Carbon 37 (1999) 301–305

Adsorption of krypton at 77 k on fullerene C ,

60
graphitized carbon black and diamond
W. Krätschmer a, J. Rathouský b,*, A. Zukal b
a Max-Planck-Institut für Kernphysik, P.O. Box 103980, 69029 Heidelberg, Germany
b J. Heyrovský Institute of Physical Chemistry, Academy of Sciences of the Czech Republic, Dolejškova 3, 182 23 Prague 8,
Czech Republic

Received 8 December 1997; accepted 30 April 1998

Abstract

Adsorption of krypton at 77 K on fullerene C , graphitized carbon black and nanocrystalline synthetic diamond
60
has been investigated. The shape of the isotherm on nanocrystalline synthetic diamond indicates that the adsorption
mechanism follows predominantly monolayer–multilayer adsorption. The isotherm on graphitized carbon black is
characterized by a step-like form, at the lowest surface coverage the amount adsorbed obeying Henry’s equation. The
isotherm on fullerene is similar to that on graphitized carbon black in the low-pressure region. At relative pressures
lower than 0.005, both isotherms have a sigmoidal shape, the only difference being that the cooperative build-up of
the first layer ends at a lower coverage on fullerene. The comparison of isotherms on fullerene and graphitized carbon
black has shown that krypton is adsorbed on both solids by the same mechanism at a surface coverage below 0.3.
© 1999 Elsevier Science Ltd. All rights reserved.

Keywords: A. Fullerene; Graphitized carbon black; Diamond; C. Krypton adsorption

1. Introduction adsorbent. As reference materials both other crystallo-

Since the pioneering work in the area of fullerenes,
there have been a number of publications addressing
many aspects of this form of carbon. Although the
adsorption properties of all other carbonaceous solids
were investigated in detail, only few studies have dealt
with those of fullerenes [1–5]. Therefore, this aspect has
remained to be investigated thoroughly. As the sublima-
tion of C occurs at a sufficient rate even at temperatures
60
as low as 673–823 K, this material represents the only
form of carbon that allows a relatively facile study of
the adsorption on a fresh surface prepared in vacuo, i.e.
on the authentic fullerene material [6 ].
In this experimental study a standard approach has
been adopted, namely the adsorption on the material
under investigation is compared to that on a reference
* Corresponding author.
0008-6223/99/$ — see front matter © 1999 Elsevier Science Ltd. All rights reserved.
PII: S0 0 0 8- 6 2 23 ( 9 8 ) 0 01 7 8 -X
graphically defined modifications of carbon, i.e. graphite
and diamond, have been chosen in the form of graphi-
tized carbon black (GCB), which has been featured as
model adsorbent in many fundamental investigations of
gas adsorption, and synthetic diamond (SD) with a
particle size of about 5 nm.
In contrast to our previous study [5], the main
attention has been centred at the analysis of the low-
pressure part of the adsorption isotherms where the
coverage of the surface is low. Then the role of lateral
interactions between adsorbed molecules can be better
clarified and adsorption data provide a better insight
into the nature of the adsorption process.
As all the C samples used are characterized by a
60
very small surface area, isotherms of krypton at 77.2 K
were measured. This adsorbate has come into wide-
spread use for the adsorption measurements on small
surface areas because its saturation vapour pressure is
quite low ( p =221.7 Pa). Consequently the ‘dead space’
o
302 W. Krätschmer et al. / Carbon 37 (1999) 301–305

correction for unadsorbed gas is small enough to permit

the measurement of quite small adsorption with reason-
able precision [7].

2. Experimental

2.1. Materials

The C ‘high grade’ was supplied by Hoechst. In

60
order to obtain C with a freshly formed surface,
60
fullerene was sublimed at ca 773 K and condensed
directly in the adsorption apparatus at 473, 573 or 623 K
in a vacuum better than 10−5 Pa, using a modified
sample flask. Thus prepared transparent fullerene films
were dark brown. (a)
Ultrafine diamond powder was produced in The All-
Russian Research Institute of Technical Physics,
Sneshinsk by a detonation of organic explosives. The
checking of the structure of this material by X-ray
diffraction and electron diffraction analysis proved that
it consisted of pure nanocrystalline diamond. Trans-
mission electron microscopy showed that the mean par-
ticle size was about 5 nm. This value is in agreement with
the results obtained from the analysis of Raman spectra
affording the average crystallite size of 4.5 nm [8].
The graphitized carbon black Carbotrap C was sup-
plied by Supelco.

2.2. Adsorption measurements

Adsorption isotherms of krypton (Technoplyn-Linde,

4.0 purity) were measured by a volumetric method with
an Accusorb 2100E instrument (Micromeritics) comple-
mented with a 133 Pa Baratron gauge (MKS
Instruments) to measure the low equilibrium pressure.
The pressure of krypton was determined with an accu-
racy of ±0.08% of the reading at 133 Pa and ±1.1% of
the reading at 0.013 Pa. The pressure transducers and
the manifold system (i.e. the ‘dead space’) were main-
tained at 307±0.25 K. The krypton isotherms were
measured at the temperature of liquid nitrogen, which
was checked by a thermistor probe. Before each run the
sample was degassed at the temperature T for at least
e of saturated vapours of krypton over the solid phase.
20 hours until a pressure of 10−4 Pa was attained.
All C samples were protected from visible light at
60
temperatures higher than 293 K to minimize photoin-
duced polymerization. The fact that thus prepared fuller-
ene films dissolved immediately and completely in
o-xylene proves that polymerization was prevented.
3. Results
3.1. Isotherms on the reference adsorbents
The adsorption isotherm of krypton on GCB
(degassed at T =623 K ) is shown in Fig. 1(a) and (b).
e
(b)
Fig. 1. (a) Adsorption isotherm of krypton at 77.2 K on graphi-
tized carbon black. (b) The low-pressure region of the adsorp-
tion isotherm of krypton at 77.2 K on graphitized carbon black.
The amount adsorbed is expressed as coverage of the
GCB surface H=a/a , where a is the capacity of the
m m
monomolecular layer. The relative pressure p/p is given
o
as a quotient of the equilibrium pressure and the pressure
In order to calculate the surface coverage H, the
monolayer capacity a should be determined.
m
Application of the BET method encounters the difficulty
that the range of linearity of the BET plot is short. The
point corresponding to monolayer completion can be
located somewhere on the tread of the first step; it is
suitable to measure the height of this tread at its point
of inflection [7]. In this way a =0.122 mmol g−1 was
m
obtained. At the point of inflection of the first tread
H=1; H#2 corresponds to the next tread. The average
area occupied by a krypton atom in the completed
monolayer depends slightly on the nature of the surface.
As its value of 0.195 nm2 remains a useful working
 W. Krätschmer et al. / Carbon 37 (1999) 301–305
figure, the GCB surface area of 14.3 m2 g−1 corresponds
to the assessed value of a .
m m
The isotherms of krypton on SD measured for three
different temperatures of evacuation T =423, 523 and
e
623 K (Fig. 2(a) and (b)) show that T does not influence
e
its adsorption properties. The capacity of the monomo-
lecular layer was determined using the BET equation,
which was valid in the usual range of relative pressure
of 0.05–0.35. The working temperature, 77.2 K, is well
below the triple point of krypton (116 K ). According
to the usual practice of processing krypton isotherms,
the saturation vapour pressure p of the supercooled
o,L
liquid was inserted into the BET equation instead of the
equilibrium pressure of the krypton vapours over the
(a)
(b)
Fig. 2. (a) Adsorption isotherms of krypton at 77.2 K on syn-
thetic diamond degassed at 423 K (solid circles), 523 K (open
circles) and 623 K (triangles). (b) The low-pressure region of
adsorption isotherms of krypton at 77.2 K on synthetic dia-
mond degassed at 423 K (solid circles), 523 K (open circles) and
623 K (triangles).
303
solid phase. The calculated capacity of the monolayer
a and the c constant equalled 2.592 mmol g−1 and 251,
respectively, the corresponding surface area of SD being
304.3 m2 g−1.
3.2. Isotherms on C
60
The adsorption isotherms of krypton on C powder
60
are shown in Fig. 3(a) and (b). As the BET equation
was applicable in a sufficiently wide interval of the
relative pressure, the monolayer capacity was determined
in the same way as with SD. On repeating the measure-
ment for T =423, 523 and 623 K, the monolayer capac-
e
ity a and the surface area slightly increased from 0.30
m
(a)
(b)
Fig. 3. (a) Adsorption isotherms of krypton at 77.2 K on C
60
powder degassed at 423 K (empty circles), 523 K (solid circles)
and 623 K (triangles). (b) The low-pressure region of adsorp-
tion isotherms of krypton at 77.2 K on C powder degassed at
60
423 K (empty circles), 523 K (solid circles) and 623 K
(triangles).
304 W. Krätschmer et al. / Carbon 37 (1999) 301–305
to 0.34 mmol g−1 and from 0.035 to 0.040 m2 g−1, respec-
tively. The BET constant c=54 remained unchanged
within the experimental error. It can be assumed that
particles of C partially disintegrate when heated in
60
vacuo. This conclusion is also supported by SEM images
which show that some disintegration of C crystals
60
occurs due to degassing at 623 K.
Considering the relatively large dead space volume of
the adsorption flask, in which the fullerene films were
prepared by sublimation, the isotherms on these films
were measured at relative pressures exceeding 0.02. The
comparison of isotherms on all films prepared and on
the powder (Fig. 4) shows that they are identical in the
pressure range under study.
4. Discussion
GCB adsorption occurs practically only on the basal
plane of graphite and the influence of energetic hetero-
geneity caused by the surface imperfections is negligible.
According to the classification of adsorption isotherms,
that of krypton on GCB belongs to Type 6 [7]. At the
lowest surface coverage, the amount adsorbed is defined
by the interaction of isolated krypton atoms with the
basal plane of the graphite (see Fig. 1(b)), i.e. by Henry’s
equation
H=K · p/p (1)
H o
From the experimental data it follows that K =50±5.
H
Increasing coverage of the GCB surface gives rise to an
ever-increasing attraction between the adsorbed krypton
atoms. The isotherm is at first convex to the p/p axis,
o
but, as the first layer becomes densely packed with the
Fig. 4. Adsorption isotherms of krypton at 77.2 K on sublimed
C . The films were condensed at 473 K (empty circles), 573 K
60
(solid circles) and 623 K (triangles). The crosses (×) show the
adsorption isotherm on C powder (all runs).
60
adsorbate atoms, the convexity of the isotherm changes
to the H axis, because of the decreased percentage of
the still uncovered surface. This regularity is repeated
in the filling of the second layer. Therefore, each layer
will give rise to a step, such that the riser corresponds
to the cooperative build-up of the layer and the tread
to the transition between the layer and the next higher
one.
The shape of the krypton isotherm on SD belongs to
the Type 2 classification [7]. This is an indication that
the adsorption mechanism is predominantly mono-
layer–multilayer adsorption. Unlike graphite, with
which Henry’s equation holds only up to H#0.04, the
linearity of the krypton isotherm on SD is preserved up
to H#0.35. The calculated Henry’s constant K equal-
H
ling 45±1 is close to that on GCB. As the particles of
SD are approximately ten times larger than the krypton
atoms, the lateral interactions between krypton atoms
can be expected to be effective to a smaller extent than
on the basal plane of graphite. Therefore, the krypton
isotherm is characterized by a relatively long linear part
corresponding to the adsorption of more or less isolated
atoms. At a greater coverage of the surface (H>0.35)
the isotherm becomes convex to the H axis due to the
completion of the first adsorbed layer.
When comparing the isotherm on C with those on
60
both reference materials, it is immediately obvious that
the former isotherm is similar to that on GCB in the
low-pressure region. At p/p <0.005, both isotherms
o
have a sigmoidal shape, the only difference being that
on C the cooperative build-up of the first layer ends
60
at a lower coverage. At p/p >0.005, similarly to the
o
case with SD, a gradual completion of the first mono-
layer occurs which comes to an end at a relative pressure
of about 0.2.
The quantitative comparison of the adsorption iso-
therms on C and GCB can be achieved with advantage
60
by the method of comparison plots [9]. Such a plot
which was constructed on the basis of isotherms in
Figs. 1 and 3 is shown in Fig. 5. The dependence
obtained at H <0.3 is close to a straight line with a
C60
slope of 1 going through the origin of coordinates.
Consequently krypton is adsorbed on both solids by the
same mechanism in this range of surface coverage. An
open question is why the adsorption on C increases
60
substantially more slowly than that on GCB at larger
coverages. The reason is to be looked for in the change
in the lateral interactions between adsorbed atoms of
krypton. The surface of C is known to have a very
60
complicated surface structure with both films and pow-
ders. In some cases distinct features developed at the
surfaces [10]. They could be characterized as dendrites,
screw dislocations, barriers at the edges of faces, lamellar
growth and cavity formation. Such complicated surface
structure then can—analogously to the case of SD—
restrict lateral interactions between atoms of krypton
 W. Krätschmer et al. / Carbon 37 (1999) 301–305
Fig. 5. Comparison of adsorption of krypton at 77.2 K on
C (H ) and GCB (H ).
60 C60 GCB
and consequently hinder the formation of the first
adsorbed layer in comparison with GCB. The isotherm
of krypton on C crystals with perfectly developed
60
facets can be expected to be very similar or even
practically identical with that on the basal plane of
graphite.
305
Acknowledgements
The authors (J. R., A. Z.) acknowledge the Grant
Agency of the Czech Republic for financial support
(Contract No. 203/95/1228). We are grateful to Hoechst
AG for providing us with the fullerene material.
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