On the role of formate species in the reactions of carbon oxides (CO−CO2) with hydrogen or water

Deluzarche, A.; Hindermann, J. P.; Kieffer, R.; Kiennemann, A.

doi:10.1007/bf03055538

Cited by 30 publications

(9 citation statements)

References 88 publications

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“…In our UV-Raman adsorption studies over Ti grafted MCM-41 the spectroscopic data show that both formic and acetic acid dissociate on the surface of the mesoporous silicalite to form a carboxylate coordinated to the grafted Ti species, most likely involving a dioxo bridge [37]. This results in the loss of the tetrahedral structure responsible for the resonance TiO 4 Raman peak.…”

Section: Discussionmentioning

confidence: 75%

Mechanistic and Adsorption Studies of Relevance to Photocatalysts on Titanium Grafted Mesoporous Silicalites

2011

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Ti-SBA-15 and Ti-MCM-41 were synthesized and evaluated as possible photocatalysts for the reduction of CO 2 , and for the photo-Kolbe decomposition of acetic acid. UV-Raman was used to study the adsorption of carbon dioxide, water, formic acid, and acetic acid over Ti-MCM-41 by monitoring the UV enhanced resonance peak of the totally symmetric stretching band of the grafted Ti species at 1,085 cm -1 . Acetic and formic acid dissociate on Ti-SBA-15 and Ti-MCM-41 to form acetate and formate, respectively. The conjugate bases subsequently interact strongly with Ti sites. Water interacts with the Ti sites, while no change in the amplitude of the 1,085 cm -1 band is observed in the presence of CO 2 . Photocatalysis experiments indicate that these mesoporous silicalites are active in the photo-Kolbe decomposition of acetic acid. CO 2 is formed by reaction of a hole with the acetate carboxylate groups. The methyl radical co-products react with a surface proton and an electron to form methane. No products resulting from the dimerization of methyl radicals are observed, presumably because of the highly dispersed active sites.

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Section: Discussionmentioning

confidence: 75%

Mechanistic and Adsorption Studies of Relevance to Photocatalysts on Titanium Grafted Mesoporous Silicalites

2011

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“…Insofar as stable products of carbon monoxide reduction are formed in two-electron transitions, relationships (2b) and (2) describe real processes only for even values of p. 3 In this case, the formation of methanol occurs at n = 1, p = 4, and z = 0.…”

Section: Methodsmentioning

confidence: 99%

“…The exchange current of this reaction on a heterogeneous surface is largely determined by most weakly bound copper adatoms [23,24]. In this connection, it is extremely difficult to unambiguously choose between 3 Hence, for p = 2m, reactions (1) and (2) become identical. the mediator catalysis mechanisms of carbon-monoxide electroreduction by the reactions (1a)-(1b) or (2a)-(2b).…”

Section: Methodsmentioning

confidence: 99%

Copper Ion Catalyzed Electroreduction of Carbon Monoxide on Iridium Electrode

Podlovchenko

Gladysheva

2005

Russ J Electrochem

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Substantial cathodic currents are observed on iridium electroplates in 0.5 M H 2 SO 4 + (0.001-0.005 M) CuSO 4 + CO (sat) at potentials positive with respect to the Cu/Cu 2+ equilibrium potential. These currents are shown to correspond to electroreduction of both CO and Cu 2+ ions to Cu + , where the latter ions are formed in amounts indicating the formation of complexes. Among the products of CO reduction, methanol and formaldehyde are identified. A possible mechanism of CO reduction is discussed. It is assumed that both copper adatoms and Cu + ions can play the role of intermediates in the mediator catalysis.

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“…Although this route was considered to be a minor one in the production of CH 4 , it Was demonstrated that formate species bonded adjacent to the Rh cannot be regarded as a totally inactive surface species in the hydrogenation of CO and CO 2 [11]. An important contribution to this field was provided by Deluzarche et al [12][13][14], who developed a sensitive method of chemical trapping for the detection of surface formate. They presented convincing evidence that the formate species is an important surface intermediate in CH 30R synthesis.…”

Section: Introductionmentioning

confidence: 99%

“…More information on the role of the formate species in the reactions of carbon oxides with H 2 on other catalysts can be found in an excellent review by Deluzarche et aI. [14].…”

Section: Introductionmentioning

confidence: 99%

Adsorption of HCOOH on Rh(111) and its reaction with preadsorbed oxygen

Solymosi¹,

Kiss²,

Kovács³

1987

Surface Science Letters

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The interaction of formic acid with clean and oxygen-dosed Rh(lll) surfaces has been investigated by electron energy loss (in the electronic range), thermal desorption and photoelectron spectroscopy. Formic acid adsorbs readily on the Rh(l1l) surface at 100 K with a high sticking probability. Three adsorbed states have been distinguished: a condensed layer (T p = 170 K), a chemisorbed layer (T p = 202 K) and the formation of formate species. The latter is stable up to 200 K, but decomposes completely at 200-250 K. The major products are: H 2 (T p = 323 K) and CO 2 (T p = 255-290 K), but H:P (T p = 263 K) and CO (1~= 530 K) are also fonned.Preadsorbed oxygen exerted a readily observable influence on the interaction of HCOOH with the Rh(l11) surface. It increased the extent of dissociation of HCOOH and extended the region of stability of surface formate by at least 80-100 K. This was demonstrated by higher stability of photoemission peaks due to formate and by simultaneous production of CO 2 and H 20 with T p = 377-385 K at saturation oxygen coverage.

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On the role of formate species in the reactions of carbon oxides (CO−CO2) with hydrogen or water

Cited by 30 publications

References 88 publications

Mechanistic and Adsorption Studies of Relevance to Photocatalysts on Titanium Grafted Mesoporous Silicalites

Mechanistic and Adsorption Studies of Relevance to Photocatalysts on Titanium Grafted Mesoporous Silicalites

Copper Ion Catalyzed Electroreduction of Carbon Monoxide on Iridium Electrode

Adsorption of HCOOH on Rh(111) and its reaction with preadsorbed oxygen

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