Amphiphilicity of Intricate Layered Graphene/g-C<sub>3</sub>N<sub>4</sub> Nanosheets

Priyadarsini, Adyasa; Mallik, Bhabani S.

doi:10.1021/acs.jpcb.1c05609

Cited by 5 publications

(6 citation statements)

References 92 publications

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“…However, the significant loss in tetrahedrality in the interfacial layer of h-BN compared to the bulk does not tone with the loss of HB donor/acceptor count. In our previous studies, 45,52 we found that the TOP and per water HB count follow the same trend. However, they do not complement each other quantitatively.…”

Section: Introductionsupporting

confidence: 62%

“…The partial charge values used for B and N atoms are +0.37/–0.37 . For g–C 3 N 4 –water interactions, we used the previously reported parameters, including the charge variation over g-C 3 N 4 . As the bilayer was simulated beforehand, with both the parallel sheets flexible, during the entire simulation with water molecules, both the layers of h-BN and g-C 3 N 4 were kept static, and the water molecules were arranged according to the instantaneous surface.…”

Section: Computational Detailsmentioning

confidence: 99%

“…64 For g−C 3 N 4 −water interactions, we used the previously reported parameters, including the charge variation over g-C 3 N 4 . 45 As the bilayer was simulated beforehand, with both the parallel sheets flexible, during the entire simulation with water molecules, both the layers of h-BN and g-C 3 N 4 were kept static, and the water molecules were arranged according to the instantaneous surface. The energy minimization was performed for h-BN-water and g−C 3 N 4 −water systems using the conjugate gradient method.…”

Section: Computational Detailsmentioning

confidence: 99%

“…26,30 In our recent classical molecular dynamics study, we revealed the amphiphilic nature of graphene and g-C 3 N 4 hybrid surfaces as well as local hydrophilicity and hydrophobicity. 45 The first principles simulations revealed that the edge and defect N centers of g-C 3 N 4 are locally hydrophilic and the carbon centers are hydrophobic. 79,80 A previous study comparing the structural properties of water molecules confined within the two layers of h-BN and graphene also found reduced HBs in the interfacial region by studying the continuous HB profile along the zaxis.…”

Section: Hydrogen Bond Statisticsmentioning

confidence: 99%

“…42 In few of our recent studies, we investigated structural, dynamic, and spectral properties with the static HB formation associated with water molecules interfacing bilayer BP and Gr@g-C 3 N 4 . 45,46 Our motive is to draw a better understanding by associating all possible physical features and set a model for hydroaffinity. Contact angle modeling requires a large set of water molecules on an expanded sheet 47−49 and provides ambiguous results regarding the hydroaffinity of the specific heterostructure.…”

Section: Introductionmentioning

confidence: 99%

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Anisotropy and Hybrid Heterosurface-Modulated Two-Dimensional Hydrogen Bond Network of Water

Priyadarsini

Mallik

2023

J. Phys. Chem. C

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We report the structure and dynamics of layered water structure near a bilayer heterosurface using classical molecular dynamics simulations and network graph theory. The heterosurfaces of our choice are technologically essential and well-studied hexagonal boron nitride (h-BN) and graphitic carbon nitride (g-C 3 N 4 ). Starting with the water density distribution profile, we have studied different hydrogen bondings (HBs) associated with distance and angle distributions and correlated them with the HB count, followed by the investigations of dynamic properties. We realize the oddity while corresponding to the tetrahedral order parameter (TOP), HB donor/acceptor count, and HB lifetime. A quantitative gap is observed between the TOP and HB counts, and we perceive another structural factor playing a significant role. We observe a 2D sheetlike arrangement of hydrogen-bonded water molecules, namely, 2D-HB, in the interfacial layer instead of 3D tetrahedral arrangements. 2D-HB qualitatively acts as a key descriptor of the hydrophobicity of the interface. The probability of higher TOP among the interfacial layer water molecules is less for h-BN compared to g-C 3 N 4 . However, the per-water HBs for both the heterosurfaces remain indistinguishable, implying the existence of another significant physical factor related to HB. Hence, 2D-HB serves as a deciding factor. In the case of h-BN, water molecules in the first layer form extended 2D sheets compared to the second and bulk, which is not a scenario for g-C 3 N 4 . Following the network graph theory, we calculated the temporal evolution of the maximum number of water molecules connected in a single network. The layer 1 water molecules have slower orientational dynamics, higher HB lifetime, and consequently slower translational diffusion than layer 2 and bulk water molecules. The experimental studies suggested that the contact angle of water on h-BN can vary from 61.4 to 85.8°, higher than that of g-C 3 N 4 , depending on the surface stacking, support material, and exposure to air, which effectively makes h-BN more hydrophobic compared to g-C 3 N 4 . The interfacial water molecules have a smaller HB lifetime and a faster diffusion coefficient than g-C 3 N 4 . The HB lifetime of water molecules in bulk is less than that in the interface, irrespective of the surface. A slower reorientation lifetime, that is, 2.69 ps, for g-C 3 N 4 interfacial water molecules is observed versus 2.20 ps for h-BN. Our results agree with the experimental observations and can help to understand the hydrophobicity of other relevant materials.

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Section: Introductionsupporting

confidence: 62%

Section: Computational Detailsmentioning

confidence: 99%