Effect of Pd surface structure on the activation of methyl acetate

Journal Article · Fri Dec 31 23:00:00 EST 2010 · Catalysis Today

DOI:https://doi.org/10.1016/j.cattod.2010.12.021· OSTI ID:1081695

Xu, Lijun ^[1]; Xu, Ye ^[1]

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1. ORNL

The activation of methyl acetate (CH3COOCH3; MA) has been studied using periodic density functional theory calculations to probe the effect of Pd surface structure on the selectivity in MA activation. The adsorption of MA, dehydrogenated derivatives, enolate (CH2COOCH3; ENL) and methylene acetate (CH3COOCH2; MeA), and several dissociation products (including acetate, acetyl, ketene, methoxy, formaldehyde, CO, C, O, and H); and C-H and C-O (mainly in the RCO-OR position) bond dissociation in MA, ENL, and MeA, are calculated on Pd(111) terrace, step, and kink; and on Pd(100) terrace and step. The adsorption of most species is not strongly affected between (111)- to (100)-type surfaces, but is clearly enhanced by step/kink compared to the corresponding terrace. Going from terrace to step edge and from (111)- to (100)-type surfaces both stabilize the transition states of C-O bond dissociation steps. Going from terrace to step edge also stabilizes the transition states of C-H bond dissociation steps, but going from (111)- to (100)-type surfaces does not clearly do so. We propose that compared to the Pd(111) terrace, the Pd(100) terrace is more selective for C-O bond dissociation that is desirable for alcohol formation, whereas the Pd step edges are more selective for C-H bond dissociation.

• Research Organization: Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States). Oak Ridge Leadership Computing Facility (OLCF); Oak Ridge National Laboratory (ORNL); Center for Nanophase Materials Sciences
• Sponsoring Organization: DOE Office of Science; ORNL work for others
• DOE Contract Number: AC05-00OR22725
• OSTI ID: 1081695
• Journal Information: Catalysis Today, Journal Name: Catalysis Today Journal Issue: 1 Vol. 165; ISSN 0920-5861
• Country of Publication: United States
• Language: English