QR‐SCMEH‐MO calculations on the complex [Pt (SnCl3)5]3−: Electronic structure, UV–visible spectrum, magnetic properties, and bond energy

Boudreaux, Edward A.

doi:10.1002/qua.24004

Cited by 3 publications

(3 citation statements)

References 21 publications

(31 reference statements)

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“…At high Sn/Pt ratio, the chemical formula of the Sn-Pt complex is [Pt(SnCl 3 ) 5 ] 3À , while at low Pt/Sn ratios SnCl would be expected based upon stoichiometry. The structures proposed here are consistent with those identied by other authors, 55,56,59,60,67,68 but not previously probed with EXAFS. The ts and parameters including space group, bond lengths, and bond angles are given in ESI Table 1 and ESI Fig.…”

Section: Sn-pt Complex Stoichiometrysupporting

confidence: 93%

“…Electron transfer from the Sn 6p orbital to the Pt 5d orbital can be followed by monitoring changes in the Sn-Pt complex UV-vis spectrum at 410 nm. 59,60 However, the absorption behavior at 410 nm is convoluted with the broad absorption typical of Pt metal nanoparticles. Therefore, we can use the absorption at ca.…”

Section: Determining Sn-pt Complex Reduction Kinetics Using Ex Situ U...mentioning

confidence: 99%

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A nanoscale-modified LaMer model for particle synthesis from inorganic tin–platinum complexes

John

Nan

et al. 2013

J. Mater. Chem. A

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The size-tunable structure and properties of Pt nanoparticles at the atomic length scale have attracted significant attention across a wide variety of fields including magnetics, electrocatalysis, optics, and gasphase synthesis. Mechanisms responsible for the formation Pt nanoparticles remain unclear because of the difficulty generating in situ data for the time-evolution of size, shape, distribution, volume fraction, particle number density, and oxidation state from the starting complexes. We here demonstrate the use of simultaneous small-and wide-angle X-ray scattering combined with UV-vis spectroscopy to measure these key synthesis metrics for the reduction of Pt(IV) by Sn(II) in aqueous solution. This synthesis approach has been previously shown to permit continuous control over Pt nanoparticle size from 0.9 to 2.6 nm to within 10% standard deviation. Such fine control led to the discovery of densely packed amorphous structures at ca. 1.7 nm with substantially enhanced electrocatalytic oxygen reduction relative to nanocrystals and commercial electrocatalysts. Ex situ UV-vis and in situ X-ray scattering are here shown to reveal four distinct stages during synthesis: (1) autoreduction of a ligand/noble metal complex with a unique structure that depends on the Sn(II)/Pt(II) ratio, (2) generation of Pt primary particles and the formation of Pt nuclei at a rate that depends on the structure of the initial complex,(3) nanoparticle growth via LaMer's diffusion of these primary particles to the nuclei, and (4) growth termination due to capping from a stabilizing, two-layer ligand shell. We derive a set of consecutive rate equations and associated kinetic parameters that describe each step. The kinetics of ligand rearrangement has been previously found to limit the rate of nanoparticle growth. We incorporate this phenomenon into LaMer's classic diffusion-limited growth scheme to extend it to the nanoscale regime.This new model provides detailed understanding of how metal ligands serve as both reducing and stabilizing agents and allow for unprecedented, continuous control over both size and distribution. Systematic variation of temperature permits detailed time resolution at the very onset of Pt primary particle formation, as well as a means to determine temperature sensitivity of nanoparticle growth.

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Section: Sn-pt Complex Stoichiometrysupporting

confidence: 93%

Section: Determining Sn-pt Complex Reduction Kinetics Using Ex Situ U...mentioning

confidence: 99%

A nanoscale-modified LaMer model for particle synthesis from inorganic tin–platinum complexes

John

Nan

et al. 2013

J. Mater. Chem. A

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“…The overall charge on the structure is −3. Pt coordination was proposed based on literature data for condensed Pt–Sn organometallic complexes. − The Pt L 2 edge ( k 2 -weighted) Fourier transform of the EXAFS scattering from the proposed Pt–Sn complex in R -space (b) and k -space (c).…”

Section: Resultsmentioning

confidence: 99%

Time-Resolved, in Situ, Small- and Wide-Angle X-ray Scattering To Monitor Pt Nanoparticle Structure Evolution Stabilized by Adsorbed SnCl₃^– Ligands During Synthesis

John

Schaefer

et al. 2013

J. Phys. Chem. C

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Understanding and controlling nanoparticle formation mechanisms is important because of increasing reports of unusual material properties in this critical size region in fields ranging from magnetics, electrocatalysis, optics, and heterogeneous synthesis. Here we use real-time, in situ smallangle and wide-angle X-ray scattering to dynamically monitor the production of Pt critical nuclei from Sn−Pt complexes on a length scale approaching 0.6 nm. A time resolution of 20 s is achieved due to the slow reduction and growth processes of this unique system. The structure and evolution of inorganic Sn ligands on these Pt nanoparticle cores is of particular interest because of the ability of Sn to mitigate poisoning of electrocatalyst surfaces by adsorbed CO intermediates (CO ads ) on the anode of direct alcohol fuel cells. Coherent scattering from the stabilizing ligand shell is identified in the wide-angle scattering data and suggests segregation of Sn ligands at the surface of the nanoparticles synthesized using our approach. We correlate the autoreduction kinetics of precursor complexes with number density, polydispersity, and Pt volume fraction, thereby establishing the mechanism of particle size control at the onset of atomic coalescence. Particle growth is shown to terminate when a Sn shell of well-defined thickness (about 0.6 nm) is completed for a range of Pt core diameters in this critical size range.

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119Sn Mössbauer spectroscopy of the time-resolved evolution of SnCl3− ligand structure on the surface of growing platinum nanoparticles

John

Ravindren

Nan

et al. 2018

Applied Surface Science

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QR‐SCMEH‐MO calculations on the complex [Pt (SnCl₃)₅]³⁻: Electronic structure, UV–visible spectrum, magnetic properties, and bond energy

Cited by 3 publications

References 21 publications

A nanoscale-modified LaMer model for particle synthesis from inorganic tin–platinum complexes

A nanoscale-modified LaMer model for particle synthesis from inorganic tin–platinum complexes

Time-Resolved, in Situ, Small- and Wide-Angle X-ray Scattering To Monitor Pt Nanoparticle Structure Evolution Stabilized by Adsorbed SnCl₃^– Ligands During Synthesis

119Sn Mössbauer spectroscopy of the time-resolved evolution of SnCl3− ligand structure on the surface of growing platinum nanoparticles

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QR‐SCMEH‐MO calculations on the complex [Pt (SnCl3)5]3−: Electronic structure, UV–visible spectrum, magnetic properties, and bond energy

Cited by 3 publications

References 21 publications

A nanoscale-modified LaMer model for particle synthesis from inorganic tin–platinum complexes

A nanoscale-modified LaMer model for particle synthesis from inorganic tin–platinum complexes

Time-Resolved, in Situ, Small- and Wide-Angle X-ray Scattering To Monitor Pt Nanoparticle Structure Evolution Stabilized by Adsorbed SnCl3– Ligands During Synthesis

119Sn Mössbauer spectroscopy of the time-resolved evolution of SnCl3− ligand structure on the surface of growing platinum nanoparticles

Contact Info

Product

Resources

About

QR‐SCMEH‐MO calculations on the complex [Pt (SnCl₃)₅]³⁻: Electronic structure, UV–visible spectrum, magnetic properties, and bond energy

Time-Resolved, in Situ, Small- and Wide-Angle X-ray Scattering To Monitor Pt Nanoparticle Structure Evolution Stabilized by Adsorbed SnCl₃^– Ligands During Synthesis