Density Functional Studies of Methanol Decomposition on Subnanometer Pd Clusters

Journal Article · Thu Dec 31 04:00:00 EST 2009 · Journal of Physical Chemistry C, 113(52):21789-21796

DOI:https://doi.org/10.1021/jp907772c· OSTI ID:1001531

Mehmood, Faisal; Greeley, Jeffrey P; Curtiss, Larry A

A density functional theory study of the decomposition of methanol on subnanometer palladium clusters (primarily Pd4) is presented. Methanol dehydrogenation through C-H bond breaking to form hydroxymethyl (CH2OH) as the initial step, followed by steps involving formation of hydroxymethylene (CHOH), formyl (CHO), and carbon monoxide (CO), is found to be the most favorable reaction pathway. A competing dehydrogenation pathway with O-H bond breaking as the first step, followed by formation of methoxy (CH3O) and formaldehyde (CH2O), is slightly less favorable. In contrast, pathways involving C-O bond cleavage are much less energetically favorable, and no feasible pathways involving C-O bond formation to yield dimethyl ether (CH3OCH3) are found. Comparisons of the results are made with methanol decomposition products adsorbed on more extended Pd surfaces; all reaction intermediates are found to bind slightly more strongly to the clusters than to the surfaces.

• Research Organization: Pacific Northwest National Laboratory (PNNL), Richland, WA (US), Environmental Molecular Sciences Laboratory (EMSL)
• Sponsoring Organization: USDOE
• DOE Contract Number: AC05-76RL01830
• OSTI ID: 1001531
• Journal Information: Journal of Physical Chemistry C, 113(52):21789-21796, Journal Name: Journal of Physical Chemistry C, 113(52):21789-21796 Journal Issue: 52 Vol. 113; ISSN 1932-7447
• Country of Publication: United States
• Language: English

Related Subjects

10 SYNTHETIC FUELS
CARBON MONOXIDE
CLEAVAGE
DEHYDROGENATION
Environmental Molecular Sciences Laboratory
FORMALDEHYDE
FUNCTIONALS
METHANOL
METHYL ETHER
PALLADIUM
REACTION INTERMEDIATES