Lotya et al

Liquid phase production of graphene by exfoliation of graphite in surfactant/water solutions

Mustafa Lotya, Yenny Hernandez, Paul J King, Ronan J Smith, Valeria Nicolosi, Lisa S Karlsson, Fiona
M Blighe, Sukanta De, Zhiming Wang, IT McGovern, Georg S Duesberg and Jonathan N Coleman*
colemaj@tcd.ie

Supporting Information for Publication

Derivation of attractive van der Waals potential for two parallel, two-dimensional sheets.

Imagine a two-dimensional circular sheet of radius R as shown in figure 1. Consider an atom sitting a
distance D above the centre of the sheet. We label this the “free atom”. Now consider a ring of atoms, of
radius x and thickness dx, in the sheet. The free atom is attracted to the atoms in the sheet by van der
Waals (vdW) interactions. The energy of interaction between the free atom and any one of the atoms in
the ring is1
C C
V =− =−
( x + D2 )
6 3
r 2

The number of atoms in the ring is dN:

dN = ρ 2π xdx
where ρ is the areal number density of atoms in the sheet.
This means the total vdW interaction between the free atom and all the atoms in the ring is dVatom-sheet:
xdx
dVatom − sheet = −2π C ρ
(x + D2 )
2 3

We can find the total interaction energy by integrating over the area of the sheet ie from x=0 to x=R. As
vdW interactions are short ranged, we can take the upper limit of integration as ∞ rather than R.

r
D

x
R dx

Figure 1

This gives the total interaction energy as

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Lotya et al

∞
xdx
Vatom − sheet = −2π C ρ ∫
(x + D2 )
2 3
0

This integrates to
πCρ
Vatom − sheet = −
2D4

Now imagine another sheet, radius R, parallel and above the first a distance D away as shown in figure
2. Consider a ring of atoms in the second sheet of radius x and thickness dx. Every atom in this ring is
attracted to the lower sheet with potential energy of attraction:
πCρ
Vatom − sheet = −
2D4
As before there are dN = ρ 2π xdx atoms in the ring. This means the total potential energy of interaction
of all the atoms in the ring with the lower sheet is
πCρ
dVsheet − sheet = − ρ 2π xdx
2D4
We can find the total interaction energy between the two sheets by integrating between x=0 and x=R.

R x dx

Figure 2

We will refer to this energy as VvdW:

2π 2C ρ 2 π 2 ρ 2 R 2C
R

2 D 4 ∫0
VvdW = − xdx = −
2D 4

The potential energy per unit area is then

VvdW πρ 2C
=−
A 2D4
We note that this model is not strictly correct for a number of reasons. Firstly, it is based on the London
inter-atomic potential. This potential is incomplete for a variety of reasons. One obvious example is that
it ignores retardation effects. This means that the r-6 dependence is not valid at intermediate inter-particle

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Lotya et al

separations. In addition, van der Waals interactions are not totally pairwise additive. Assuming
additivity can result in errors of order 20%.
We can estimate ρ2C as follows. For graphite, the energy required to separate two sheets from their van
der Waals minimum separation, d0, to infinity is given by the surface energy, γ. This means
πρ 2C
γ=
2d 04
The surface energy has been estimated to be ~70 mJ/m2.2
This means we can calculate ρ2C from
2d 04γ
ρ C=
2

π
Taking d0=0.35nm we can calculate ρ2C=6.69×10-40 Jm2.

We note that this value for ρ2C is relatively inaccurate. The main reason for this is that the surface
energy of graphite is not very well known. In addition, the surface energy is defined in vacuuo, rather
than in a solvent medium. Van der Waals interactions are screened in a solvent medium. The interaction
energy is reduced, relative to vacuum, by a factor that depends on the refractive indices of graphene and
the medium.1 This factor can be relatively large. Thus, the expression for VvdW given above should be
considered as an upper bound.

The complete citation for reference 14 is as follows:

(14) Hernandez, Y.; Nicolosi, V.; Lotya, M.; Blighe, F. M.; Sun, Z.; De, S.; McGovern, I. T.;
Holland, B.; Byrne, M.; Gun'Ko, Y. K.; Boland, J. J.; Niraj, P.; Duesberg, G.; Krishnamurthy, S.;
Goodhue, R.; Hutchison, J.; Scardaci, V.; Ferrari, A. C.; Coleman, J. N. Nature Nanotechnology 2008,
3, 563-568.

References
(1) Israelachvili, J. Intermolecular and Surface Forces; Academic Press, 1991.
(2) Hernandez, Y.; Nicolosi, V.; Lotya, M.; Blighe, F. M.; Sun, Z.; De, S.; McGovern, I. T.;
Holland, B.; Byrne, M.; Gun'Ko, Y. K.; Boland, J. J.; Niraj, P.; Duesberg, G.; Krishnamurthy, S.;
Goodhue, R.; Hutchison, J.; Scardaci, V.; Ferrari, A. C.; Coleman, J. N. Nature Nanotechnology 2008,
3, 563-568.