Adsorption of hydrogen, chlorine, and sulfur atoms on α-Cr2O3(0 0 0 1) surfaces: A density functional theory investigation

Nigussa, K.N.; Nielsen, Kjetil L.; Borck, Øyvind; Støvneng, Jon Andreas

doi:10.1016/j.corsci.2011.07.005

Cited by 18 publications

(13 citation statements)

References 34 publications

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“…For the specific systems here (rocksalt and corundum structures), a number of calculations have considered by ab initio methods the base hydroxylated oxide structures, e.g., references, [67][68][69][70][71][72][73][74][75][76][77][78][79][80][81][82][83] both dissociated and molecular adsorption of water, others the additional effects of chloride. 15,51,77,[84][85][86][87] In many respects these papers are at the opposite end compared to the others, as they do not involve so much the Mechanism, Dependencies, and Triggers. Instead they discuss the Driver/thermodynamics for specific crystallographies.…”

Section: Introductionmentioning

confidence: 99%

“…In the presence of chloride, some papers have analyzed slightly different chemistries such as the adsorption of small molecules 15,[67][68]70,77,[84][85][86][87][88] on oxide surfaces, which is a different chemical problem. There has been less analysis on the specific problem of importance, the interaction of chloride with the hydroxylated surface.…”

Section: Introductionmentioning

confidence: 99%

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Competitive Chloride Chemisorption Disrupts Hydrogen Bonding Networks: DFT, Crystallography, Thermodynamics, and Morphological Consequences

Marks¹

2017

Corrosion

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The consequence for aqueous corrosion of chloride ions in an aqueous environment on the surface structure and thermodynamics of hydroxylated magnesia (001) and alpha-alumina (001) and (100) is analyzed using density functional methods. It is shown that there is competitive chemisorption between hydroxide and chloride, with the chloride disrupting the hydrogen bonding network on the surface. There is a significant crystallographic dependence, as well as dependencies upon the environment in terms of the pH and chloride molarity. An analysis of the results in terms of existing, competing models in the literature for the effect of chloride indicates that rather than the existing models being competitors, most are correct but incomplete. Rather than the different models being viewed as competitors, or each being rate determining for some specific set of conditions, the majority are simultaneously correct. Conventional oxide surface science extrapolation of the results yields qualitative conclusions for the effects of, for instance, alloy dopants which are consistent with existing experimental data. The analysis also indicates the existence of a number of new phenomena in corrosion, for instance local galvanic couples due to the work-function change with chloride chemisorption, as well as thermodynamic dewetting of the oxide film.

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Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Competitive Chloride Chemisorption Disrupts Hydrogen Bonding Networks: DFT, Crystallography, Thermodynamics, and Morphological Consequences

Marks¹

2017

Corrosion

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“…In the reported work, authors highlight the sensing performance of Cl 2 sensor in air based NASICON and oxide electrode. They report that Cr 2 O 3 single oxide shows a high sensitivity to chlorine gas in air atmosphere at 300 • C. Nigussa et al 24 proposed the adsorption of hydrogen, chlorine, and sulfur on α-Cr 2 O 3 (0001) surfaces through density functional theory. Chlorine, hydrogen and sulfur get adsorbed on Cr 2 O 3 and Cr terminated α-Cr 2 O 3 surfaces in the reported work.…”

Section: Adsorption Characteristics Of CL 2 On α-Cr 2 O 3 Nanostructuresmentioning

confidence: 97%

A first-principles study of chlorine adsorption characteristics on α-Cr2O3 nanostructures

Nagarajan

Chandiramouli

2015

J Chem Sci

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The structural stability, electronic and adsorption properties of chlorine on pristine, Zn, W and Nsubstituted α-Cr 2 O 3 nanostructures are successfully optimized and simulated with the help of density functional theory utilizing B3LYP/ LanL2DZ basis set. The structural stability of α-Cr 2 O 3 nanostructures are discussed in terms of formation energy. The electronic properties of pristine, Zn, W and N-substituted α-Cr 2 O 3 nanostructures are described with HOMO-LUMO gap, ionization potential and electron affinity. Dipole moment and point symmetry group of pristine, Zn, W and N-substituted α-Cr 2 O 3 nanostructures are reported. The adsorption characteristics of Cl 2 on α-Cr 2 O 3 materials are investigated and the prominent adsorption sites of Cl 2 on α-Cr 2 O 3 nanostructures are identified. The important parameters such as adsorbed energy, energy gap, average energy gap variation and Mulliken population analysis are used to find the favourable adsorption site of Cl 2 on α-Cr 2 O 3 base material. The substitution of impurities such as Zn, W and N in α-Cr 2 O 3 nanostructures enhances the Cl 2 adsorption characteristics in the mixed gas environment.

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“…Two Cr-terminated surfaces were considered, one with a Cr 2 -layer, and another where half of the Cr-atoms have been removed, the latter being the more commonly studied surface termination of (0001) Cr 2 O 3 surfaces [27,28]. Several oxygen terminated surfaces have been studied [29,30]…”

Section: Cr 2 O 3 Surfacesmentioning

confidence: 99%

Surface and bulk properties of chromium oxide: Implications for reduction by methane

Skjelbred

Åstrand

Støvneng

et al. 2015

AIP Conference Proceedings

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A computational method for Cr 2 O 3 and Cr 3 C 2 has been established based on a systematic investigation of functionals, basis sets and corrections for dispersion, self-interaction and relativistic effects. The suggested method comprises of the PBE functional with Grimme's dispersion correction, the TZ2P basis set with a frozen core of up to 2p for chromium and 1s for oxygen and carbon, and with the zeroth-order regular approximation for relativistic effects, and is in good agreement with experimental results for both bulk crystals and surface structures. Self-interactions have been corrected for by the DFT + U approach, but it still gives band gaps significantly different from the experimental band gap. We have also calculated the adsorption energy of methane on a chromium terminated (0001) Cr 2 O 3 surface, and the significance of dispersion and self-interaction corrections for the adsorption of methane on Cr 2 O 3 was found to be substantial.

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Adsorption of hydrogen, chlorine, and sulfur atoms on α-Cr2O3(0 0 0 1) surfaces: A density functional theory investigation

Cited by 18 publications

References 34 publications

Competitive Chloride Chemisorption Disrupts Hydrogen Bonding Networks: DFT, Crystallography, Thermodynamics, and Morphological Consequences

Competitive Chloride Chemisorption Disrupts Hydrogen Bonding Networks: DFT, Crystallography, Thermodynamics, and Morphological Consequences

A first-principles study of chlorine adsorption characteristics on α-Cr2O3 nanostructures

Surface and bulk properties of chromium oxide: Implications for reduction by methane

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