The research described in this product was performed in part in the Environmental Molecular Sciences Laboratory, a national scientific user facility sponsored by the Department of Energy's Office of Biological and Environmental Research and located at Pacific Northwest National Laboratory. The dual path mechanism for methanol decomposition on well-defined low Miller index platinum single
crystal planes, Pt(111), Pt(110), and Pt(100), was studied using a combination of chronoamperometry, fast
scan cyclic voltammetry, and theoretical methods. The main focus was on the electrode potential range when
the adsorbed intermediate, COad, is stable. At such “CO stability” potentials, the decomposition proceeds
through a pure dehydrogenation reaction, and the dual path mechanism is then independent of the electrodesubstrate
surface structure. However, the threshold potential where the decomposition of methanol proceeds
via parallel pathways, forming other than COad products, depends on the surface structure. This is rationalized
theoretically. To gain insights into the controlling surface chemistry, density functional theory calculations
for the energy of dehydrogenation were used to approximate the potential-dependent methanol dehydrogenation
pathways over aqueous-solvated platinum interfaces.
Revised: April 7, 2011 |
Published: June 16, 2005
Citation
Cao D., G.Q. Lu, A. Wieckowski, S.A. Wasileski, and M. Neurock. 2005. "Mechanisms of Methanol Decomposition on Platinum: A Combined Experimental and ab
Initio Approach." Journal of Physical Chemistry B 109, no. 23:11622-11633. doi:10.1021/jp0501188