction. The kinetic model is used to investigate the meth- anol synthesis rate as a function of temperature and pressure. The results show qualitative agreement with experiment and yield information on the optimal working conditions of ZnO catalysts.
Funding sources