Density functional studies of methanol decomposition on subnanometer Pd clusters.

Journal Article · Thu Dec 31 04:00:00 EST 2009 · J. Phys. Chem. C

DOI:https://doi.org/10.1021/jp907772c· OSTI ID:977365

Mehmood, F; Greeley, J; Curtiss, L A

A density functional theory study of the decomposition of methanol on subnanometer palladium clusters (primarily Pd{sub 4}) is presented. Methanol dehydrogenation through C-H bond breaking to form hydroxymethyl (CH{sub 2}OH) 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 (CH{sub 3}O) and formaldehyde (CH{sub 2}O), 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 (CH{sub 3}OCH{sub 3}) 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: Argonne National Laboratory (ANL)
• Sponsoring Organization: SC
• DOE Contract Number: AC02-06CH11357
• OSTI ID: 977365
• Report Number(s): ANL/MSD/JA-65467
• Journal Information: J. Phys. Chem. C, Journal Name: J. Phys. Chem. C Journal Issue: 52 ; Dec. 31, 2009 Vol. 113; ISSN 1932-7447
• Country of Publication: United States
• Language: ENGLISH

Related Subjects

10 SYNTHETIC FUELS
CARBON MONOXIDE
CLEAVAGE
DEHYDROGENATION
FORMALDEHYDE
FUNCTIONALS
METHANOL
METHYL ETHER
PALLADIUM
REACTION INTERMEDIATES