Structure of the (110) 
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 surfaces

Mansley, Zachary R.; Mizzi, Christopher A.; Koirala, Pratik; Wen, Jianguo; Marks, Laurence D.

doi:10.1103/physrevmaterials.4.045003

Cited by 5 publications

(10 citation statements)

References 31 publications

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“…The support particles primarily form faceted, cuboidal shapes that expose the pseudocubic (100) planes [note: the Pbnm LnScO 3 unit cell contains 2 pseudocubic units defined by the {110} and (002) planes]. The structure of the (110) surface has been previously studied, − ,− and the double layer structure observed in Figure b agrees well with the results of those studies. Analysis by BET yields surface areas of approximately 6 m 2 /g for all of the supports.…”

Section: Resultssupporting

confidence: 80%

“…Secondary electron images of the different LnScO 3 support nanoparticles (a), with an aberration-corrected profile image of the surface of SmScO 3 (b). Highlighted in red is an inset multislice simulation generated using the MacTempasX program based on a double layer surface structure. ,, …”

Section: Resultsmentioning

confidence: 99%

“…Additionally, some microscopy was performed using a JEOL ARM300F at 300 kV for nanoparticle morphology determination, and a Hitachi HD-2300 scanning transmission electron microscope at 200 kV was used to observe the morphology of the support using secondary electrons. Image simulations were performed using the MacTempasX software package using typical ACAT working conditions (<10 μm Cs, 40 nm focal spread) and the previously reported surface structure with atomic positions minimized from DFT calculations. − …”

Section: Methodsmentioning

confidence: 99%

“…DFT calculations were performed for the bulk materials using the all-electron augmented plane wave + local orbitals WIEN2K package , with on-site hybrids , and the PBEsol functional . As discussed previously, − , the LnScO 3 system is adequately described using on-site hybrid fractions of 0.38, 0.50, and 0.80 for the Ln 4f, Ln 5d, and Sc 3d orbitals, respectively, and muffin-tin radii of 2.02, 1.82, and 1.68 for the Ln, Sc, and O atoms, respectively. Note that the lanthanide 4f electrons are included in the valence band in these calculations, not forced into the core; previous work , clearly indicated that this matters.…”

Section: Methodsmentioning

confidence: 99%

“…We aim to minimize these complicating factors using a series of structurally similar LnScO 3 supports (Ln = La, Nd, and Sm). These supports share the Pbnm orthorhombic perovskite structure, , a Sc-rich surface termination, − have similar electronic structures, − and are a good lattice match for many noble metal catalysts in terms of the pseudocubic unit cell. As a result, many of the aforementioned independent variables, such as structural symmetry and surface chemistry, are close to identical across the series, and catalytic effects stemming from any changes to the support can be isolated and identified.…”

Section: Introductionmentioning

confidence: 99%

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Identifying Support Effects in Au-Catalyzed CO Oxidation

et al. 2021

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Some catalytic oxide supports are more equal than others, with numerous variable properties ranging from crystal symmetry to surface chemistry and electronic structure. As a consequence, it is often very difficult to determine which of these act as the driver of performance changes observed in catalysis. In this work, we hold many of these variable properties constant with structurally similar LnScO3 (Ln = La, Sm, and Nd) nanoparticle supports with cuboidal shapes and a common Sc-rich surface termination. Using CO oxidation over supported Au nanoparticles as a probe reaction, we observe higher activation energy and a slower rate using NdScO3 as the support material. This change is found to correlate to the strength of CO2 binding to the support surface, identified by temperature-programmed desorption measurements. The change is due to differences in the 4f electrons of the lanthanide cations, the cations’ Lewis acidity, and the inductive effect they impose.

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Section: Resultssupporting

confidence: 80%

Section: Resultsmentioning

confidence: 99%

Section: Methodsmentioning

confidence: 99%

Section: Methodsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Identifying Support Effects in Au-Catalyzed CO Oxidation

et al. 2021

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Wet to Dry Controls Lanthanide Scandate Synthesis

2023

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The choice of temperature and gas conditions used in a water pressure-controlled reactor is guided by density functional theory (DFT) to synthesize nearly phase-pure lanthanide scandate nanoparticles (LnScO3, Ln = La, Nd, Sm, Gd). In this synthetic method, low water-vapor partial pressures, well below water’s gas liquidus, inhibit particle growth, while an excess of water vapor results in undesired rare-earth hydroxide and oxyhydroxide secondary phases. The optimal humidity for high-purity LnScO3 particle synthesis is shown to vary with the lanthanide; DFT is used to calculate the thermodynamics of secondary phase formation for each lanthanide tested such that the role of water vapor may be quantified and used to maintain phase purity (greater than 96 mol %) across the series. The combination of thermodynamic calculation and experimental confirmation with this pressure-controlled reactor provides an opportunity to explore analogous syntheses of other inorganic perovskite nanoparticles.

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Binding Strengths and Orientations in CO₂ Adsorption on Cationic Scandium Oxides: Governing Factor Revealed by a Combined Infrared Spectroscopy and Theoretical Study

Liu,

Han,

Chen

et al. 2024

J. Phys. Chem. A

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Carbon dioxide (CO2) adsorption is a critical step to curbing carbon emissions from fossil fuel combustion. Among various options, transition metal oxides have received extensive attention as promising CO2 adsorbents due to their affordability and sustainability for large-scale use. Here, the nature of binding interactions between CO2 molecules and cationic scandium oxides of different sizes, i.e., ScO+, Sc2O2 +, and Sc3O4 +, is investigated by mass-selective infrared photodissociation spectroscopy combined with quantum chemical calculations. The well-accepted electrostatic considerations failed to provide explanations for the trend in the binding strengths and variations in the binding orientations between CO2 and metal sites of cationic scandium oxides. The importance of orbital interactions in the driving forces for CO2 adsorption on cationic scandium oxides was revealed by energy decomposition analyses. A molecular surface property, known as the local electron attachment energy, is introduced to elucidate the binding affinity and orientation-specific reactivity of cationic scandium oxides upon the CO2 attachment. This study not only reveals the governing factor in the binding behaviors of CO2 adsorption on cationic scandium oxides but also serves as an archetype for predicting and rationalizing favorable binding sites and orientations in extended surface–adsorbate systems.

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Structure of the (110) LnScO3 (Ln=Gd,Tb,Dy) surfaces

Cited by 5 publications

References 31 publications

Identifying Support Effects in Au-Catalyzed CO Oxidation

Identifying Support Effects in Au-Catalyzed CO Oxidation

Wet to Dry Controls Lanthanide Scandate Synthesis

Binding Strengths and Orientations in CO₂ Adsorption on Cationic Scandium Oxides: Governing Factor Revealed by a Combined Infrared Spectroscopy and Theoretical Study

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Structure of the (110) LnScO3 (Ln=Gd,Tb,Dy) surfaces

Cited by 5 publications

References 31 publications

Identifying Support Effects in Au-Catalyzed CO Oxidation

Identifying Support Effects in Au-Catalyzed CO Oxidation

Wet to Dry Controls Lanthanide Scandate Synthesis

Binding Strengths and Orientations in CO2 Adsorption on Cationic Scandium Oxides: Governing Factor Revealed by a Combined Infrared Spectroscopy and Theoretical Study

Contact Info

Product

Resources

About

Binding Strengths and Orientations in CO₂ Adsorption on Cationic Scandium Oxides: Governing Factor Revealed by a Combined Infrared Spectroscopy and Theoretical Study