The formation of acetic anhydride by decomposition of acetic acid adsorbed on Ni(111)

Erley, W.; Chen, J. G.; Sander, Dirk

doi:10.1116/1.576906

Cited by 13 publications

(4 citation statements)

References 0 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…This assignment is consistent with a study on Ru(0001) that reported a similar peak for the same chelating acetate at 1450 cm –1 . Furthermore, a similar peak was observed on Ni(111) . The argument against the chelating acetate assignment is that our calculations suggest high instability of this structure.…”

Section: Discussionsupporting

confidence: 74%

“…Furthermore, a similar peak was observed on Ni(111). 33 The argument against the chelating acetate assignment is that our calculations suggest high instability of this structure. It readily converts to a much more stable bridge-bonded bidentate acetate in Figure 8b and can be stable only on single Ni atoms surrounded by strongly bound adsorbates, such as atomic oxygen (Figure 10c).…”

Section: Discussionmentioning

confidence: 83%

See 1 more Smart Citation

Acetic Acid Adsorption and Reactions on Ni(110)

et al. 2020

View full text Add to dashboard Cite

Acetic acid adsorption and reactions at multiple surface coverage values on Ni(110) were studied with temperatureprogrammed desorption (TPD) and infrared reflection absorption spectroscopy (IRAS) at 90−500 K. The experimental measurements were interpreted with density functional theory (DFT) calculations that provided information on adsorbate geometries, energies, and vibrational modes. Below the monolayer saturation coverage of 0.36 ML at 90 K, acetic acid adsorbs mostly molecularly. Above this coverage, a physisorbed layer is formed with dimers and catemers, without detectable monomers. Dimers and catemers desorb as molecular acetic acid at 157 and 172 K, respectively. Between 90 and 200 K, the O−H bond in acetic acid breaks to form bridge-bonded bidentate acetate that becomes the dominant surface species. Desorption-limited hydrogen evolution is observed at 265 K. However, even after the acetate formation, acetic acid desorbs molecularly at 200−300 K due to recombination. Minor surface species observed at 200 K, acetyls or acetates with a carbonyl group, decompose below 350 K and generate adsorbed carbon monoxide. At 350 K, the surface likely undergoes restructuring, the extent of which increases with acetic acid coverage. The initial dominant bridge-bonded bidentate acetate species formed below 200 K remain on the surface, but they now mostly adsorb on the restructured sites. The acetates and all other remaining hydrocarbon species decompose simultaneously at 425 K in a narrow temperature range with concurrent evolution of hydrogen, carbon monoxide, and carbon dioxide. Above 425 K, only carbon remains on the surface.

show abstract

Section: Discussionsupporting

confidence: 74%

Section: Discussionmentioning

confidence: 83%

Acetic Acid Adsorption and Reactions on Ni(110)

et al. 2020

View full text Add to dashboard Cite

show abstract

“…Dehydrogenation of acetate to give H 2 and CO 2 , and in some cases CO and surface C as well, has been reported on Ni{111}, Ni{110}, Ni{100}, Pt{111}, Pd{111}, Pd{110}, Rh{111}, , and Rh{110} . In some cases autocatalytic decomposition has been observed, ,− and the involvement of an acetic anhydride intermediate has also been proposed. , …”

Section: Introductionmentioning

confidence: 98%

Surface-Bound Helical Polyacetaldehyde Chains and Bidentate Acetate Intermediates on Ag{111}

1996

View full text Add to dashboard Cite

The interaction of acetic acid and acetaldehyde with preoxidized Ag{111} has been studied using reflection absorption infrared spectroscopy. A bidentate bridging acetate species which shows no coverage-dependent orientation can be formed either by direct deprotonation of acetic acid by surface atomic O at 240 K or via O-induced polymerization of acetaldehyde at 140 K, followed by decomposition of the polyacetaldehyde intermediate into ethane-1,1-dioxy fragments that dehydrogenate at 220 K. A symmetry analysis reveals that the vibrational spectra of polyacetaldehyde and paraformaldehyde on many metal surfaces can be best interpreted in terms of helical chain structures bound to the surface by skeletal O atoms located along various points of the polymer backbones.

show abstract

“…The chemistry of carboxylic acids on single-crystal transition metal surfaces has been widely studied. − Deprotonation of these acids to form carboxylates has been observed on clean metal surfaces. − The carboxylate later decomposes to yield CO 2 and other hydrocarbon products. The motivation behind previous work has been that the formation of a carboxylate intermediate is important in several catalytic reactions, e.g., alcohol synthesis and the methanation of CO , and CO 2 . − Because the chemistry of CH 3 CO 2 H on Ag surfaces has been studied previously, − these surfaces are good candidates for the study carried out in this work.…”

Section: Introductionmentioning

confidence: 99%

Carboxylic Acid Deprotonation on the Ag(110) and Ag(111) Surfaces

2001

View full text Add to dashboard Cite

The surface chemistry of hydrocarbon carboxylic acids has been compared with that of perfluorinated carboxylic acids on the Ag(110) and Ag(111) surfaces. The hydrocarbon acids adsorb reversibly on the clean silver surfaces. On Ag(110) their desorption energies increase linearly with increasing alkyl chain length (n) and are given by the expression ∆Edes ) 10.6 + 0.9n kcal/mol. The surface chemistry of the perfluorinated acids is quite different from that of the hydrocarbon acids in the sense that they deprotonate to form perfluorocarboxylate species on both Ag(110) and Ag(111) surfaces. The perfluorocarboxylates are stable until the surface temperature reaches ∼620 K, at which point they decompose yielding desorption of CO2 and other decomposition fragments. On both Ag surfaces 2,2,2-trifluoroacetate (CF3CO2) generated by deprotonation of 2,2,2-trifluoroacetic acid (CF3CO2H) has been identified by its vibrational spectrum. The fact that fluorinated acids deprotonate on the Ag surfaces while the hydrocarbon acids desorb during heating indicates that fluorination lowers the deprotonation barrier, ∆E ‡ dep, to the point that it is lower than the desorption energy, ∆Edes.

show abstract

The formation of acetic anhydride by decomposition of acetic acid adsorbed on Ni(111)

Cited by 13 publications

References 0 publications

Acetic Acid Adsorption and Reactions on Ni(110)

Acetic Acid Adsorption and Reactions on Ni(110)

Surface-Bound Helical Polyacetaldehyde Chains and Bidentate Acetate Intermediates on Ag{111}

Carboxylic Acid Deprotonation on the Ag(110) and Ag(111) Surfaces

Contact Info

Product

Resources

About