The sorption and subsequent desorption of 4He gas by grapheme oxide (GO) and hydrazine-reduced grapheme oxide (RGO-Hz) powders have been investigated in the temperature interval 2 – 25 K. It is found that the Hz-reduction of GO increases the sorptive capacitance of RGO-Hz by a factor of 3.3 in com-parison with GO. It is assumed that the sorptive capacity of the RGO-Hz sample increases because the O2-containing groups are removed in the process of Hz-reduction of GO, which makes the interlayer space ac-cessible for sorption
When you are citing the document, use the following link http://essuir.sumdu.edu.ua/handle/123456789/3520

Basnukaeva, R.M.

Benito, Ana

Dolbin, A.V.

Eselson, V.B.

Gavrilko, V.G.

Manzhelii, V.G.

Vinnikov, N.A.

Electronic Sumy State University Institutional Repository

PROCEEDINGS OF THE INTERNATIONAL CONFERENCE  NANOMATERIALS: APPLICATIONS AND PROPERTIES Vol. 2 No 3, 03NCNN06(2pp) (2013)   2304-1862/2013/2(3)03NCNN06(2) 03NCNN06-1  2013 Sumy State University 4He Sorption in Graphene Oxide at Low Temperatures  A.V. Dolbin1, V.B. Esel'son1, V.G. Gavrilko1, V.G. Manzhelii1, N.A.Vinnikov1,  R.M. Basnukaeva1, Ana Benito2  1 B. Verkin Institute for Low Temperature Physics and Engineering of the National Academy of Sciences of Ukraine, 47 Lenin Ave., Kharkov 61103, Ukraine 2 Instituto de Carboquímica, 4 Miguel Luesma Castán, E-50018 Zaragoza, Spain  (Received 02 February 2013; revised manuscript received 17 June 2013; published online 29 August 2013)  The sorption and subsequent desorption of 4He gas by grapheme oxide (GO) and hydrazine-reduced grapheme oxide (RGO-Hz) powders have been investigated in the temperature interval 2 – 25 K. It is found that the Hz-reduction of GO increases the sorptive capacitance of RGO-Hz by a factor of 3.3 in com-parison with GO. It is assumed that the sorptive capacity of the RGO-Hz sample increases because the O2-containing groups are removed in the process of Hz-reduction of GO, which makes the interlayer space ac-cessible for sorption    Keywords: Quantum effects, Sorption kinetics, Graphene oxide, Helium.    PACS number: 68.43.Mn   1. INTRODUCTION  Oxidation of graphite and the subsequent ultrasonic dispersion of the graphite oxide to the state of graphene oxide (GO) is one of the simple technologies of large-scale production of graphene-based materials [1]. Gra-phene oxide consists of intact graphite areas with in-clusions of sp3-hybridized carbon atoms. The inclusions contain hydroxyl and epoxy functional groups at the upper and bottom surfaces of every graphene sheet and sp2-hybridized carbon containing carboxyl and carbonyl groups located mainly at the edges of the graphene sheet.  Graphene oxide, like graphite, has a layered struc-ture consisting normally of several graphene layers. The layer spacing vary within 6-8 Å depending on the technology of GO preparation and the oxidation level [2, 3]. The carbon layers of GO are deformed by the sp2 → sp3 transitions of the C atoms. Normally, GO contains a great number of topological structural de-fects and ruptures. The GO layers are weakly related to each other. The O2 – containing groups can be removed partial-ly by reducing graphene oxide, for example, with hy-drazine, dimethyl hydrazine, hydroquinone, sodium boron hydride and so on. It is however essential that the residual oxide groups and the surface defects inevi-table in the process of GO reduction affect seriously the structure of the graphene plane. This suggests that reduced graphene oxide (RGO) and graphene can hard-ly be taken as completely similar substances. The RGO technology is one of the methods used to produce mac-roscopic quantities of a graphene –like material for wide – range applications. Owing to their large specific area of surface [4, 5], GO and RGO can be used as high – efficiency sorbents.  In this context investigations of the sorptive charac-teristics of GO and RGO reactive toward a helium im-purity at low temperatures rank among the urgent re-search problems, especially for the use of GO in cryo-genic engineering.   2. EXPERIMENTAL TECHNIQUE  The sorptive properties and the saturation-desorption kinetics of He impurity in graphene oxide (GO) and hydrazine – reduced graphene oxide (RGO-Hz) have been investigated experimentally using a la-boratory stand (its design and operation are detailed in [6, 7]). The temperature interval was 2-25 K. The GO and RGO-Hz samples were powders with ~ 10 μm grains and masses of ~40 mg. Immediately before start-ing the investigation, the powder samples were evacu-ated for five days at room temperature in the measur-ing cell of the stand to remove the possibly available gas impurities and moisture. The pressure of GO saturation with each impurity was ~ 1 Torr. As soon as the sample absorbed the gas, a new portion of impurity was added to the cell. The sat-uration temperature was chosen so that the pressure of the gas impurity in the measuring cell remained in the process of saturation 2.5 – 3 times lower than the satu-ration vapor pressure of the impurity at this tempera-ture. These sorption condition excluded condensation of the impurity vapors and the formation of films at the grain surfaces and the cell walls. Feeding the gas im-purity was stopped when the equilibrium pressure 10-2 Torr was achieved in the cell. The cell was then sealed and the changes in the pressure were recorded in the process of impurity desorption from the powder on its stepwise heating. The gas impurity evolved due to the heating was taken to an evacuated calibrated vessel. The pressure in it was measured with two capacitance manometer (MKS-627B) capable of measuring pressure in the range 10-3 – 1000 Torr, the error being 1·10-4 Torr. When the pressure was stabilized, the vessel was detached from the sample, evacuated and then joined to it again. The gas extraction was continued until the gas pressure over the sample reduced to 10-2 Torr. Then the measurement was repeated at the next value of tem-perature.  3. RESULTS AND DISCUSSION   The temperature dependences of the quantities of  A.V. DOLBIN, V.B. ESEL'SON, V.G. GAVRILKO, ET AL. PROC. NAP 2, 03NCNN06 (2013)   03NCNN06-2 4He gas desorbed from the GO and RGO-Hz samples are illustrated in Fig.1. The number of impurity particles NA is normalized to the total number NC of C atoms in the samples. Note that the total quantities of the sorbed and desorbed impurities coincide within the experimental error.  0 4 8 12 16 20 240.0000.0010.0020.003NA/NC He-GO He-RGOHzT (K)   Fig. 1 – The temperature dependences of the relative quantity of 4He impurity desorbed from the GO and RGO-Hz samples.  The total concentrations of the 4He impurity atoms in the GO and RGO-Hz samples were 0.0026 and 0.00867, respectively (in molar fractions, i.e. the number of impu-rity particles per C atom). It is seen in Fig.1 that the temperature intervals of the dominant bulk of 4He desorption are different for the GO and RGO-Hz samples. This may be due to the fea-tures of the sample structures. It is probable that the access of the impurity particles to the interplanar space of GO is limited by the oxide groups. As a result, the sorption of impurities proceeds mainly at the outer sur-faces of the grapheme planes. The Hz-reduction reduces the distance between the layers to 0.55 nm [8] or even 0.44 nm when the epoxy and hydroxyl groups are nearly fully removed from both sides of the grapheme plane [9]. The Hz-reduction of GO changes drastically the charac-ter of the desorption curves by shifting the desorption maximum towards higher temperatures for all of the investigated impurities. Most likely the Hz-reduction of GO is an efficient way of removing the functional groups which block the access to the space between the graph-eme planes. Since the impurity particles in the inter-planar space of the RGO-Hz sample have higher binding energies than those at the outer grapheme surface [10], the particle desorption from the interplanar space pro-ceeds at a higher temperature. The assumption of a greater possibility for sorption in the interplanar space of the RGO-Hz sample is supported by the higher (3.3 times) sorptive capacity of this sample in comparison with the GO one.  4. CONCLUSIONS  The sorption and the subsequent desorption of 4He gas by the powders of grapheme oxide (GO) and hydrazine – reduced grapheme oxide (RGO-Hz) have been investi-gated in the temperature interval 2-25K. It has been found that Hz-reduction of GO causes signification changes in the sorptive properties: the total sorptive capacity of the RGO-Hz sample is 3.3 times higher than that of the GO sample. The increase is most likely due to removal of oxygen-containing groups in the Hz-reduction of GO, which makes the interplanar space of GO accessible for sorption.   REFERENCES  1. S. Mao, H. Pu and J. Chen, RSC Advances 2, 2643, (2012). 2. A. B. Bourlinos, D. Gournis, D. Petridis, T. Szabo, A. Szeri, I. Dekany, Langmuir 19, 6050 (2003). 3. M. Hirata, T. Gotou, S. Horiuchi, M. Fujiwara, M. Ohba, Carbon 42, 2929 (2004). 4. G. Srinivas, J. Burres, T. Yildirim, Energy Environ. Sci. 5, 6453 (2012). 5. G. Srinivas, J. W. Burress, J. Ford, T. Yildirim, J. Mater. Chem. 21, 11323 (2011). 6. A.V. Dolbin, V.B. Esel’son, V.G. Gavrilko, V.G. Manzhelii, N.A. Vinnikov, S.N. Popov, JETP Lett. 93, 577 (2011). 7. A.V. Dolbin, V. B. Esel'son, V. G. Gavrilko, V. G. Man-zhelii, N. A. Vinnikov and S. N. Popov, Fiz. Nizk. Temp.  36, 1352 (2010) [Low Temp. Phys. 36, 1091 (2010)].  8. O. Akhavan, E. Ghaderi, S. Aghayee, Y. Fereydooni,  A. Talebi, J. Mater. Chem. 22, 13773 (2012). 9. M.X. McAllister, J.L. Li, D.H. Adamson, H.C. Schniepp, A.A. Abdala, J. Liu, M. Herrera-Alonso, D.L. Milius, R. Car, R.K. Prud'homme, I.A. Aksay, Chem. Mater. 19, 4396 (2007). 10. V. Tozzini, V. Pellegrini, Phys. Chem. Chem. Phys. 15, 80 (2013).  

4He Sorption in Graphene Oxide at Low Temperatures

SocioEconomic Challenges Journal (Sumy State University)

PROCEEDINGS OF THE INTERNATIONAL CONFERENCE  
NANOMATERIALS: APPLICATIONS AND PROPERTIES 
Vol. 2 No 3, 03NCNN06(2pp) (2013) 
 
 
2304-1862/2013/2(3)03NCNN06(2) 03NCNN06-1  2013 Sumy State University 
4He Sorption in Graphene Oxide at Low Temperatures 
 
A.V. Dolbin1, V.B. Esel'son1, V.G. Gavrilko1, V.G. Manzhelii1, N.A.Vinnikov1,  
R.M. Basnukaeva1, Ana Benito2 
 
1 B. Verkin Institute for Low Temperature Physics and Engineering of the National Academy of Sciences of Ukraine, 
47 Lenin Ave., Kharkov 61103, Ukraine 
2 Instituto de Carboquímica, 4 Miguel Luesma Castán, E-50018 Zaragoza, Spain 
 
(Received 02 February 2013; revised manuscript received 17 June 2013; published online 29 August 2013) 
 
The sorption and subsequent desorption of 4He gas by grapheme oxide (GO) and hydrazine-reduced 
grapheme oxide (RGO-Hz) powders have been investigated in the temperature interval 2 – 25 K. It is 
found that the Hz-reduction of GO increases the sorptive capacitance of RGO-Hz by a factor of 3.3 in com-
parison with GO. It is assumed that the sorptive capacity of the RGO-Hz sample increases because the O2-
containing groups are removed in the process of Hz-reduction of GO, which makes the interlayer space ac-
cessible for sorption   
 
Keywords: Quantum effects, Sorption kinetics, Graphene oxide, Helium. 
 
  PACS number: 68.43.Mn 
 
 
1. INTRODUCTION 
 
Oxidation of graphite and the subsequent ultrasonic 
dispersion of the graphite oxide to the state of graphene 
oxide (GO) is one of the simple technologies of large-
scale production of graphene-based materials [1]. Gra-
phene oxide consists of intact graphite areas with in-
clusions of sp3-hybridized carbon atoms. The inclusions 
contain hydroxyl and epoxy functional groups at the 
upper and bottom surfaces of every graphene sheet and 
sp2-hybridized carbon containing carboxyl and carbonyl 
groups located mainly at the edges of the graphene 
sheet.  
Graphene oxide, like graphite, has a layered struc-
ture consisting normally of several graphene layers. 
The layer spacing vary within 6-8 Å depending on the 
technology of GO preparation and the oxidation level 
[2, 3]. The carbon layers of GO are deformed by the 
sp2 → sp3 transitions of the C atoms. Normally, GO 
contains a great number of topological structural de-
fects and ruptures. The GO layers are weakly related to 
each other. 
The O2 – containing groups can be removed partial-
ly by reducing graphene oxide, for example, with hy-
drazine, dimethyl hydrazine, hydroquinone, sodium 
boron hydride and so on. It is however essential that 
the residual oxide groups and the surface defects inevi-
table in the process of GO reduction affect seriously the 
structure of the graphene plane. This suggests that 
reduced graphene oxide (RGO) and graphene can hard-
ly be taken as completely similar substances. The RGO 
technology is one of the methods used to produce mac-
roscopic quantities of a graphene –like material for 
wide – range applications. 
Owing to their large specific area of surface [4, 5], 
GO and RGO can be used as high – efficiency sorbents.  
In this context investigations of the sorptive charac-
teristics of GO and RGO reactive toward a helium im-
purity at low temperatures rank among the urgent re-
search problems, especially for the use of GO in cryo-
genic engineering. 
  
2. EXPERIMENTAL TECHNIQUE 
 
The sorptive properties and the saturation-
desorption kinetics of He impurity in graphene oxide 
(GO) and hydrazine – reduced graphene oxide (RGO-
Hz) have been investigated experimentally using a la-
boratory stand (its design and operation are detailed in 
[6, 7]). The temperature interval was 2-25 K. The GO 
and RGO-Hz samples were powders with ~ 10 μm 
grains and masses of ~40 mg. Immediately before start-
ing the investigation, the powder samples were evacu-
ated for five days at room temperature in the measur-
ing cell of the stand to remove the possibly available 
gas impurities and moisture. 
The pressure of GO saturation with each impurity 
was ~ 1 Torr. As soon as the sample absorbed the gas, a 
new portion of impurity was added to the cell. The sat-
uration temperature was chosen so that the pressure of 
the gas impurity in the measuring cell remained in the 
process of saturation 2.5 – 3 times lower than the satu-
ration vapor pressure of the impurity at this tempera-
ture. These sorption condition excluded condensation of 
the impurity vapors and the formation of films at the 
grain surfaces and the cell walls. Feeding the gas im-
purity was stopped when the equilibrium pressure 10-2 
Torr was achieved in the cell. The cell was then sealed 
and the changes in the pressure were recorded in the 
process of impurity desorption from the powder on its 
stepwise heating. The gas impurity evolved due to the 
heating was taken to an evacuated calibrated vessel. 
The pressure in it was measured with two capacitance 
manometer (MKS-627B) capable of measuring pressure 
in the range 10-3 – 1000 Torr, the error being 1·10-4 
Torr. When the pressure was stabilized, the vessel was 
detached from the sample, evacuated and then joined to 
it again. The gas extraction was continued until the gas 
pressure over the sample reduced to 10-2 Torr. Then the 
measurement was repeated at the next value of tem-
perature. 
 
3. RESULTS AND DISCUSSION  
 
The temperature dependences of the quantities of 
 A.V. DOLBIN, V.B. ESEL'SON, V.G. GAVRILKO, ET AL. PROC. NAP 2, 03NCNN06 (2013) 
 
 
03NCNN06-2 
4He gas desorbed from the GO and RGO-Hz samples are 
illustrated in Fig.1. The number of impurity particles NA 
is normalized to the total number NC of C atoms in the 
samples. Note that the total quantities of the sorbed and 
desorbed impurities coincide within the experimental 
error. 
 
0 4 8 12 16 20 24
0.000
0.001
0.002
0.003
N
A
/N
C
 He-GO
 He-RGOHz
T (K)  
 
Fig. 1 – The temperature dependences of the relative quantity 
of 4He impurity desorbed from the GO and RGO-Hz samples. 
 
The total concentrations of the 4He impurity atoms in 
the GO and RGO-Hz samples were 0.0026 and 0.00867, 
respectively (in molar fractions, i.e. the number of impu-
rity particles per C atom). 
It is seen in Fig.1 that the temperature intervals of 
the dominant bulk of 4He desorption are different for the 
GO and RGO-Hz samples. This may be due to the fea-
tures of the sample structures. It is probable that the 
access of the impurity particles to the interplanar space 
of GO is limited by the oxide groups. As a result, the 
sorption of impurities proceeds mainly at the outer sur-
faces of the grapheme planes. The Hz-reduction reduces 
the distance between the layers to 0.55 nm [8] or even 
0.44 nm when the epoxy and hydroxyl groups are nearly 
fully removed from both sides of the grapheme plane [9]. 
The Hz-reduction of GO changes drastically the charac-
ter of the desorption curves by shifting the desorption 
maximum towards higher temperatures for all of the 
investigated impurities. Most likely the Hz-reduction of 
GO is an efficient way of removing the functional groups 
which block the access to the space between the graph-
eme planes. Since the impurity particles in the inter-
planar space of the RGO-Hz sample have higher binding 
energies than those at the outer grapheme surface [10], 
the particle desorption from the interplanar space pro-
ceeds at a higher temperature. The assumption of a 
greater possibility for sorption in the interplanar space 
of the RGO-Hz sample is supported by the higher (3.3 
times) sorptive capacity of this sample in comparison 
with the GO one. 
 
4. CONCLUSIONS 
 
The sorption and the subsequent desorption of 4He gas 
by the powders of grapheme oxide (GO) and hydrazine 
– reduced grapheme oxide (RGO-Hz) have been investi-
gated in the temperature interval 2-25K. It has been 
found that Hz-reduction of GO causes signification 
changes in the sorptive properties: the total sorptive 
capacity of the RGO-Hz sample is 3.3 times higher than 
that of the GO sample. The increase is most likely due 
to removal of oxygen-containing groups in the Hz-
reduction of GO, which makes the interplanar space of 
GO accessible for sorption. 
 
 
REFERENCES 
 
1. S. Mao, H. Pu and J. Chen, RSC Advances 2, 2643, (2012). 
2. A. B. Bourlinos, D. Gournis, D. Petridis, T. Szabo, A. Szeri, 
I. Dekany, Langmuir 19, 6050 (2003). 
3. M. Hirata, T. Gotou, S. Horiuchi, M. Fujiwara, M. Ohba, 
Carbon 42, 2929 (2004). 
4. G. Srinivas, J. Burres, T. Yildirim, Energy Environ. Sci. 5, 
6453 (2012). 
5. G. Srinivas, J. W. Burress, J. Ford, T. Yildirim, J. Mater. 
Chem. 21, 11323 (2011). 
6. A.V. Dolbin, V.B. Esel’son, V.G. Gavrilko, V.G. Manzhelii, 
N.A. Vinnikov, S.N. Popov, JETP Lett. 93, 577 (2011). 
7. A.V. Dolbin, V. B. Esel'son, V. G. Gavrilko, V. G. Man-
zhelii, N. A. Vinnikov and S. N. Popov, Fiz. Nizk. Temp.  
36, 1352 (2010) [Low Temp. Phys. 36, 1091 (2010)].  
8. O. Akhavan, E. Ghaderi, S. Aghayee, Y. Fereydooni,  
A. Talebi, J. Mater. Chem. 22, 13773 (2012). 
9. M.X. McAllister, J.L. Li, D.H. Adamson, H.C. Schniepp, 
A.A. Abdala, J. Liu, M. Herrera-Alonso, D.L. Milius, R. 
Car, R.K. Prud'homme, I.A. Aksay, Chem. Mater. 19, 4396 
(2007). 
10. V. Tozzini, V. Pellegrini, Phys. Chem. Chem. Phys. 15, 80 
(2013). 
 


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4He Sorption in Graphene Oxide at Low Temperatures

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