Dust Effects on Nucleation Kinetics and Nanoparticle Product Size Distributions: Illustrative Case Study of a Prototype Ir(0)(n) Transition-Metal Nanoparticle Formation System


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ÖZKAR S., Finke R. G.

LANGMUIR, vol.33, no.26, pp.6550-6562, 2017 (SCI-Expanded) identifier identifier identifier

  • Publication Type: Article / Article
  • Volume: 33 Issue: 26
  • Publication Date: 2017
  • Doi Number: 10.1021/acs.langmuir.7b01219
  • Journal Name: LANGMUIR
  • Journal Indexes: Science Citation Index Expanded (SCI-EXPANDED), Scopus
  • Page Numbers: pp.6550-6562
  • Middle East Technical University Affiliated: Yes

Abstract

The question is addressed if dust is kinetically important in the nucleation and growth of Ir(0) nanoparticles formed from [Bu4N](5)Na-3(1,5-COD)(IrP2W15Nb3O62)-P-I center dot (hereafter [(COD)Ir center dot POM](8-)), reduced by H-2 in propylene carbonate solvent. Following a concise review of the (often neglected) literature addressing dust in nucleation phenomena dating back to the late 1800s, the nucleation and growth kinetics of the [(COD)Ir center dot POK8- precatalyst system are examined for the effects of 0.2 mu m microfiltration of the solvent and precatalyst solution, of rinsing the glassware with that microfiltered solvent, of silanizing the glass reaction vessel, for the addition of <0.2 mu m gamma-Al2O3 (inorganic) dust, for the addition of flame-made carbon-based (organic) dust, and as a function of the starting, microfiltered [(COD)Ir center dot POM8-] concentration. Efforts to detect dust and its removal by dynamic light scattering and by optical microscopy are also reported. The results yield a list of eight important conclusions, the four most noteworthy of which-are (i) that the nucleation apparent rate "constant" k(lobs(brnol)) is shown to be slowed by a factor of similar to 5 to similar to 7.6, depending on the precise experiment and its conditions, just by the filtration of the precatalyst solution using a 0.20 mu m filter and rinsing the glassware surface with 0.20 pm filtered propylene carbonate solvent; (ii) that simply employing a 0.20 tan filtration step narrows the size distribution of the resulting Ir(0) nanoparticles by a factor of 2.4 from 19 to 8%, a remarkable result; (iii) that the narrower size distribution can be oboimoo, accounted for by the slowed nucleation rate constant, kl and by the unchanged autocatalytic growth rate constant, that is, by the increased ratio of k(2obs(bimol))/k(lob(biomal)) that further separates nucleation from growth in time for filtered vs unfiltered solutions; and (iv) that five lines of evidence indicate that the filterable component of the solution, which has nucleation rate-enhancing and size-dispersion broadening effects, is dust.