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Interfacial water participates in a wide range of phenomena involving graphite, graphite-like and 2D material interfaces. Recently, several high-spatial resolution experiments have questioned the existence of hydration layers on graphite, graphite-like and 2D material surfaces. Here, 3D AFM was applied to follow in real-time and with atomic-scale depth resolution the evolution of graphite–water interfaces. Pristine graphite surfaces upon immersion in water showed the presence of several hydration layers separated by a distance of 0.3 nm. Those layers were short-lived. After several minutes, the interlayer distance increased to 0.45 nm. At longer immersion times (∼50 min) we observed the formation of a third layer. An interlayer distance of 0.45 nm characterizes the layering of predominantly alkane-like hydrocarbons. Molecular dynamics calculations supported the experimental observations. The replacement of water molecules by hydrocarbons on graphite is spontaneous. It happens whenever the graphite–water volume is exposed to air.
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Atomically resolved interfacial water structures on crystalline hydrophilic and hydrophobic surfaces
Hydration layers are formed on hydrophilic crystalline surfaces immersed in water. Their existence has also been predicted for hydrophobic surfaces, yet the experimental evidence is controversial. Using 3D-AFM imaging, we probed the interfacial water structure of hydrophobic and hydrophilic surfaces with atomic-scale spatial resolution. We demonstrate that the atomic-scale structure of interfacial water on crystalline surfaces presents two antagonistic arrangements. On mica, a common hydrophilic crystalline surface, the interface is characterized by the formation of 2 to 3 hydration layers separated by approximately 0.3 nm. On hydrophobic surfaces such as graphite or hexagonal boron nitride (h-BN), the interface is characterized by the formation of 2 to 4 layers separated by about 0.5 nm. The latter interlayer distance indicates that water molecules are expelled from the vicinity of the surface and replaced by hydrocarbon molecules. This creates a new 1.5–2 nm thick interface between the hydrophobic surface and the bulk water. Molecular dynamics simulations reproduced the experimental data and confirmed the above interfacial water structures.
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- Award ID(s):
- 1945589
- PAR ID:
- 10279611
- Date Published:
- Journal Name:
- Nanoscale
- Volume:
- 13
- Issue:
- 10
- ISSN:
- 2040-3364
- Page Range / eLocation ID:
- 5275 to 5283
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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- Free Publicly Accessible Full Text
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Accepted Manuscript1.0
- Journal Article:
- https://doi.org/10.1039/d1nr00351h
