PMID- 31556606
OWN - NLM
STAT- PubMed-not-MEDLINE
DCOM- 20200611
LR  - 20200611
IS  - 1520-5126 (Electronic)
IS  - 0002-7863 (Linking)
VI  - 141
IP  - 40
DP  - 2019 Oct 9
TI  - Mechanism-Enabled Population Balance Modeling of Particle Formation en Route to 
      Particle Average Size and Size Distribution Understanding and Control.
PG  - 15827-15839
LID - 10.1021/jacs.9b06364 [doi]
AB  - The concept of Mechanism-Enabled Population Balance Modeling (ME-PBM) is 
      reported, illustrated by its application to a prototype Ir(0)(n) nanoparticle 
      formation reaction. ME-PBM is defined herein as the use of now available, 
      experimentally established, disproof-based, deliberately minimalistic mechanisms 
      of particle formation as the required input for more rigorous Population Balance 
      models, critically including an experimentally established nucleation mechanism. 
      ME-PBM achieves the long-sought goal of connecting such now available 
      experimental minimum mechanisms to the understanding and rational control of 
      particles size and size distributions. Twelve pseudoelementary step, 
      particle-formation mechanisms are considered so that the approach to the ME-PBM 
      is also extensively disproof-based. Resurrection of Smoluchowski's 1918 full 
      Ordinary Differential Equation (ODE) approach to the PBM is another, critical 
      aspect of our approach which, in turn, allows unbiased fitting of the 
      information-laden particle-size distribution (PSD) including its shape. The 
      results provide one solution to the "inverse problem" in which the PSD informs 
      one as to the correct particle formation mechanism: A new, deliberately 
      minimalistic 3-step particle-formation mechanism has been uncovered that is a 
      single-additional-step expansion of the now broadly used Finke-Watzky (FW) 2-step 
      mechanism, the new 3-step mechanism being: A --> B (rate constant k(1)), A + B --> C 
      (rate constant k(2)), and A + C --> 1.5C (rate constant k(3)), where A represents 
      the monomeric nanoparticle precursor, B represents "small" nanoparticles, and C 
      represents "larger" nanoparticles. The results strongly support three paradigm 
      shifts for nucleation and growth of particles, the most critical paradigm shift 
      being that the "burst" nucleation assumption in LaMer's 1950s model of particle 
      formation is not required to produce narrow, near-monodisperse PSDs. Instead, 
      narrow PSDs can be and are achieved despite continuous nucleation because smaller 
      particles grow faster than larger ones, k(2) > k(3), thereby allowing the smaller 
      particles to catch up in size to the more slowly growing larger particles.
FAU - Handwerk, Derek R
AU  - Handwerk DR
AUID- ORCID: 0000-0003-4614-9954
FAU - Shipman, Patrick D
AU  - Shipman PD
AUID- ORCID: 0000-0003-4741-9370
FAU - Whitehead, Christopher B
AU  - Whitehead CB
FAU - Ozkar, Saim
AU  - Ozkar S
AUID- ORCID: 0000-0002-6302-1429
AD  - Department of Chemistry , Middle East Technical University , 06800 Ankara , 
      Turkey.
FAU - Finke, Richard G
AU  - Finke RG
AUID- ORCID: 0000-0002-3668-7903
LA  - eng
PT  - Journal Article
PT  - Research Support, Non-U.S. Gov't
PT  - Research Support, U.S. Gov't, Non-P.H.S.
DEP - 20190926
PL  - United States
TA  - J Am Chem Soc
JT  - Journal of the American Chemical Society
JID - 7503056
SB  - IM
EDAT- 2019/09/27 06:00
MHDA- 2019/09/27 06:01
CRDT- 2019/09/27 06:00
PHST- 2019/09/27 06:00 [pubmed]
PHST- 2019/09/27 06:01 [medline]
PHST- 2019/09/27 06:00 [entrez]
AID - 10.1021/jacs.9b06364 [doi]
PST - ppublish
SO  - J Am Chem Soc. 2019 Oct 9;141(40):15827-15839. doi: 10.1021/jacs.9b06364. Epub 
      2019 Sep 26.