Carbon monoxide and carbon dioxide adsorption on cerium oxide studied by Fourier-transform infrared spectroscopy. Part 1.—Formation of carbonate species on dehydroxylated CeO2, at room temperature

Li, Can; Sakata, Yoshihisa; Arai, T.; Domen, Kazunari; Maruya, Ken‐ichi; Onishi, Takaharu

doi:10.1039/f19898500929

Cited by 492 publications

(410 citation statements)

References 2 publications

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“…15,[38][39][40][41][42] Due to the complexity of this band structure, the deconvolution and interpretation of this region was not attempted. The bands in the 3650-3500 cm -1 region were due to the stretching vibration of the ceria surface hydroxyl groups, while that around 2360 cm -1 was associated with gas-phase (and possibly some weakly adsorbed) CO 2 .…”

Section: Resultsmentioning

confidence: 99%

Spectrokinetic Investigation of Reverse Water-Gas-Shift Reaction Intermediates over a Pt/CeO₂ Catalyst

Goguet¹,

Meunier²,

Tibiletti³

et al. 2004

J. Phys. Chem. B

326

230

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The reactivity of the surface species present over a 2%Pt/CeO 2 catalyst during the reverse water-gas-shift (RWGS) reaction was investigated by a detailed operando spectrokinetic analysis. A single reactor common for the kinetic and the spectroscopic measurements was used. The reactor employed was a modified hightemperature diffuse reflectance FT-IR (DRIFT) cell from SpectraTech. The reactivity of the surface species was monitored by DRIFT spectroscopy (DRIFTS) and mass spectrometry (MS) using steady-state isotopic transient kinetic analysis (SSITKA) techniques, i.e., switching between 1% CO 2 + 4% H 2 reaction mixtures containing either 13 CO 2 or 12 CO 2 . The combination of these techniques allowed time-resolved simultaneous monitoring of the variation of the coverage of 12 C and 13 C-containing surface intermediates and the concentration of the gas-phase products 12 CO(g) and 13 CO(g) due to the isotope exchange. These results clearly indicated that surface formates observed by DRIFTS were not the main reaction intermediates for the formation of CO(g) over the present catalyst under these experimental conditions, although the formation of CO(g) from formates was likely to occur to a limited extent. A quantitative analysis of the number of reactive surface species also showed that Pt-bound carbonyls could not be the only reaction intermediate. Surface carbonates are shown as being a main surface intermediate in the formation of CO(g). A reaction scheme involving a direct reoxidation of the ceria support by the CO 2 via surface carbonates is suggested. A parallel between these results and mechanisms previously proposed for CO 2 hydrogenation and CO 2 -reforming (i.e., dryreforming) of methane on redox oxide-supported noble metal is made. In a more general perspective, the present data underlines the feasibility and appropriateness of the DRIFT-MS-SSITKA technique based on a single reactor in providing critical information about the nature of surface species (e.g., kinetic intermediate as opposed to spectator) on catalysts when the surface species are observable by DRIFT spectroscopy.

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Section: Resultsmentioning

confidence: 99%

Spectrokinetic Investigation of Reverse Water-Gas-Shift Reaction Intermediates over a Pt/CeO₂ Catalyst

Goguet¹,

Meunier²,

Tibiletti³

et al. 2004

J. Phys. Chem. B

326

230

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“…47 Compared with previous Diffuse Reflectance Infrared Fourier Transform Spectroscopy (DRIFTS) study of powder Ni-CeO2, 8 the formation of acetates species at room temperature and its subsequent transformation to carbonates species at higher temperature are evident in both cases, but the all the features on the powder system are more pronounced and could be retained at higher temperature, probably due to the multiple crystal facets of powder ceria affect the adsorption/desorption selectivity. In addition, a small peak at 2680 cm -1 corresponding to the ν(OD) derived from the dissociation of D2O, is resolved at 700 K. 48 Correlating this with the Ce(OH)x demonstrated in the AP-XPS results above, the observation of hydroxyls (-OD) verifies the participation of water in the formation of ceria hydroxides while water can be the hydroxyl feed stock for the reforming reaction.…”

Section: Ethanol Reaction On Ceo2(111)mentioning

confidence: 99%

Ambient pressure XPS and IRRAS investigation of ethanol steam reforming on Ni–CeO₂(111) catalysts: an in situ study of C–C and O–H bond scission

Liu

Duchoň

Wang

et al. 2016

Phys. Chem. Chem. Phys.

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“…monodentate, bidentate, tridentate, bridging, and chelating carbonates, carboxylates and carbonites. [17][18][19][20][21][22][23][24][25][26] In such cases the identification of the species and their adsorption sites is often assisted by density functional calculations. [25][26][27][28][29] In particular, interaction of CO molecules with planar CeO 2 (111), CeO 2 (110), and CeO 2 (100) surfaces 27 as well as CeO 2 particles 28 has been modelled by density functional theory (DFT).…”

Section: Introductionmentioning

confidence: 99%

Surface sites on Pt–CeO₂mixed oxide catalysts probed by CO adsorption: a synchrotron radiation photoelectron spectroscopy study

Neitzel

Lykhach

Škála

et al. 2014

Phys. Chem. Chem. Phys.

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By means of synchrotron radiation photoemission spectroscopy, we have investigated Pt-CeO 2 mixed oxide films prepared on CeO 2 (111)/Cu(111). Using CO molecules as a probe, we associate the corresponding surface species with specific surface sites. This allows us to identify the changes in the composition and morphology of Pt-CeO 2 mixed oxide films caused by annealing in an ultrahigh vacuum.Specifically, two peaks in C 1s spectra at 289.4 and 291.2 eV, associated with tridentate and bidentate carbonate species, are formed on the nanostructured stoichiometric CeO 2 film. The peak at 290.5-291.0 eV in the C 1s spectra indicates the onset of restructuring, i.e. coarsening, of the Pt-CeO 2 film. This peak is associated with a carbonate species formed near an oxygen vacancy. The onset of cerium oxide reduction is indicated by the peak at 287.8-288.0 eV associated with carbonite species formed near Ce 3+ cations. The development of surface species on the Pt-CeO 2 mixed oxides suggests that restructuring of the films occurs above 300 K irrespective of Pt loadings. We do not find any adsorbed CO species associated with Pt 4+ or Pt 2+ . The onset of Pt 2+ reduction is indicated by the peak at 286.9 eV in the C 1s spectra due to CO adsorption on metallic Pt particles. The thermal stability of Pt 2+ in Pt-CeO 2 mixed oxide depends on Pt loading. We find excellent stability of Pt 2+ for 12% Pt content in the CeO 2 film, whereas at a Pt concentration of 25% in the CeO 2 film, a large fraction of the Pt 2+ is converted into metallic Pt particles above 300 K.

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Carbon monoxide and carbon dioxide adsorption on cerium oxide studied by Fourier-transform infrared spectroscopy. Part 1.—Formation of carbonate species on dehydroxylated CeO2, at room temperature

Cited by 492 publications

References 2 publications

Spectrokinetic Investigation of Reverse Water-Gas-Shift Reaction Intermediates over a Pt/CeO₂ Catalyst

Spectrokinetic Investigation of Reverse Water-Gas-Shift Reaction Intermediates over a Pt/CeO₂ Catalyst

Ambient pressure XPS and IRRAS investigation of ethanol steam reforming on Ni–CeO₂(111) catalysts: an in situ study of C–C and O–H bond scission

Surface sites on Pt–CeO₂mixed oxide catalysts probed by CO adsorption: a synchrotron radiation photoelectron spectroscopy study

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Carbon monoxide and carbon dioxide adsorption on cerium oxide studied by Fourier-transform infrared spectroscopy. Part 1.—Formation of carbonate species on dehydroxylated CeO2, at room temperature

Cited by 492 publications

References 2 publications

Spectrokinetic Investigation of Reverse Water-Gas-Shift Reaction Intermediates over a Pt/CeO2 Catalyst

Spectrokinetic Investigation of Reverse Water-Gas-Shift Reaction Intermediates over a Pt/CeO2 Catalyst

Ambient pressure XPS and IRRAS investigation of ethanol steam reforming on Ni–CeO2(111) catalysts: an in situ study of C–C and O–H bond scission

Surface sites on Pt–CeO2mixed oxide catalysts probed by CO adsorption: a synchrotron radiation photoelectron spectroscopy study

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Product

Resources

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Spectrokinetic Investigation of Reverse Water-Gas-Shift Reaction Intermediates over a Pt/CeO₂ Catalyst

Spectrokinetic Investigation of Reverse Water-Gas-Shift Reaction Intermediates over a Pt/CeO₂ Catalyst

Ambient pressure XPS and IRRAS investigation of ethanol steam reforming on Ni–CeO₂(111) catalysts: an in situ study of C–C and O–H bond scission

Surface sites on Pt–CeO₂mixed oxide catalysts probed by CO adsorption: a synchrotron radiation photoelectron spectroscopy study