<mml:math xmlns:mml="http://www.w3.org/1998/Math/MathML"><mml:msub><mml:mi>ScO</mml:mi><mml:mi>x</mml:mi></mml:msub></mml:math>
 rich surface terminations on lanthanide scandate nanoparticles

Mansley, Zachary R.; Paull, Ryan J.; Greenstein, Emily P.; Wen, Jianguo; Poeppelmeier, Kenneth R.; Marks, Laurence D.

doi:10.1103/physrevmaterials.5.125002

Cited by 3 publications

(6 citation statements)

References 53 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…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%

“…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%

See 3 more Smart Citations

Identifying Support Effects in Au-Catalyzed CO Oxidation

et al. 2021

Self Cite

View full text Add to dashboard Cite

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.

show abstract

Section: Resultssupporting

confidence: 80%

Section: Resultsmentioning

confidence: 99%

Section: Methodsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 2 more Smart Citations

Identifying Support Effects in Au-Catalyzed CO Oxidation

et al. 2021

Self Cite

View full text Add to dashboard Cite

show abstract

“…14−16 Across the LnScO 3 series, they also share similar electronic structures and surface terminations. 17,18 However, while it is common to extrapolate or assume linear trends across the lanthanide series because of linearly changing properties like Ln 3+ cation radius or Ln−O bond length, 19,20 evidence suggests that the Ln 3+ electronic structure 21−25 and resulting properties such as Lewis acidity 11,26 do not trend linearly with Ln. Thus, without a robust understanding of the thermodynamics of their formation, it is difficult to predict how synthetic conditions for LnScO 3 will vary as the lanthanide is changed.…”

Section: ■ Introductionmentioning

confidence: 99%

Wet to Dry Controls Lanthanide Scandate Synthesis

2023

Self Cite

View full text Add to dashboard Cite

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.

show abstract

Observing the Surface Termination of LaScO₃ Perovskite Using Solid-State Nuclear Magnetic Resonance

Zhao,

Greenstein,

Peczak

et al. 2024

J. Am. Chem. Soc.

View full text Add to dashboard Cite

Materials with well-defined surfaces are drawing increased attention for the design of bespoke catalysts and nanomaterials. Gaining a detailed understanding of the surfaces of these materials is an important challenge, which is often complicated by surface polymorphism and dynamic restructuring. We introduce the use of surface-enhanced NMR spectroscopy for the observation of such surfaces, focusing on LaScO3 as an example. We show that double-resonance NMR experiments correlating surface oxygen and probe molecules to the 139La and 45Sc nuclei at the surface reveal the material to be terminated by a ScO x monolayer. Surface-selective 17O and 45Sc NMR experiments further showed the material to be hydroxyl terminated and that the surface may be prone to dynamic restructuring as a result of moisture exposure. Perhaps most interestingly, surface-selective 139La NMR experiments revealed the existence of previously undetected surface lanthanum defects, suggesting that surface-enhanced NMR may be useful as a guide in the synthesis of defect-free surfaces in the design of various nanomaterials.

show abstract

ScOx rich surface terminations on lanthanide scandate nanoparticles

Cited by 3 publications

References 53 publications

Identifying Support Effects in Au-Catalyzed CO Oxidation

Identifying Support Effects in Au-Catalyzed CO Oxidation

Wet to Dry Controls Lanthanide Scandate Synthesis

Observing the Surface Termination of LaScO₃ Perovskite Using Solid-State Nuclear Magnetic Resonance

Contact Info

Product

Resources

About

ScOx rich surface terminations on lanthanide scandate nanoparticles

Cited by 3 publications

References 53 publications

Identifying Support Effects in Au-Catalyzed CO Oxidation

Identifying Support Effects in Au-Catalyzed CO Oxidation

Wet to Dry Controls Lanthanide Scandate Synthesis

Observing the Surface Termination of LaScO3 Perovskite Using Solid-State Nuclear Magnetic Resonance

Contact Info

Product

Resources

About

Observing the Surface Termination of LaScO₃ Perovskite Using Solid-State Nuclear Magnetic Resonance