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Title: Impact of Solution Chemistry and Particle Anisotropy on the Collective Dynamics of Oriented Aggregation

Abstract

While oriented aggregation (OA) of particles is a widely recognized mechanism of crystal growth, the impact of many fundamental parameters, such as crystallographically distinct interfacial structures, solution composition, and nanoparticle morphology on the governing mechanisms and assembly kinetics are largely unexplored. Thus, the collective dynamics of systems exhibiting OA has not been predicted. In this context, we investigated the structure and dynamics of boehmite aggregation as a function of solution pH and ionic strength. Cryogenic transmission electron microscopy reveals that boehmite nanoplatelets assemble by oriented attachment on (010) planes. The coagulation rate constants obtained from dynamic light scattering during the early stages of aggregation span seven orders of magnitude and cross both the reaction-limited and diffusion-limited regimes. Combining a simple scaling analysis with calculations for stability ratios and rotational/translational diffusivities of irregular particle shapes, the effects of orientation for irregular-shaped particles on the early stages of aggregation is understood via angular dependence of van der Waals, electrostatic, and hydrodynamic interactions. Using Monte Carlo simulations, we discovered that a simple geometric parameter, namely the contact area between two attaching nanoplatelets, presents a useful tool for correlating nanoparticle morphologies to the emerging larger-scale aggregates, hence explaining the unusually high fractal dimensions measuredmore » for boehmite aggregates. Our results on nanocrystal transport and interactions provide insights towards the predictive understanding of nanoparticle growth, assembly, and aggregation, which will important critical challenges in the developing synthesis strategies for nanostructured materials, understanding the evolution of geochemical reservoirs, and addressing many environmental problems.« less

Authors:
ORCiD logo [1]; ORCiD logo [1];  [2]; ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [3]; ORCiD logo [1]; ORCiD logo [4]; ORCiD logo [2]; ORCiD logo [1]
  1. Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
  2. Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Univ. of Washington, Seattle, WA (United States)
  3. Washington State Univ., Pullman, WA (United States)
  4. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Publication Date:
Research Org.:
Energy Frontier Research Centers (EFRC) (United States). Interfacial Dynamics in Radioactive Environments and Materials (IDREAM); Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1558377
Report Number(s):
PNNL-SA-138292
Journal ID: ISSN 1936-0851
Grant/Contract Number:  
AC05-76RL01830
Resource Type:
Accepted Manuscript
Journal Name:
ACS Nano
Additional Journal Information:
Journal Volume: 12; Journal Issue: 10; Journal ID: ISSN 1936-0851
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; oriented; aggregation; boehmite; attachment

Citation Formats

Nakouzi, Elias, Soltis, Jennifer A., Legg, Benjamin A., Schenter, Gregory K., Zhang, Xin, Graham, Trent R., Rosso, Kevin M., Anovitz, Lawrence M., De Yoreo, James J., and Chun, Jaehun. Impact of Solution Chemistry and Particle Anisotropy on the Collective Dynamics of Oriented Aggregation. United States: N. p., 2018. Web. doi:10.1021/acsnano.8b04909.
Nakouzi, Elias, Soltis, Jennifer A., Legg, Benjamin A., Schenter, Gregory K., Zhang, Xin, Graham, Trent R., Rosso, Kevin M., Anovitz, Lawrence M., De Yoreo, James J., & Chun, Jaehun. Impact of Solution Chemistry and Particle Anisotropy on the Collective Dynamics of Oriented Aggregation. United States. doi:10.1021/acsnano.8b04909.
Nakouzi, Elias, Soltis, Jennifer A., Legg, Benjamin A., Schenter, Gregory K., Zhang, Xin, Graham, Trent R., Rosso, Kevin M., Anovitz, Lawrence M., De Yoreo, James J., and Chun, Jaehun. Tue . "Impact of Solution Chemistry and Particle Anisotropy on the Collective Dynamics of Oriented Aggregation". United States. doi:10.1021/acsnano.8b04909. https://www.osti.gov/servlets/purl/1558377.
@article{osti_1558377,
title = {Impact of Solution Chemistry and Particle Anisotropy on the Collective Dynamics of Oriented Aggregation},
author = {Nakouzi, Elias and Soltis, Jennifer A. and Legg, Benjamin A. and Schenter, Gregory K. and Zhang, Xin and Graham, Trent R. and Rosso, Kevin M. and Anovitz, Lawrence M. and De Yoreo, James J. and Chun, Jaehun},
abstractNote = {While oriented aggregation (OA) of particles is a widely recognized mechanism of crystal growth, the impact of many fundamental parameters, such as crystallographically distinct interfacial structures, solution composition, and nanoparticle morphology on the governing mechanisms and assembly kinetics are largely unexplored. Thus, the collective dynamics of systems exhibiting OA has not been predicted. In this context, we investigated the structure and dynamics of boehmite aggregation as a function of solution pH and ionic strength. Cryogenic transmission electron microscopy reveals that boehmite nanoplatelets assemble by oriented attachment on (010) planes. The coagulation rate constants obtained from dynamic light scattering during the early stages of aggregation span seven orders of magnitude and cross both the reaction-limited and diffusion-limited regimes. Combining a simple scaling analysis with calculations for stability ratios and rotational/translational diffusivities of irregular particle shapes, the effects of orientation for irregular-shaped particles on the early stages of aggregation is understood via angular dependence of van der Waals, electrostatic, and hydrodynamic interactions. Using Monte Carlo simulations, we discovered that a simple geometric parameter, namely the contact area between two attaching nanoplatelets, presents a useful tool for correlating nanoparticle morphologies to the emerging larger-scale aggregates, hence explaining the unusually high fractal dimensions measured for boehmite aggregates. Our results on nanocrystal transport and interactions provide insights towards the predictive understanding of nanoparticle growth, assembly, and aggregation, which will important critical challenges in the developing synthesis strategies for nanostructured materials, understanding the evolution of geochemical reservoirs, and addressing many environmental problems.},
doi = {10.1021/acsnano.8b04909},
journal = {ACS Nano},
number = 10,
volume = 12,
place = {United States},
year = {2018},
month = {9}
}

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