Effect of Hydrophilicity and Interfacial Water Structure on Particle Attachment
Open accessAbstract
Oriented attachment (OA) of nanoparticles is an important and common crystallization pathway. Efforts to isolate and quantify the interparticle forces that underlie OA have only recently been initiated, and the role played by the interfacial solvent structure in the confined region between nanocrystal surfaces in enabling and controlling OA remains an open question. In this work, classical molecular dynamics (MD) simulations were performed to compute the free energy landscape of nanoparticles approaching mineral substrates in both vacuum and pure water. Periclase (MgO), muscovite (KAl 3 Si 3 O 10 (OH) 2 ), and pyrophyllite (Al 2 Si 4 O 10 (OH) 2 ) nanoparticles exposing the (100), (001), and (001) surfaces, respectively, were brought to contact with substrates exposing the same surfaces. These mineral surfaces were selected to investigate a range of hydrophilicities (periclase > muscovite > pyrophyllite). The MD simulations revealed that the interfacial water structure created free energy minima for nanoparticle approach that corresponded to integer numbers of intervening water layers. The depth of the free energy minima and the free energy barriers between minima correlated positively with the hydrophilicity of the mineral surface. While the range of solvent-mediated interactions was predicted to be short (a few intervening water layers at most for MgO), the free energy barriers were calculated to be large (fraction of an eV per nm 2 ), and the effect of misalignment diminished rapidly with the number of intervening water layers. The results help explain the formation of mesocrystals and the observed ability of nanoparticles to rotate before attachment while in a long-lived solvent-separated state.
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Molecular-scale mechanisms of CO2 mineralization in nanoscale interfacial water films
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- Authors
- Kerisit, S. N., & De Yoreo, J. J.
- Affiliations
- Physical and Computational Sciences Directorate, Pacific Northwest National Laboratory, Richland, Washington 99354, United States
- Venue
- The Journal of Physical Chemistry C
- Publisher
- American Chemical Society (ACS)
- Published
- 2020-02-13
- Volume
- 124
- Issue
- 9
- Pages
- 5480-5488
- ISSN
- 1932-7447 (ISSN-L)
- 1932-7455
- OpenAlex
- W3006153813
- Semantic Scholar
- 6344f090df83f38f5776dd80c21f2da5ddea3494
- Cited by
- 28
- References
- 57
- Citations by year
- 2026: 2 · 2025: 4 · 2024: 3 · 2023: 10 · 2022: 2 · 2021: 6 · 2020: 1
- FWCI
- 1.24
- Type
- journal article
- Language
- en
- Open access
- green
- www.osti.gov
- Licence
- Locations
- The Journal of Physical Chemistry C (publishedVersion)
- OSTI OAI (U.S. Department of Energy Office of Scientific and Technical Information) (submittedVersion)
- The Journal of Physical Chemistry
- Funders
- Basic Energy Sciences
- Battelle (DE-AC05-76RL01830)
- Topics
- Physical Sciences › Materials Science › Biomaterials › Calcium Carbonate Crystallization and Inhibition
- Physical Sciences › Earth and Planetary Sciences › Atmospheric Science › nanoparticles nucleation surface interactions
- Physical Sciences › Environmental Science › Water Science and Technology › Minerals Flotation and Separation Techniques
- Keywords
- oriented attachment, nanoparticle attachment, interfacial water structure, hydrophilicity, free energy landscape, mineral surfaces, periclase, muscovite, pyrophyllite, interparticle interactions, solvent-mediated interactions, water layering, nanoparticle rotation
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