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

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


Dust Effects on Nucleation Kinetics and Nanoparticle Product Size Distributions: Illustrative Case Study of a Prototype Ir(0)(n) Transition-Metal Nanoparticle Formation System
Özkar, Saim (American Chemical Society (ACS), 2017-07-04)
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 effec...
Robust Covalent Coupling Scheme for the Development of FRET Aptasensor based on Amino-Silane-Modified Graphene Oxide
Kahyaoğlu, Leyla Nesrin (American Chemical Society (ACS), 2018-12-04)
In recent years, numerous aptamers have been physisorbed on graphene oxide (GO) to develop fluorescence resonance energy transfer-based aptasensors using the fluorescence quenching property of GO. However, physisorbed aptasensors show poor signal reversibility and reproducibility as well as nonspecific probe displacement, and thereby are not suitable for many analytical applications. To overcome these problems when working with complex biological samples, we developed a facile and robust covalent surface fu...
Amphoteric surface hydrogels derived from hydrogen-bonded multilayers: Reversible loading of dyes and macromolecules
Kharlampieva, Eugenia; Erel Göktepe, İrem; Sukhishvili, Svetlana A. (American Chemical Society (ACS), 2007-01-02)
We used hydrogen-bonded multilayers of poly(N-vinylpyrrolidone) (PVPON) and poly(methacrylic acid) (PMAA) as precursors for producing surface-bound hydrogels and studied their pH-dependent swelling and protein uptake behavior using in situ attenuated total reflection Fourier transform infrared spectroscopy and in situ ellipsometry. The hydrogels were produced by selective chemical cross-linking between PMAA units using carbodiimide chemistry and ethylenediamine (EDA) as a cross-linking reagent, followed by ...
Hasanlı, Nızamı; CULFAZ, A (Wiley, 1995-01-01)
TlInSe2 and TlInTe2 crystallize in a tetragonal cell (space group 14/mcm) (Muller et al.). A primitive cell of these ternary crystals contains two formula units. All the Tl atoms in these compounds are univalent. The In atoms are trivalent being in a tetrahedral environment consisting of Se or Te atoms. InSe4 or InTe4 fragments of a unit cell form the chains extended along c-axis coinciding with [001] directions. Such chains are bonded to each other by Tl atoms.
Active Janus Particles at Interfaces of Liquid Crystals
Mangal, Rahul; Nayani, Karthik; Kim, Young-Ki; Büküşoğlu, Emre; Cordova-Figueroa, Ubaldo M.; Abbott, Nicholas. L. (American Chemical Society (ACS), 2017-10-17)
We report an investigation of the active motion of silica palladium Janus particles (JPs) adsorbed at interfaces formed between nematic liquid crystals (LCs) and aqueous phases containing hydrogen peroxide (H2O2). In comparison to isotropic oil aqueous interfaces, we observe the elasticity and anisotropic viscosity of the nematic phase to change qualitatively the active motion of the JPs at the LC interfaces. Although contact line pinning on the surface of the JPs is observed. to restrict out-of-plane rotat...
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.