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Title: Medium controlled aggregative growth as a key step in mesoporous silica nanoparticle formation

Abstract

Near monodisperse mesoporous silica nanoparticles (MSN) represent a promising and rapidly developing type of mesoporous silica materials; however, the vast data on their synthesis remains unorganized and ill-understood. We systematically studied the formation of MSN under basic and neutral conditions using various temperatures, CTAB concentrations, hydrolyzing agents (triethanolamine, ammonia, phosphate buffers), and media with different colloidal stabilization properties (with ethanol as a cosolvent and monovalent salts). In the typical conditions for the preparation of stable MSN colloids, the particle size was controlled by colloidal stabilization by the medium (solvent type, ionic strength, and surfactant concentration) in agreement with the “aggregative growth” mechanism, rather than by solely the hydrolysis and condensation rates conventionally used for data interpretation in the classical nucleation theory. Medium properties (pH, ion types and concentration, polarity) also defined the efficiency of silica-surfactant cooperative self-assembly, which directly affected the porosity, mesopore size and pore wall thickness. Interestingly, this traditional silica-surfactant route showed a limited effect on the particle size, emphasizing the dominating role of colloidal stabilization in the studied reaction conditions. In situ pH measurements showed that every reaction medium has unique pH evolution profiles depending on the buffer capacity, hydrolysis and condensation rates. Reaction systems that failmore » to maintain the working pH can lead to non-porous products or undesired particle morphology and size distribution. The established particle formation mechanism allowed us to formulate comprehensive guidelines for preparing relatively concentrated colloids of near monodisperse (PDI 5–15%) mesoporous 30–700 nm silica spheres with variable porosity and mesopore size. Here, these findings will be particularly useful in designing new mesoporous silica-containing materials for biomedical applications.« less

Authors:
 [1];  [1]
  1. Univ. of Utah, Salt Lake City, UT (United States)
Publication Date:
Research Org.:
Univ. of Utah, Salt Lake City, UT (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1864182
Alternate Identifier(s):
OSTI ID: 1866280
Grant/Contract Number:  
SC0019285; -SC0019285
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Colloid and Interface Science
Additional Journal Information:
Journal Volume: 615; Journal ID: ISSN 0021-9797
Publisher:
Elsevier
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Mesoporous silica nanoparticles; MSN; Colloidal stability; Nucleation; Aggregative growth; Cooperative assembly; Charge matching; Aggregation

Citation Formats

Semeykina, Viktoriya, and Zharov, Ilya. Medium controlled aggregative growth as a key step in mesoporous silica nanoparticle formation. United States: N. p., 2022. Web. doi:10.1016/j.jcis.2022.01.166.
Semeykina, Viktoriya, & Zharov, Ilya. Medium controlled aggregative growth as a key step in mesoporous silica nanoparticle formation. United States. https://doi.org/10.1016/j.jcis.2022.01.166
Semeykina, Viktoriya, and Zharov, Ilya. Mon . "Medium controlled aggregative growth as a key step in mesoporous silica nanoparticle formation". United States. https://doi.org/10.1016/j.jcis.2022.01.166. https://www.osti.gov/servlets/purl/1864182.
@article{osti_1864182,
title = {Medium controlled aggregative growth as a key step in mesoporous silica nanoparticle formation},
author = {Semeykina, Viktoriya and Zharov, Ilya},
abstractNote = {Near monodisperse mesoporous silica nanoparticles (MSN) represent a promising and rapidly developing type of mesoporous silica materials; however, the vast data on their synthesis remains unorganized and ill-understood. We systematically studied the formation of MSN under basic and neutral conditions using various temperatures, CTAB concentrations, hydrolyzing agents (triethanolamine, ammonia, phosphate buffers), and media with different colloidal stabilization properties (with ethanol as a cosolvent and monovalent salts). In the typical conditions for the preparation of stable MSN colloids, the particle size was controlled by colloidal stabilization by the medium (solvent type, ionic strength, and surfactant concentration) in agreement with the “aggregative growth” mechanism, rather than by solely the hydrolysis and condensation rates conventionally used for data interpretation in the classical nucleation theory. Medium properties (pH, ion types and concentration, polarity) also defined the efficiency of silica-surfactant cooperative self-assembly, which directly affected the porosity, mesopore size and pore wall thickness. Interestingly, this traditional silica-surfactant route showed a limited effect on the particle size, emphasizing the dominating role of colloidal stabilization in the studied reaction conditions. In situ pH measurements showed that every reaction medium has unique pH evolution profiles depending on the buffer capacity, hydrolysis and condensation rates. Reaction systems that fail to maintain the working pH can lead to non-porous products or undesired particle morphology and size distribution. The established particle formation mechanism allowed us to formulate comprehensive guidelines for preparing relatively concentrated colloids of near monodisperse (PDI 5–15%) mesoporous 30–700 nm silica spheres with variable porosity and mesopore size. Here, these findings will be particularly useful in designing new mesoporous silica-containing materials for biomedical applications.},
doi = {10.1016/j.jcis.2022.01.166},
journal = {Journal of Colloid and Interface Science},
number = ,
volume = 615,
place = {United States},
year = {Mon Jan 31 00:00:00 EST 2022},
month = {Mon Jan 31 00:00:00 EST 2022}
}

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