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

Abstract

The question is addressed if dust is kinetically important in the nucleation and growth of Ir(0) n nanoparticles formed from [Bu 4N] 5Na 3(1,5-COD)Ir I·P 2W 15Nb 3O 62 (hereafter [(COD)Ir·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·POM] 8- precatalyst system are examined for the effects of 0.2 μm 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 μm γ-Al 2O 3 (inorganic) dust, for the addition of flame-made carbon-based (organic) dust, and as a function of the starting, microfiltered [(COD)Ir·POM 8-] 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 1obs(bimol) is shown to be slowed by a factor of ~5 to ~7.6, depending on the precise experiment and its conditions, just by the filtration of the precatalystmore » solution using a 0.20 μm filter and rinsing the glassware surface with 0.20 μm filtered propylene carbonate solvent; (ii) that simply employing a 0.20 μm filtration step narrows the size distribution of the resulting Ir(0) n nanoparticles by a factor of 2.4 from ±19 to ±8%, a remarkable result; (iii) that the narrower size distribution can be accounted for by the slowed nucleation rate constant, k 1obs(bimol), and by the unchanged autocatalytic growth rate constant, k 2obs(bimol), that is, by the increased ratio of k 2obs(bimol)/k 1obs(bimol) 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.« less

Authors:
 [1]; ORCiD logo [2]
  1. Department of Chemistry, Middle East Technical University, 06800 Ankara, Turkey
  2. Department of Chemistry, Colorado State University, Fort Collins, Colorado 80523, United States
Publication Date:
Research Org.:
Colorado State Univ., Fort Collins, CO (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1415069
Alternate Identifier(s):
OSTI ID: 1529563
Grant/Contract Number:  
FG402-03ER15453; FG02-03ER15453
Resource Type:
Published Article
Journal Name:
Langmuir
Additional Journal Information:
Journal Name: Langmuir Journal Volume: 33 Journal Issue: 26; Journal ID: ISSN 0743-7463
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Özkar, Saim, and Finke, Richard G. Dust Effects on Nucleation Kinetics and Nanoparticle Product Size Distributions: Illustrative Case Study of a Prototype Ir(0) n Transition-Metal Nanoparticle Formation System. United States: N. p., 2017. Web. doi:10.1021/acs.langmuir.7b01219.
Özkar, Saim, & Finke, Richard G. Dust Effects on Nucleation Kinetics and Nanoparticle Product Size Distributions: Illustrative Case Study of a Prototype Ir(0) n Transition-Metal Nanoparticle Formation System. United States. doi:10.1021/acs.langmuir.7b01219.
Özkar, Saim, and Finke, Richard G. Thu . "Dust Effects on Nucleation Kinetics and Nanoparticle Product Size Distributions: Illustrative Case Study of a Prototype Ir(0) n Transition-Metal Nanoparticle Formation System". United States. doi:10.1021/acs.langmuir.7b01219.
@article{osti_1415069,
title = {Dust Effects on Nucleation Kinetics and Nanoparticle Product Size Distributions: Illustrative Case Study of a Prototype Ir(0) n Transition-Metal Nanoparticle Formation System},
author = {Özkar, Saim and Finke, Richard G.},
abstractNote = {The question is addressed if dust is kinetically important in the nucleation and growth of Ir(0)n nanoparticles formed from [Bu4N]5Na3(1,5-COD)IrI·P2W15Nb3O62 (hereafter [(COD)Ir·POM]8-), reduced by H2 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·POM]8- precatalyst system are examined for the effects of 0.2 μm 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 μm γ-Al2O3 (inorganic) dust, for the addition of flame-made carbon-based (organic) dust, and as a function of the starting, microfiltered [(COD)Ir·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” k1obs(bimol) is shown to be slowed by a factor of ~5 to ~7.6, depending on the precise experiment and its conditions, just by the filtration of the precatalyst solution using a 0.20 μm filter and rinsing the glassware surface with 0.20 μm filtered propylene carbonate solvent; (ii) that simply employing a 0.20 μm filtration step narrows the size distribution of the resulting Ir(0)n nanoparticles by a factor of 2.4 from ±19 to ±8%, a remarkable result; (iii) that the narrower size distribution can be accounted for by the slowed nucleation rate constant, k1obs(bimol), and by the unchanged autocatalytic growth rate constant, k2obs(bimol), that is, by the increased ratio of k2obs(bimol)/k1obs(bimol) 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.},
doi = {10.1021/acs.langmuir.7b01219},
journal = {Langmuir},
number = 26,
volume = 33,
place = {United States},
year = {2017},
month = {6}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record
DOI: 10.1021/acs.langmuir.7b01219

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