Adsorption and Reaction of CO2 on Metal Surfaces. Detection of an Intrinsic Precursor to Dissociation

Bartoś, B.; Freund, Hannsjörg; Kuhlenbeck, Helmut; Neumann, M.

doi:10.1007/978-3-642-72675-0_13

Cited by 12 publications

(10 citation statements)

References 25 publications

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“…7). These peaks are distinctly different from those observed following CO, adsorption on a clean Rh surface, and agree well with those derived theoretically [34] and established experimentally for bent CO; bonded to a clean Ni(ll0) surface [20]. As no signals due to adsorbed CO and 0 were detected in the photoemission spectra at this temperature, the above features can be attributed unambiguously to the formation of the undissociated CO; radical anion.…”

Section: High K Coueruge 8 = 033supporting

confidence: 85%

“…The adsorption of CO2 on a clean Rh(lll) surface at 90 K suppressed the intensity of the emission of the d-band of Rh, and three new lines appeared in the UPS spectrum, at 6.6, 10.7 and 12.1 eV with respect to the Fermi energy ( fig. 1 [20] and Fe 121.221. The intensities of the peaks increased slightly with exposure and they reached a saturation value at around 60 L. The positions of the peaks did not show any variation with the surface concentration of COz.…”

Section: Resultsmentioning

confidence: 96%

“…Recently, a very thorough theoretical work was devoted to the bonding and reactivity of CO, on clean metal surfaces and the formation of the CO; anion in the interaction of CO, with Ni metal has also been postulated [34]. This postulation was confirmed experimentally on Ni( 110) by subsequent angle-resolved photoemission studies [20]. The formation of CO; has also been detected on a reactive Fe(ll1) surface [22].…”

Section: Generul Churucteristicsmentioning

confidence: 96%

“…the reactivity of K-promoted Rh is similar to those of clean Ni(ll0) and Fe(l11) surfaces. where CO, was found to dissociate at 250 and 180 K. respectively [20,22].…”

Section: High K Coueruge 8 = 033mentioning

confidence: 99%

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Photoelectron spectroscop1c studies of the adsorption of CO2 on potassium-promoted Rh(111) surface

1988

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Adsorption of CO, has been studied on clean and potassium-dosed Rh( 11 1) surface\ bv mean\ of UPS and XPS. CO1 adsorb.\ molecularly at 90 K on clean Rh without a xtrang influence on the electronic structure of the adsorbed layer. Adsorptton of C'02 on potassium-dosed Rh(l II) (6, = 0.33) at 100 K and annealing the adsorbed iayr zt 131 K producrd thrw pwks st 5.2. ti 7 and 10.9 CV in the Hell spectrum and 532.X for O(lh) and 290.5 cV for C( Is) in XPS. rhcw emissions were attributed to the formation of CO; radical antons. At higher temperaturrz the CO, radical is transformed into carbonate and CO. Carbonate species i\ charxterired hq the 3.5. X.4 and 10.2 eV peaks in UPS. and by C(ls) at 2X9.0 eV and O(ls) at 531.X eV levels III XPS. At lower potassium coverage ( 8 K = 0.1). carhonatr formatwn was not ohxrved, but the C'O1 anion radical dissociated to CO and 0 at I31 179 K. This pnuxs was accompanied hy the ;tppearanc~! t)f photoemission peaks at X.2. 11.2 and 6.0 eV.

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Section: High K Coueruge 8 = 033supporting

confidence: 85%

Section: Resultsmentioning

confidence: 96%

Section: Generul Churucteristicsmentioning

confidence: 96%

“…the reactivity of K-promoted Rh is similar to those of clean Ni(ll0) and Fe(l11) surfaces. where CO, was found to dissociate at 250 and 180 K. respectively [20,22].…”

Section: High K Coueruge 8 = 033mentioning

confidence: 99%

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Photoelectron spectroscop1c studies of the adsorption of CO2 on potassium-promoted Rh(111) surface

1988

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“…The formation of reduced species can result following a series of dissociation steps upon CO 2 adsorption via CO species to adventitious-like (C–C/C–H) species (Figure C, left branch). In ultra-high vacuum (UHV) studies conducted on single-crystal metals, it is postulated that the work function strongly dictates the formation of chemisorbed CO 2 – , where a clean metal with a work function lower than 5 eV can activate CO 2 , as a precursor to dissociation . These effects have been widely observed on oriented Ni single crystals and extended to oxides such as Fe 2 O 3 for conversion of CO 2 to reduced CO and C species by dissociation at high temperatures (500 °C) and high rates .…”

Section: Resultsmentioning

confidence: 99%

CO₂ Reactivity on Cobalt-Based Perovskites

Hwang¹,

Rao²,

Katayama

et al. 2018

J. Phys. Chem. C

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Understanding the interaction of CO2 with perovskite metal oxide surfaces is crucial for the design of various perovskite (electro)chemical functionalities, such as solid oxide fuel cells, catalytic oxidation reactions, and gas sensing. In this study, we experimentally investigated the reactivity of CO2 with a series of cobalt-based perovskites (i.e., LaCoO3, La0.4Sr0.6CoO3, SrCoO2.5, and Pr0.5Ba0.5CoO3−δ) by a combined ambient-pressure XPS (AP-XPS) and diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) approach. Isobaric measurements by AP-XPS on epitaxial pulsed laser deposition-grown (100)-oriented thin films under 1 mTorr CO2 showed the formation and uptake of adsorbed adventitious-like C–C/C–H, −CO species, monodentate carbonate, and bidentate (bi)carbonates. DRIFTS measurements on powder samples under CO2 atmosphere revealed the presence of multiple configurations of carbonate in the asymmetric O–C–O stretching region with peak splittings of ∼100 and ∼300 cm–1 correlated to the monodentate- and bidentate-bound carbonate adsorbates, respectively. The synergy between chemical state identification by AP-XPS and vibrational state detection by DRIFTS allows both the carbonaceous species type and the configuration to be identified. We further demonstrate that the surface chemistry of the A-site cation strongly influences CO2 reactivity; the La, Sr, and Ba cations in the LaCoO3, La0.4Sr0.6CoO3, SrCoO2.5, and Pr0.5Ba0.5CoO3 thin films showed significant carbon adsorbate speciation. Additionally, we link the La0.4Sr0.6CoO3 surface chemistry to its surface reactivity toward formation of bidentate (bi)carbonate species via exchange of lattice oxygen with carbonate oxygen. In conclusion, we show that the perovskite electronic structure ultimately dictates the driving force for formation of oxidized oxo-carbonaceous species (CO3) versus reduced species (C–C/C–H). A higher O 2p-band center relative to the Fermi level was correlated with a higher degree of (bi)carbonate formation relative to the other carbonaceous species observed (C–C/C–H and −CO) due to a more facile charge transfer from oxygen states at the Fermi level to free CO2 gas.

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Reactivity of CO₂ on Clean and Hydrogen‐Covered Rhenium Single Crystal Surfaces

Chacham

Asscher

1989

Israel Journal of Chemistry

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The adsorption and dissociationof CO 2 were studied on clean and H r precovered Re(OOOI) and Re(I 120)surfaces. MolecularCO 2 lies linear and parallel to the surface at crystal temperatures below 115 K, as indicated by high-resolution electron energy loss spectroscopy. Upon heating the surface during temperatureprogrammed desorption experiments, a fraction of the molecules dissociates. It is found that dissociationis more effective on the smooth Re(OOOI) surfacethan on the rough Re(1120) one. A model for a possibleactive site which may account for the observedstructure sensitivityis discussed. At adsorption temperatures above 150K, a sharp decrease in the dissociation probability is observed, which is explained in terms of a faster competing desorption process. H 2 preadsorbed on Re(OOOI) was found mostly to block the adsorption of molecular CO 2 and to destabilize the adsorbate. Asa result, the dissociationof CO 2 decreaseswith increasingH 2 coverage.

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Adsorption and Reaction of CO2 on Metal Surfaces. Detection of an Intrinsic Precursor to Dissociation

Cited by 12 publications

References 25 publications

Photoelectron spectroscop1c studies of the adsorption of CO2 on potassium-promoted Rh(111) surface

Photoelectron spectroscop1c studies of the adsorption of CO2 on potassium-promoted Rh(111) surface

CO₂ Reactivity on Cobalt-Based Perovskites

Reactivity of CO₂ on Clean and Hydrogen‐Covered Rhenium Single Crystal Surfaces

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Adsorption and Reaction of CO2 on Metal Surfaces. Detection of an Intrinsic Precursor to Dissociation

Cited by 12 publications

References 25 publications

Photoelectron spectroscop1c studies of the adsorption of CO2 on potassium-promoted Rh(111) surface

Photoelectron spectroscop1c studies of the adsorption of CO2 on potassium-promoted Rh(111) surface

CO2 Reactivity on Cobalt-Based Perovskites

Reactivity of CO2 on Clean and Hydrogen‐Covered Rhenium Single Crystal Surfaces

Contact Info

Product

Resources

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CO₂ Reactivity on Cobalt-Based Perovskites

Reactivity of CO₂ on Clean and Hydrogen‐Covered Rhenium Single Crystal Surfaces