Probing the Role of Oxygen Coordination in Hydrocarbon Oxidation:  Methyl Radical Addition to Oxygen on Mo(110)

Queeney, K. T.; Chen, Donna; Friend, Cynthia M.

doi:10.1021/ja9707771

Cited by 40 publications

(45 citation statements)

References 28 publications

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“…Therefore, they proposed that there were similar adsorption sites for oxygen on the two surfaces. The same phenomenon can be found in O-Mo (110) [10][11][12] and O-W (110) [13][14][15] systems. There also were many studies on O-Cr (100) system.…”

Section: 3supporting

confidence: 73%

Adsorption of O Atom on Cr (100), (110), (111), and (211) Surfaces: An 5-Parameter Morse Potential Method Study

Han¹,

Liu²

2012

Bulletin of the Korean Chemical Society

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The 5-parameter Morse potential (5-MP) method for the interaction between O atom and Cr surfaces is constructed in the present work. The adsorption of O on Cr (100), (110), (111), and (211) surfaces are studied with 5-MP in detail. The fourfold hollow site of the Cr (100) surface is favored for O atom. On Cr (110), quasithreefold site is favored with the parallel frequencies (the frequencies of O atom paralleling the metal surface) of 342 and 538 cm . On Cr (111), the most favored mode for O atom is found to be the quasi-threefold site with the perpendicular frequency at 553 cm −1 and the parallel frequencies at 253 and 399 cm −1. According to our calculation results, we speculate the most preferred mode for O adsorption on Cr (211) surface is the quasithreefold site with the perpendicular frequency at 583 cm −1 and the parallel frequencies at 449 and 185 cm −1.

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Section: 3supporting

confidence: 73%

Adsorption of O Atom on Cr (100), (110), (111), and (211) Surfaces: An 5-Parameter Morse Potential Method Study

Han¹,

Liu²

2012

Bulletin of the Korean Chemical Society

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“…The ease with which the oxygen insertion step takes place, as implied here, has also been documented by us on Ni(100) [67][68][69][70][71], in that case by using branched alkyl groups to produce ketones (which are more stable and do not rapidly decompose further upon their formation). It should also be pointed out that an alternative alkyl-oxygen bond formation mechanism via an Eley-Rideal step involving gas-phase methyl radicals has been reported on Mo(110) [51,72]. Nevertheless, because of the great affinity of early transition metals toward oxygen, the reverse C-O bond scission reaction is still more favorable on the surfaces of early transition metals, as we discuss next.…”

Section: Oxygen Insertion Stepsmentioning

confidence: 80%

“…Methane production is seen in both cases, a clear indication of the potential for vanadium surfaces to promote certain hydrogenation reactions. Similar chemistry has been documented on the surfaces of single-crystals of other transition metals, both for methylene groups on Cu(100) [21], Cu(110) [22], Ag(111) [23], Ni(100) [24], Ni(110) [25], Pd(100) [26], Pt(111) [27][28][29], Rh(111) [30,31], Ru(001) [32,33], Mo(100) [34,35], and Mo(110) [36], and for methyl moieties on Cu(100) [37], Cu(111) [37,38], Cu(110) [22,37], Ni(100) [24,39], Ni(111) [40,41], Ni(110) [42], Pd(100) [43,44], Pt(111) [27,28,45,46], Rh(111) [47,48], Ru(001) [49], Mo(100) [35,50], and Mo(110) [51]. Ethylene production via coupling of methylene is also seen in Fig.…”

Section: Surface Chemistry Of Methylene and Methyl Groupsmentioning

confidence: 99%

Bond Forming Reactions Involving C1 Moieties: Late Versus Early Transition Metal Surfaces

2011

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A brief survey is provided on the contrast in the surface chemistry of C 1 adsorbed species on vanadium versus nickel and platinum single crystals. Mechanistic insights from modern surface-studies under ultrahigh vacuum are offered to explain reaction selectivities in terms of relative rates for different types of surface elementary steps, namely, hydrogenation, dehydrogenation, coupling, and methylene and oxygen insertions. It is clear from the surface chemistry reviewed here that early transition metals such as vanadium are quite reactive, but also that they are still able to promote interesting bond-forming reactions, and could possibly be used to prepare novel catalysis.

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“…Studies by Bol et al show that methyl radicals form methoxy and desorb as gas-phase methyl radicals from O-covered Mo(110) [13], while methyls directly add to surface oxygen [14], producing CO 2 , CO, and formaldehyde on the O-covered Rh(111) surface [15]. Kim et al observed a migratory insertion route for higher alkene production by methylene formed by the dehydrogenation of methyls on Mo(100) with near monolayer coverages of atomic oxygen in 4-fold hollow sites, but also saw this reaction route suppressed at higher oxygen coverages leading to terminal (Mo = O) surface species [16].…”

Section: Introductionmentioning

confidence: 99%

Reactions of methyl groups on a non-reducible metal oxide: The reaction of iodomethane on stoichiometric α-Cr2O3(0001)

et al. 2015

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The reaction of iodomethane on the nearly stoichiometric α-Cr 2 O 3 (0001) surface produces gas phase ethylene, methane, and surface iodine adatoms. The reaction is initiated by the dissociation of iodomethane into surface methyl fragments, −CH 3 , and iodine adatoms. Methyl fragments bound at surface Cr cation sites undergo a rate-limiting dehydrogenation reaction to methylene, =CH 2 . The methylene intermediates formed from methyl dehydrogenation can undergo coupling reactions to produce ethylene via two principle reaction pathways:(1) direct coupling of methylene and (2) methylene insertion into the methyl surface bond to form surface ethyl groups which undergo β-H elimination to produce ethylene. The liberated hydrogen also combines with methyl groups to form methane. Iodine adatoms from the dissociation of iodomethane deactivate the surface by simple site blocking of the surface Cr 3+ cations.

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Probing the Role of Oxygen Coordination in Hydrocarbon Oxidation: Methyl Radical Addition to Oxygen on Mo(110)

Cited by 40 publications

References 28 publications

Adsorption of O Atom on Cr (100), (110), (111), and (211) Surfaces: An 5-Parameter Morse Potential Method Study

Adsorption of O Atom on Cr (100), (110), (111), and (211) Surfaces: An 5-Parameter Morse Potential Method Study

Bond Forming Reactions Involving C1 Moieties: Late Versus Early Transition Metal Surfaces

Reactions of methyl groups on a non-reducible metal oxide: The reaction of iodomethane on stoichiometric α-Cr2O3(0001)

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