Adsorption of carbonate species on silver. I. Nature of the surface bond

Patrito, E.M.; Olivera, P.Paredes

doi:10.1016/s0013-4686(98)00227-8

Cited by 19 publications

(12 citation statements)

References 32 publications

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“…For the bicoordinated (bicoord) perpendicular configuration, the adsorption energy is calculated to be 91.2 kcal mol −1 , which is 18.7 kcal mol −1 larger than a value found for its monocoordinated (monocoord) analogue. The present calculations show the same site preference, bicoord > monocoord, as predicted by MP2, but the calculated adsorption energy is 25.8 kcal mol −1 smaller than the MP2 value [9]. Previous study has displayed that MP2 misestimated the relative energy of the C 2v isomer of CO 3 to its D 3h analogue and the adsorption energy of CO 3 on Ag(100) could then be largely overestimated by MP2.…”

Section: Adsorption Of Co 3 On Ag(100)supporting

confidence: 66%

“…The calculated structures in Ref. 9 are both perpendicular to the surface, instead of a near parallel configuration on Ag(110). Density functional theory (DFT) methods with generalized gradient approximations (GGA) for the exchange-correlation potential have shown great successes in describing adsorbate-surface systems.…”

Section: Playsmentioning

confidence: 96%

“…Its adsorption energy on Ag(100) is calculated to be 117 kcal mol −1 for the bicoordinated perpendicular configuration at the MP2 level by Patrito and Olivera [9], which is 21 kcal mol −1 larger than that of its monocoordinated analogue. Upon the adsorption, a charge of 0.518 e and 0.488 e has been transferred from Ag(100) to CO 3 , respectively.…”

Section: Playsmentioning

confidence: 99%

“…Therefore, the adsorption energy of CO 3 on Ag(100) could be largely overestimated in Ref. 9 since the wrong MP2 energy of C 2v was used as a reference value.…”

Section: Playsmentioning

confidence: 99%

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Adsorption and dissociation of carbon trioxide on Ag(100)

Soo

Qin

2009

Int J of Quantum Chemistry

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ABSTRACT:Using density functional theory methods, we have studied carbon trioxide, its adsorption and dissociation on Ag(100). In the gas phase, two isomers are found, D 3h and C 2v , with the latter of 2.0 kcal mol −1 lower in energy at the PW91PW91/6-31G(d) level. For CO 3 on Ag(100), the calculated adsorption energy is 91.2 and 89.1 kcal mol −1 for the bi-coord perpendicular and tri-coord parallel structures, respectively. Upon the adsorption, 0.50 ∼ 0.56 electron is transferred from silver to CO 3 , indicative of significant ionic characters of the adsorbate-surface bonding. In addition, the geometry of CO 3 is largely changed by its strong interaction with silver. For CO 3(ad) → O (ad) + CO 2(gas) , the energy barrier is calculated to be 19.8 kcal mol −1 through the bi-coord path. The process is endothermic with an enthalpy change of +17.3 ∼ +26.7 kcal mol −1 and the weakly chemisorbed CO 2 is identified as an intermediate on the potential energy surface.

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Section: Adsorption Of Co 3 On Ag(100)supporting

confidence: 66%

Section: Playsmentioning

confidence: 96%

Section: Playsmentioning

confidence: 99%

“…Therefore, the adsorption energy of CO 3 on Ag(100) could be largely overestimated in Ref. 9 since the wrong MP2 energy of C 2v was used as a reference value.…”

Section: Playsmentioning

confidence: 99%

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Adsorption and dissociation of carbon trioxide on Ag(100)

Soo

Qin

2009

Int J of Quantum Chemistry

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“…Spectra in Fig. 6 suggest that SO x species can readily substitute relatively weakly adsorbed carbonyl functionalities on the Pd sites [45,53], while carbonate species formed on the perovskite sites reveal a stronger resistance against displacement due to their relatively higher adsorption energy [54]. In addition, these results also do not rule out the possibility that Pd sites can be relatively more prone to sulfur poisoning with respect to that of the perovskite adsorption sites during the initial stages of poisoning.…”

Section: Quantitative Surface Analysis Via Xpsmentioning

confidence: 89%

Sulfur Poisoning and Regeneration Behavior of Perovskite-Based NO Oxidation Catalysts

et al. 2016

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SO x uptake and release properties of LaMnO 3 , Pd/LaMnO 3 , LaCoO 3 and Pd/LaCoO 3 perovskites were investigated via in situ Fourier transform infrared (FTIR) spectroscopy, temperature programmed desorption and X-ray photoelectron spectroscopy. Sulfation of the perovskite leads to the formation of surface sulfite/sulfate and bulk-like sulfate species. Pd addition to LaMnO 3 and LaCoO 3 significantly increases the sulfur adsorption capacity. Pd/LaMnO 3 sample accumulates significantly more sulfur than LaMnO 3 ; however it can also release a larger fraction of the accumulated SO x species in a reversible fashion at elevated temperatures in vacuum. This is not the case for Co-based materials, where thermal regeneration of bulk sulfates on poisoned LaCoO 3 and Pd/ LaCoO 3 is extremely ineffective under similar conditions. However, in the presence of an external reducing agent such as H 2 (g), Pd/LaMnO 3 requires much lower temperature (873 K) for complete sulfur regeneration as compared to that of Pd/LaCoO 3 (973 K). Sequential CO and SO x adsorption experiments performed via in situ FTIR indicate that in the presence of carbonyls and/or carbonates, Pd adsorption sites may have a stronger affinity for SO x as compared to that of the perovskite surface, particularly in the early stages of sulfur poisoning.

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