Dust Effects on Ir(0)(n) Nanoparticle Formation Nucleation and Growth Kinetics and Particle Size-Distributions: Analysis by and Insights from Mechanism-Enabled Population Balance Modeling

Date

2020-02-18

Author

Handwerk, Derek R.
Shipman, Patrick D.
Özkar, Saim
Finke, Richard G.

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The effects of microfiltration removal of filterable dust on nanoparticle formation kinetics and particle-size distribution, in a polyoxometalate polyanion (P2W15Nb3O629-)-stabilized Ir(0)(n) nanoparticle formation system, are analyzed by the newly developed method of Mechanism-Enabled Population Balance Modeling (ME-PBM). The [(Bu4N)(5)Na-3(1,5-COD)Ir center dot P2W15Nb3O62] precatalyst system produces on average Ir(0)(similar to 200) nanoparticles of 1.74 +/- 0.33 nm and hence a particle-size distribution (PSD) of +/- 19% dispersion when the precatalyst is reduced under H-2 in unfiltered propylene carbonate solvent. But if the precatalyst is reduced in microfiltered solvent and microfiltered reagent solutions (where the filtered solvent is then also used to rinse dust from the glassware), then larger Ir(0)(similar to 300) 1.96 +/- 0.16 nm nanoparticles are produced with a remarkable, 2.4-fold lowered +/- 8% dispersion. The results and effects of the microfiltration reduction of dust are analyzed by the newly developed method of ME-PBM. More specifically, the studies reported herein address eight outstanding questions that are listed in the Introduction. Those questions include: how easy or difficult it is to fit PSD data? What is the ability of the recently discovered alternative termolecular nucleation and two size-dependent growth steps mechanism to account for the effects of dust on the PSD? What types and amount of PSD kinetics data are needed to deconvolute the PSD into the parameters of the ME-PBM? What is the reliability of the resulting rate constants? Additional questions addressed include: if the ME-PBM results offer insights into the remarkable 2.4-fold narrowing of the PSD post simple microfiltration lowering of the dust, and if the results are likely to be more general? The Summary and Conclusions section lists nine specific insights that include comments on needed future studies.

Subject Keywords

Spectroscopy, Electrochemistry, General Materials Science, Surfaces and Interfaces, Condensed Matter Physics

URI

https://hdl.handle.net/11511/38828

Journal

LANGMUIR

DOI

https://doi.org/10.1021/acs.langmuir.9b03193

Collections

Department of Chemistry, Article

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Citation Formats

D. R. Handwerk, P. D. Shipman, S. Özkar, and R. G. Finke, “Dust Effects on Ir(0)(n) Nanoparticle Formation Nucleation and Growth Kinetics and Particle Size-Distributions: Analysis by and Insights from Mechanism-Enabled Population Balance Modeling,” LANGMUIR, pp. 1496–1506, 2020, Accessed: 00, 2020. [Online]. Available: https://hdl.handle.net/11511/38828.