Stability field diagrams for Ln–O–Cl systems

Jacob, Κ. T.; Dixit, Apoorva; Rajput, Arneet

doi:10.1007/s12034-016-1219-6

Cited by 18 publications

(7 citation statements)

References 16 publications

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“…In the Ln 2 O 3 sequioxide materials favored by most lanthanoids [CeO 2 is more stable than Ce 2 O 3 ; europium favors a mixed Eu(ii, iii) oxide over Eu 2 O 3 ], the partially filled 4f band generally lies within the conventional band gaps. [50][51][52][53][54] For Ce 2 O 3 , each Ce center has a singly occupied 4f orbital, and Sm 2 O 3 has a 4f 5 occupancy (the atomic number of Sm is 62, the atomic number of Ce is 58). However, the trend from Ce 2 O 3 to Sm 2 O 3 is that the bulk 4f band energy moves closer to the valence band, and in the case of Sm 2 O 3 , the 4f band energy lies very near the valence band.…”

Section: A Sm 4f Subshell Occupancymentioning

confidence: 99%

The electron shuffle: Cerium influences samarium 4f orbital occupancy in heteronuclear Ce–Sm oxide clusters

Kafader

Topolski

Marrero-Colon

et al. 2017

The Journal of Chemical Physics

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The anion photoelectron (PE) spectra along with supporting results of density functional theory (DFT) calculations on SmO, SmCeO, and SmO (y = 1, 2) are reported and compared to previous results on CeO [M. Ray et al., J. Chem. Phys. 142, 064305 (2015)] and CeO (y = 1, 2) [J. O. Kafader et al., J. Chem. Phys. 145, 154306 (2016)]. Similar to the results on CeO clusters, the PE spectra of SmO, SmCeO, and SmO (y = 1, 2) all exhibit electronic transitions to the neutral ground state at approximately 1 eV eBE. The Sm centers in SmO and SmO neutrals can be described with the 4f6s superconfiguration, which is analogous to CeO and CeO neutrals in which the Ce centers can be described with the 4f 6s superconfiguration (Z = Z - 4). The Sm center in CeSmO, in contrast, has a 4f occupancy, while the Ce center maintains the 4f 6s superconfiguration. The less oxidized Sm centers in both SmO and SmCeO have 4f 6s occupancies. The 4f subshell occupancy results in relatively weak Sm-O bond strengths. If this extra 4f occupancy also occurs in bulk Sm-doped ceria, it may play a role in the enhanced O ionic conductivity in Sm-doped ceria. Based on the results of DFT calculations, the heteronuclear Ce-Sm oxides have molecular orbitals that are distinctly localized Sm 4f, Sm 6s, Ce 4f, and Ce 6s orbitals. The relative intensity of two electronic bands in the PE spectrum of SmO exhibits an unusual photon energy-dependence, and the PE spectrum of SmO exhibits a photon energy-dependent continuum signal between two electronic transitions. Several explanations, including the high magnetic moment of these suboxide species and the presence of low-lying quasi-bound anion states, are considered.

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Section: A Sm 4f Subshell Occupancymentioning

confidence: 99%

The electron shuffle: Cerium influences samarium 4f orbital occupancy in heteronuclear Ce–Sm oxide clusters

Kafader

Topolski

Marrero-Colon

et al. 2017

The Journal of Chemical Physics

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“…Thermodynamically, in the Ce−O−Cl system, cerium is able to chemically transform between various oxides and chlorides depending on the partial pressure of oxygen and chlorine in the system. 56 Given sufficiently high O 2 partial pressure and a kinetically available pathway, CeOCl can be converted to CeO 2 and Cl 2 .…”

Section: ■ Results and Discussionmentioning

confidence: 99%

Polyhedral Organic Silsesquioxane Cage Structures Formed via Reaction of Methylchlorosilanes with Re/CeO₂ in Catalytic Oxygen Depletion–Regeneration Cycle

Larsen

McLaughlin

Katsoulis

2022

Ind. Eng. Chem. Res.

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Polyhedral oligomeric silsesquioxane (POSS) cage structures were exclusively generated as the reaction products of methyltrichlorosilane, CH 3 SiCl 3 (or MeSiCl 3 where Me denotes a CH 3 -group), with a supported Re/CeO 2 catalyst at 500 °C. The cage structures are generated by the exchange of oxygen for chlorine in the ceria support under a H 2 reducing atmosphere. Regeneration of the support can occur by passing air over the catalyst at 500 °C, and then the reaction can be repeated. This presents a novel way of generating cage structures exclusively via a gas-phase reaction. Gas chromatography-mass spectrometry (GC-MS) of the reaction products indicates that the cage structures that are formed are Me 6 -T 6 , Me 8 -T 8 , and Me 10 -T 10 . The reaction proceeds at high conversion and high yield toward these POSS cages. When dimethyldichlorosilane ((CH 3 ) 2 SiCl 2 or Me 2 SiCl 2 ) is used as the reactant, mostly cyclic siloxanes D 4 −D 6 are produced. Hydrido-chlorosilane, methyldichlorosilane (CH 3 SiHCl 2 or MeHSiCl 2 ), generates cage structures through an additional Si−H−O ligand exchange reaction that is facilitated by the oxygen vacancies on the ceria support. When Si−H ligands are present, rearrangement reactions are also observed under these conditions and constitute a supplementary process for the formation of the POSS cage structures. Trichlorosilane (HSiCl 3 ) does not form cage structures, but it does undergo rearrangement. It also undergoes Si−H−O ligand exchange with oxygen vacancies on the ceria support to form cristobalite (crystalline SiO 2 ) on the support.

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“…The transformation from SmCl 3 to SmOCl is thermodynamically stable according to the calculated stability field diagram for Sm-O-Cl system. [8] We employ this reaction to prepare SmOCl nanoplates in the present experiment.…”

Section: Resultsmentioning

confidence: 99%

Synthesis Of Samarium Oxychloride Nanoplates By Chemical Vapour Deposition

Chu

Xing

2019

Journal of Experimental Nanoscience

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Samarium oxychloride (SmOCl) is a promising photocatalyst for environment remediation. It is difficult to form SmOCl nanoplate by sophisticated wet chemical techniques used to prepare other layer-structured rare earth oxychloride nanoplates. Here, we report the synthesis of SmOCl nanoplates by chemical vapour deposition (CVD). Transmission electron microscopy characterization reveals that the nanoplates are single crystalline SmOCl with exposed f001g facets. Two-dimensional growth of SmOCl nanoplates is improved by adding decaborane in the atmosphere of CVD system. The largest size of SmOCl nanoplates approaches $5 lm. The growth process of SmOCl nanoplates is studied. This result shows that CVD is a suitable method to grow large SmOCl nanoplates.

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Stability field diagrams for Ln–O–Cl systems

Abstract: Isothermal stability field diagrams for Ln−O−Cl systems

Cited by 18 publications

References 16 publications

The electron shuffle: Cerium influences samarium 4f orbital occupancy in heteronuclear Ce–Sm oxide clusters

The electron shuffle: Cerium influences samarium 4f orbital occupancy in heteronuclear Ce–Sm oxide clusters

Polyhedral Organic Silsesquioxane Cage Structures Formed via Reaction of Methylchlorosilanes with Re/CeO₂ in Catalytic Oxygen Depletion–Regeneration Cycle

Synthesis Of Samarium Oxychloride Nanoplates By Chemical Vapour Deposition

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Stability field diagrams for Ln–O–Cl systems

Abstract: Isothermal stability field diagrams for Ln−O−Cl systems

Cited by 18 publications

References 16 publications

The electron shuffle: Cerium influences samarium 4f orbital occupancy in heteronuclear Ce–Sm oxide clusters

The electron shuffle: Cerium influences samarium 4f orbital occupancy in heteronuclear Ce–Sm oxide clusters

Polyhedral Organic Silsesquioxane Cage Structures Formed via Reaction of Methylchlorosilanes with Re/CeO2 in Catalytic Oxygen Depletion–Regeneration Cycle

Synthesis Of Samarium Oxychloride Nanoplates By Chemical Vapour Deposition

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Polyhedral Organic Silsesquioxane Cage Structures Formed via Reaction of Methylchlorosilanes with Re/CeO₂ in Catalytic Oxygen Depletion–Regeneration Cycle