BUDAPEST UNIVERSITY OF TECHNOLOGY AND ECONOMICS

Faculty of Chemical Technology and Biotechnology

George A. Olah Doctoral School

PROPERTIES OF GRAPHENE OXIDE AND GRAPHENE OXIDE

DERIVATIVES

PhD thesis booklet

Author:
SHEREEN FARAH AHMED FARAH

Supervisor: Prof. Krisztina László

Budapest, Hungary 2022

1 PhD Thesis
2 PhD Thesis

1. Introduction

Although for many years graphene oxide (GO) has been mainly considered as a precursor
of graphene, recently, it has gained its own well-deserved recognition. The planar structure
with a 2D atomic layer composed of crumpled sheets of sp2- and sp3- hybridized carbon atoms,
that enriched with oxygen functionalities such as epoxide, hydroxyl, ketone, carboxyl and
lactonic groups on the basal plane and at the edges (Fig. 1)[1].

Figure 1. Structure of GO layer proposed by Aliyev et al.[1].

Consequently, GO is usually better dispersed than other graphene nanomaterial in aqueous

solution [2], due to its hydrophilic nature. The active sites of GO can be easily functionalized
opening an avenue, e.g., for site specific applications [3]. Due to its amphiphilic nature, the
preparation of stable aqueous GO dispersions is an effective method for graphene processing,
leading to a wide variety of applications, for example desalination, water treatment and energy
storage [4]. In addition to, GO is promising material in various area including: direct ink writing,
3D printing, film casting, wet spinning [5]. Nevertheless, although GO is mainly used for its
easy processability, for several applications a final modification step is needed for partially
restoration of graphitic structure and can be accomplished by chemical or/ and physical
reduction methods [6] resulting in reduced graphene oxide (RGO). However, the graphenic
structure is not fully restored using these techniques, and significant defects are introduced.
The intriguing chemical-physical properties of GO have also attracted strong interest in
biological studies. Moreover, among its other talents, the ability of graphene to protect

1
Aliyev, E.; Filiz, V.; Khan, M. M..; Lee, Y. J.; Abetz, C.; Abetz, V. Structural Characterization of Graphene
Oxide: Surface Functional Groups and Fractionated Oxidative Debris. Nanomaterials 2019, 9, 1180;
https://doi.org/10.3390/nano9081180.
2
Zou, Y.; Wang, X.; Ai, Y.; Liu, Y.; Li, J.; Ji, Y.; Wang, X. Coagulation Behavior of Graphene Oxide on
Nanocrystallined Mg/Al Layered Double Hydroxides: Batch Experimental and Theoretical Calculation Study.
Environ. Sci. Technol. 2016, 50, 3658−67. https://doi.org/10.1021/acs.est.6b00255.
3
Dreyer, DR, Park, S, Bielawski, CW, Ruoff RS. The chemistry of graphene oxide. Chem. Soc. Rev. 2010; 39,
228–40. https://doi.org/10.1039/B917103G.
4
Zhu Y.; Murali S.; Cai W.; Li X.; Suk J. W.; Potts J. R.; Ruoff, R S. Graphene and Graphene Oxide: Synthesis,
Properties, and Applications. 2020, 30, 1907678. https://doi.org/10.1002/adma.201001068.
5
Corker, A.; Ng, H.C.-H.; Poole, R.J.; García-Tuñón, E. 3D printing with 2D colloids: Designing rheology
protocols to predict ‘printability’ of soft-materials. Soft Matter 2019, 15, 1444−56.
https://doi.org/10.1039/C8SM01936C.
6
Chua CK.; Pumera M. Chemical reduction of graphene oxide. A synthetic chemistry viewpoint. Chem. Soc. Rev.
2014; 43, 291–312. https://doi.org/10.1039/C3CS60303B.
3 PhD Thesis

biomolecules from enzymatic cleavage has revealed the potential applications of graphene
derivatives in biological studies [7].
GO is the material with nonstoichiometric composition, commonly produced by oxidation
of graphite in highly acidic medium, which weakens the van der Walls interactions between
the stacked carbon planes, followed by exfoliation of the sheets into monolayers or few-layered
stacks. The obtained GO shows controlled properties depending on the graphite precursor [8],
the exfoliation method applied [9] and the consecutive purification process [10]. Among the
various wet chemical exfoliation methods of graphite to obtained GO, an “improved”
Hummers’ method is the winner as it does not generate toxic gases and the temperature is easily
controlled. The obtained GO has fewer defects compared to Hummers’ GO [9].
Although GO was proved to be a promising material for numerous application, there are still
challenges to overcome. Among these challenges the properties of GO obtained by wet
chemical methods need to be tuned. More research is required to reveal long-term aging and it
is mechanism. Moreover, understanding the restoration process of the graphitic structure during
reduction of GO, healing the defects, and consequently obtaining large area GO sheets and less
defective for electronic applications are still obstacles. Overcoming these challenging, will
extend the area of applications and open the modern industry for graphene based materials
technologies.
In my thesis, three challenges, (i) hydrophilic/hydrophobic properties of GO will be tuned
to recover aromatic structure (ii) long-term aging and its mechanism will be addressed (iii) the
heterogeneity of the particles of an “improved” Hummers’ aqueous GO suspension will be
revealed.

2. Motivation

Graphene oxide (GO) obtained by a particular wet chemical exfoliation is heterogeneous in

the terms of lateral extensions, thickness and surface chemistry, etc. It is well-known that these
properties fundamentally govern the physical performance of micro/macro-scale material. In
this study, we fractionate aqueous GO into 5 fractions and compared their morphology and
chemical behavior.
Nowadays, GO can be applied as a membrane for filtration and separation. GO is also
considered the path way to obtain reduce graphene oxides (RGO). The latter materials are
promising in sensors, energy storage devices, optics etc. that can be realized only after chemical
or/ and physical modification of GO. For these applications, the most important problem is the
restoration of aromatic structure. Two ways were adopted to reduce the GO by energetically
reasonable thermal and green chemical methods. The morphology, thermal stability, surface
functional groups, defects of RGO, as well as the efficiency and selectivity of the reductions
were compared.
Direct ink writing, 3D printing, film casting, wet spinning are the techniques that require
GO in a suspended form. Therefore, studying the rheological behavior of aqueous GO
suspension is needed i.e. following mechanical stability and the microstructure. Diverse
rheological methods were applied to investigate shear thinning, viscoelastic and recovery

7
Wang, Y.; Li, Z.; Wang, J.; Li, J.; Lin, Y.; Graphene and graphene oxide: biofunctionalization and applications
in biotechnology. Trends in Biotechnology 2011, 29, 205-212. https://doi.org/10.1016/j.tibtech.2011.01.008.
8
Botas, C.; Álvarez, P.; Blanco, C.; Santamaria, R.; Granda, M.; Ares, P. et al. The effect of the parent graphite
on the structure of graphene oxide. Carbon. 2012, 50, 275–82. https://doi.org/10.1016/j.carbon.2011.08.045.
9
Marcano, D.C.; Kosynkin, D.V.; Berlin, J.M.; Sinitskii, A.; Sun, Z.; Slesarev, A.; et al. Improved synthesis of
graphene oxide. ACS Nano 2010, 4, 4806–14. https://doi.org/10.1021/nn1006368.
10
Chua, CK.; Sofer, Z.; Pumera, M. Graphite Oxides: Effects of permanganate and chlorate oxidants on the
oxygen composition. Chem. Eur. J. 2012, 18, 13453–9. https://doi.org/10.1002/chem.201202320
4 PhD Thesis

behavior of concentrated aqueous GO suspension which are relevant in the mentioned

applications.
Due to the above mentioned applications, it is important to know how the properties of this
suspension change during storage. In order to get information about the shelf-life of aqueous
GO, the aging of GO suspensions was followed in two-year time scale form the prospective of
mechanical and chemical stabilities as well as the microstructure.
The morphology, chemical properties and rheological behavior of the GO samples were
studied in wet and freeze-dried forms using wide range of techniques listed in Section 3.2.

3. Experimental methods
3.1. Wet exfoliation of graphite

Natural graphite powder (GR) was purchased from Tyn, China, with purity of 99.5% and
with 90% <63 µm. Graphene oxide (GO) was prepared according to an “improved” Hummers’
method [9, 11]. The product was washed thoroughly until a close to neutral pH (~ 6) of the
supernatant was achieved. The brown 0.72 v/v% (10 mg mL-1) aqueous suspensions were
stored in sealed amber bottles at ambient conditions (~25 °C). Part of the aqueous GO was
freeze-dried to obtain GO rods. The freeze-dried GO was kept in a desiccator over silica gel
[12]
.The real density of freeze-dried is 1.39 g cm-3 [13]. 0.0285 g of freeze-dried GO was heated
in an air atmosphere oven at temperature of 110 °C for 8 h resulting in 78.6% of GO110.
3.2. Methods

Scanning electron microscopy (SEM), transmission scanning microscopy (TEM) and

powder X-ray diffraction (XRD) were used to characterize the morphology of GO.
Thermogravimetry/differential thermal analysis (TG/DTA) combined with mass spectroscopy
(MS) were applied to reveal the thermal behavior and provides information about the overall
oxidation level of GO and its reduced derivatives. Attenuated total reflection Fourier transform
infrared (ATR-FTIR), Raman and X-ray photoelectron (XP) spectroscopies, and
potentiometric titration were applied to study chemical behavior of GO samples. Rheological
methods were applied to study rheological behavior and the aging of concentrated aqueous GO
suspensions.
4. Results and discussion
4.1. Graphene oxide

Figure 2 shows sheet-like morphology graphene oxide (GO). The well-defined sheets look
translucent, with some wrinkles on the surface. The TEM image reveals that the particles are
heterogeneous both in thickness (layer number) and in lateral extension. The particle size
changes over a wide range, from about 2 x 2 nm to ca 9 x 2 μm [13].

11
Hummers, Jr. W. S.; Offeman, R. E. Preparation of graphitic oxide. J. Am. Chem. Soc. 1958, 80, 1339−1339.
https://doi.org/10.1021/ja01539a0171.
12
Farah, S.; Farkas, A.; Madarász, J.; László, K. Comparison of thermally and chemically reduced graphene
oxides by thermal analysis and Raman spectroscopy. J. Thermal Analysis and Calorimetry, 2020, 142, 331–337.
https://doi.org/10.1007/s10973-020-09719-3.
13
Gyarmati, B.; Farah, S.; Farkas, A.; Sáfrán, G.; Voelker-Pop, M. L.; László, K.
Long-Term Aging of Concentrated Aqueous Graphene Oxide Suspensions Seen by Rheology and Raman
Spectroscopy. Nanomaterials. 2022, 12:916. https://doi.org/10.3390/nano12060916.
5 PhD Thesis

Figure 2. TEM image of the GO. Scale bare 2 µm and 200 nm from left to right [13].
The acid-base properties of GO sample were characterized by potentiometric titration in
CO2-free dilute aqueous 0.1 M KCl background solution. The titration data obtained in
triplicate and is presented in the form of proton excess isotherm of GO (Fig. 3 A). The negative
sign of the surface excess isotherm means that the GO is negatively charged in the whole pH
range. The increasing of the pH leads to subsequent the deprotonation according to pKa values.
Similarly decreasing the pH results in (re) protonation. The hysteresis loop between the forward
and backward implying the protonation lead to irreversible changes. Based on the pKa data
(Fig. 3 B) derived from distribution most probably this change is in the range of lactonic groups
6-10 [14] similar to hydrolysis of benzofuranone and ε-caprolactone.
The pKa distribution curves have maxima around 4, 6, 7, 9 and 10 (Fig. 3 B). They belong
to stronger carboxylic acid pKa ˂ 6, cyclic ester or lactonic pKa ˃ 6 and phenolic hydroxyl
groups (pKa ˃ 10). The pKa range 6-10, which is not resolved in the traditional Boehm titration
[14]
is treated as a single peak. It was resolve into three peaks corresponding to lactonic groups
in different environments. The titration results confirm the recent finding of Aliyev et al.
(Fig 1) [15]. 14
pH 2.5 up
3 4 5 6 7 8 9 10 11 down
0
f(pKa), (mmol/pka/g)

2.0
Proton excess (mmol/g)

-1
1.5
-2
Down Up 1.0
-3
0.5
-4
0.0
-5 2 4 6 8 10
pKa

(A) (B)
Figure 3. Potentiometric titration curves (A) and pKa distribution curves of the surface
oxygen groups (calculated with the SAlEUS software [16]) (B)

Further properties will be evaluated in comparison with reduced derivatives. Here I only
discuss the acid-base properties of the GO sample.

14
Boehm, H.-P.; Diehl, E.; Heck, W.; Sappok, R. Surface Oxides of Carbon. Angew. Chem. Internat. Edit. 1964,
3, 669-77. https://doi.org/10.1002/anie.196406691.
15
Aliyev, E.; Filiz, V.; Khan, M. M.; Lee, Y. J.; Abetz, C.; Abetz, V. Structural Characterization of Graphene
Oxide: Surface Functional Groups and Fractionated Oxidative Debris. Nanomaterials 2019, 9, 1180;
https://doi.org/10.3390/nano9081180
16
Jagiello, J. Stable numerical solution of the adsorption integral equation using splines. Langmuir 1994, 10,
2778–85, https://doi.org/10.1021/la00020a04545.
6 PhD Thesis

4.2. Heterogeneity of the particles in the GO suspension

The GO was separated by centrifugation at forces of 10700 g, 7000 g, 4200 g, and 2000 g
into 5 fractions (GO1-GO5). GO1 is expected the lowest density and GO5 is the highest one.
Raman results (Fig. 4 A and B) showed that the GO3 and GO5 less defected with highest La
whereas GO1 and GO2 more defected with small conjugated aromatic domains sheet. Lc XRD
was highest in GO2 and lower in GO1 and GO5 (Fig. 4 C). No systematic trend in the Raman
and XRD properties across the fractions density.
1.70 14
16

1.65
13
14
1.60
La (nm)

Lc (nm)
ID/IG

1.55 12
12

1.50
11 10
1.45
10 8
1.40 O 1 2 3 4 5
O 1 2 3 4 5 G GO GO GO GO GO

5
O
G GO GO GO GO GO

O
G
G

G
(A) (B) (C)
1.6 0.46 4.5

Surface concentration (mmol/g)

1.4

upward
0.44

downward
4.0
Intensity ratio

O/C ratio
(C=O/C=C)

1.2
(C-O-C/C=C)

0.42 3.5
1.0
0.40 3.0
0.8
2.5
0.6 0.38
O 1 2 3 4 5 O 1 2 3 4 5 O 1 2 3 4 5
G GO GO GO GO GO G GO GO GO GO GO G GO GO GO GO GO

(D) (E) (F)

Figure 4. Raman ID/IG ratio (A) and La (B) XRD Lc (C) FTIR intensity ratio of (C=O/C=C)
and (C-O-C/C=C) (D), XPS O/C (E) and total surface concentration obtained from
titration measurements using SAlEUS software [16] similar to that in Section 4.1 (F)15.

The GO1 has more abundant oxygen functional groups and GO5 has the least (Fig. 4 D-F).
Again, similarly to Raman and XRD results, there is no systematic trend from GO1-GO5.
The above findings reveal that the aromatic crystallite size, the height, the surface chemistry
of the GO platelets are heterogeneous. In some cases the differences are subtle but exceed the
experimental uncertainties. Unlike in the reported cases [17] no systematic trend was observed
in the properties studied along the fractions. A plausible explanation is that some of the
assumptions implied in the Stokes’ law may not hold for our system. The viscosity in our
fractionation particularly the 1st three steps of the fractionation is higher than that for pure water
which means that the particles are not independent from each other. The density of the hydrated
GO, not only the “naked” one governs the separation since GO obtained by wet chemical
exfoliation may contain high number of imperfections (defects and vacancies) either inherited
from GR or developed during the synthesis.

17
Bidram, E.; Sulistio, A.; Amini, A.; Fu, Q. Qiao, G. G.; Stewart, A. Fractionation of graphene oxide single
nano-sheets in water-glycerol solutions using gradient centrifugation, Carbon 2016, 103 363-71.
http://dx.doi.org/10.1016/j.carbon.2016.02.095
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4.3. Graphene oxide and its thermally and chemically reduced derivatives

Thermally reduced graphene oxide (TRGO) was obtained from freeze-dried GO after
heating from room temperature to 300 °C with heating rate of 1.5 °C min-1 in Ar for 3 h.
Chemical reduction of the suspended GO was performed by treating the suspension in 0.02 M
aqueous ascorbic acid (AA) at pH = 10 set by cc. NH4OH and at 95 °C for 1 h. The purified
suspension was freeze-dried (CRGO). The thermal and chemical reduction gave yield of 53%
and 63% respectively [12, 18].16
The Raman spectra (Fig. 5 A) reflect the alteration of the graphitic order during the wet
chemical exfoliation and the following reductions. It is deconvoluted into the following bands:
G (graphitic band, related to the breathing of the sp2 building blocks), D (defect band,
associated with the structural disorder), D', D* (Disorder from graphitic lattices and
impurities), 2D (structural order, related to the number of layers), G*, D+D' and 2D' bands.
The intensity ratio ID/IG is the hallmark of the defects, i.e., the extent of the sp2 domain size of
the graphene sheet containing sp2 and sp3 carbons. The ID/IG ratio dramatically increased (from
GR 0.17 to GO 1.46) after the oxidative exfoliation indicating a high degree of disorder and
even it increased to 1.50 and 1.60 after thermal and chemical treatments respectively. The
decrease in the extension of the in-plane sp2 domains; La (GR 113 nm to GO 13.2 nm) seems
to be more expressed during the chemical exfoliation and does not affected after thermal
treatment (12.8 nm) but does dropped after chemical reduction to 12.0 nm [18].
From the XRD pattern (Fig. 5 B), the estimated interlayer distances dropped from 0.77 nm
in GO to 0.38 and 36 nm in TRGO and CRGO respectively. The calculated number of the layer
dropped significantly after oxidation from 118 to 16 and it decreased even more after both
reductions to 3.5 ± 0.5. The Raman and XRD results unanimously confirm a delicate
morphological difference between the TRGO and CRGO. The chemical reduction results in
platelets with narrower interlayer distance, smaller lateral dimension and higher ID/IG ratio [18].
(002)
(100) CRGO
CRGO (002)
Intensity (a.u.)

Intensity (a.u.)

TRGO
(001)
TRGO
GOL n
D G (002)
GOL
D' 2D D+G n (004) GR
D* D'' G* 2D'

1000 1500 2000 2500 3000 3500 10 20 30 40 50 60 70 80

-1
Raman shift (cm ) 2 theta ()

(A) (B)
Figure 5. Raman spectra (A) and powder X-ray diffractograms (B). The normalized graphs
are vertically shifted [18].
The TGA/DTA-MS reveals that the GO is significantly less stable than its precursor,
whereas the two reduced oxides exhibit high thermal stability but with some differences.
TRGO is more stable than GO and by 900 °C there is mass lost mainly from CO2, while, CRGO
started to decay at higher temperature [12].

18
Bertóti, I., Farah S., Bulátkó, A., Farkas, A., Madarász, J., Mohai, M., Sáfrán, G., László, K.
Nitrogen implantation into graphene oxide and reduced graphene oxides using radio frequency plasma treatment
in microscale, Carbon, 199, 2022, 415-423. https://doi.org/10.1016/j.carbon.2022.08.024.
8 PhD Thesis

The ATR-FTIR spectra of reduced GO samples (Fig. 6 A) show that the oxygen
functionalities of the GO sample significantly decreased during both reductive steps explaining
the constricted interlayer distance. While all the features marking O-containing functional
groups are below the detection limit in the CRGO sample. TRGO still possesses some of the
functional groups within the 900-1800 cm-1 region, although with a reduced intensity. The
carbonyl and epoxy stretching vibrational peaks are still present in TRGO. This implies that
the more stable ketones or conjugated quinones might be retained in the bulk sample [18].
The XPS surface composition of the GO was identical to that of the GO110 sample,
revealing that the 5% water detected by TG/DTA analysis was removed during the high-
vacuum treatment in the XPS chamber. An additional evidence was the lack of signal at
BE~536 eV. The chemical reduction is more efficient, as shown by the C/O ratio (8.8 compared
to GO 3.0) and compared to TRGO (5.7) also confirmed by the FTIR results. On the other
hand, it also led to more defected graphene like platelets according to the Raman results and
also proved by XPS in which the concentration of C2 (sp3 C) is higher (Fig. 6 B). During the
reduction the surface concentration of all oxygen components decreased, most spectacularly
the C3 (C‒O‒C, C‒OH) and C4 (C=O) components as reflected by the change of the
concentrations (Fig. 6 B) [18]. 17
100 C1s
C=O
C=C

O-H
C-O-C
O-H
C-OH

C5
80 C4
CRGO C3
Intensity (a.u.)

Atomic %
TRGO
60 C2

GO
40
C1
GR
20
4000 3000 2000 1000 GO110 TRGO CRGO
Wavenumber (cm-1)

(A) (B)
Figure 6. ATR-FTIR spectra of the samples (A) Distribution of C1s species: C1 (sp2
carbon), C2 (sp3 carbon), C3 (C‒O‒C, C‒OH), C4 (C=O) and C5 (HO‒C=O) (B)[18].

Although both reductions led to the restoration of aromatic structure with similar extent,
chemical reduction results in more defected particles. AA under the applied conditions is more
efficient in reducing C5 (O-C=O) compared to thermal annealing at 300 °C, while the latter
one in partial elimination epoxy and hydroxyl groups.
4.4. Rheology of the aqueous GO suspension

To study the mechanical stability, and the microstructure of GO, the rheological behavior of
the 10 mg mL-1 aqueous GO was followed with various rheological methods. All the
rheological measurements in this Section and Section 4.5 were performed in triplicate [13]. At
this concentration, the particles are not independent from each other since our concentration is
higher than the critical concentration where the particles start to interact roughly > 0.1–1 v/v%
[19]
(1-10 mg mL-1) [13]. The steady shear rotational tests revealed strong shear-thinning behavior
(Fig. 7 A), which is explained by partial orientation of the GO flakes in the shear force field
and found to be reversible implying a reversible change in the structure. Herschel–Bulkley
(HB) (Fig. 7 B) fits well the shear rate and shear stress data above the yield stress, which means
that the GO suspension is non-Newtonian [13].

19
Bai, H.; Li, C.; Wang, X.; Shi, G. On the gelation of graphene oxide. J. Phys. Chem. C 2011, 115, 5545–5551.
https://doi.org/10.1021/jp1120299.
9 PhD Thesis

105

104

Viscosity (Pa·s)
103

102

101

100

10-1 -4 -3 -2 -1
10 10 10 10 100 101 102 103
Shear rate (s-1)
(A) (B)
300 Shear Relaxation

200

-1

Viscosity (Pas)
1.0 100 s

0.5
-1
1000 s

-1
10 000 s
0.0
0 20 40 60 80 100 120
Time (s)

(C) (D)
Figure 7. Effect of shear rate on viscosity (A), experimental shear stress–shear rate data
(symbols) and their fit to the HB model (lines), in triplicate (B), relaxation time spectrum (C)
and change of viscosity of the suspension under high shear followed by relaxation at low
shear rate (D)[13].
The frequency sweep tests displayed a fast and a slow relaxation modes of the suspension
(Fig. 7 C) and the fast relaxation related to the displacement of platelets within their
microstructure, also corroborated by the plateau viscosity in Fig. 7 D, was reached within a
short time and the slow one is attributed to escaping of the platelets from their microstructure.
Surprisingly, an irreversible increase of viscosity was observed at high shear rates ≥1000 s−1
(Fig. 7 D). We proposed that this is related to a process in which the highly oxidized external
GO sheets are mechanically peeled off from the flakes. The SEM images taken before and after
high shear treatments of freeze-dried samples confirm the microstructural change caused by
the treatment (Fig. 8 A and B): the loose structure of the GO becomes denser and somehow
more regular after the mechanical treatment [13].

(A) (B)
Figure 8. SEM images of GO samples freeze-dried from 10 mg mL-1 suspension before (A)
and after shearing at 10,000 s−1 for 5 min (B) the scale bar is 5 μm [13].
The strong shear thinning at low shear (≥100 s−1) can be explained by partial orientation and
ordering of the particles, as shown in the upper panel of Fig. 9. High shear forces (lower panel
10 PhD Thesis

Fig. 9), lead to removal of the external layers from the platelets consequently, new surfaces are
born that adsorb water from the bulk phase, resulting in an increase in viscosity. For this reason,
the process at high shear rate is considered to be irreversible as the enhanced viscosity and the
smaller hydrated debris hinder the mobility of the particles [13].

Figure 9. Proposed mechanism for microstructural changes of GO suspensions upon

shearing and relaxation. Black lines represent GO platelets, pink areas strongly
functionalized regions with high oxygen content, dark blue is bound water, light blue shows
the bulk aqueous phase [13].
4.5. Aging of the GO suspension

Three batches of ~10 mg mL-1 GO suspensions were produced with 1 year time gap . They
are distinguished as 0 y, 1 y and 2 y, respectively using the method described in 3.1 and they
were stored avoiding agitation.
Their rheological behavior was studied first (Fig. 10). The HB model gives good fit before
(Fig. 10 A) and after mechanical treatment. The HB model parameters (yield stress and
consistency index) are compared in Fig. 10 B and C. The parameters exhibit an increase after
1 year of storage, but not after an additional year. This is an indecation that the development
of the microstructure takes place mainly within the first year, and remains stable during further
storage. The mechanical treatment results in similar parameters trend of HB that of aged
samples. The aging suggests microstructural changes similar to those observed under high-
shear load [13].
Consistency index; k (Pas)
Steady shear yield stress (Pa)

200 2y 100 40
Shear stress () Pa

1y
After shearing

After shearing

160 80
Before shearing

30
Before shearing

120 60
0y 20
80 40
40 10
20
0 0 0
0 20 40 60 80 100 0y 1y 2y 0y 1y 2y
.
Shear rate () s-1
(A) (B) (C)
Figure 10. Experimental shear stress–shear rate data (symbols) and their fit to the HB model
(lines) (A) yield stress (B) and consistency index (C) [13].
To reaval further possible transformation in the suspensions during the storage Raman and
XP spectroscopies were applied. The deconvluted Raman spectra of the suspensions show tiny
but systematic concomitant increase of the ID/IG and the I2D/IG ratios indicates a slow oxidation
process. The oxidation during aging was also confirmed by XPS. The O/C atomic ratio of fresh
GO changed from 25/75 to 30/70 after 1 year and to 33/67 after 2 years. The changes also were
11 PhD Thesis

monitored by the pH, which dropped from 6 (as prepared) to 2.2 after 3 years. During long-
term storage, the dissolved oxygen present in the intrinsically acidic medium can act as an
oxidizing agent reducing further the π-π interaction between adjacent layers by increase the
distance along the edges and lead to gradual deterioration of the already oxidized graphene
sheets at the peripheries. Raman spectroscopic and XPS studies indicate that the alteration in
the rheological behavior with aging is the consequence of a slow oxidation process that occurs
in the highly acidic aqueous medium and leads to spontaneous peeling off the external sheets
from the flakes [13].

5. Applicability

The oxidation during long-term storage limit the shelf-life of GO suspensions which should
be considered in processing technologies and applications.
In centrifugation, the separation of the particles is governed by the density of the strongly
hydrated platelets, which might influence the efficiency of separation if it aims for getting
particle of different sizes.

6. New findings

1. I studied the acid-base properties of graphene oxides (GO) suspension prepared by an

improved Hummers’ method with potentiometric titration. The proton excess isotherms
showed a hysteresis loop, which, according to the calculated pKa distribution curves, stems
from the irreversible hydrolysis of the lactonic groups.
2. I separated the above mentioned GO particles into five fractions with centrifugation. No
systematic trend was found in the morphology and the chemistry of the GO platelets, including
the crystallite sizes, the layer numbers, the chemical composition and the defect concentration
along the fractions.
3. I compared two reduced graphene oxides obtained by an energetically reasonable thermal
annealing (Ar, 300 °C with heating rate of 1.5 °C min-1 for 3 h) and by a green chemical (pH
= 10, 95 °C, for 1 h) method. Ascorbic acid results in a higher yield, more efficient oxygen
removal but more defected graphitic region. It is also more selective in the partial removal of
carboxylic groups but not in the elimination of epoxide and hydroxyl groups [P1 and P3].
4. I followed the rheological behavior of the 10 mg mL-1 aqueous GO suspension. The
suspension showed shear thinning and proved to be non-Newtonian. The irreversible increase
of the viscosity at shear rates above 1000 s−1 implies change in the microstructure. I showed
that it is related to the peel off of the highly oxidized external sheets from the GO flakes. The
increased viscosity is resulted by the adsorption of bulk water on the new surfaces [P2].
5. I examined the long-term aging of the 10 mg mL-1 aqueous GO suspension over a two-
year time scale. Rheological studies showed that the 3D structure of the suspension becomes
stronger, a feature similar to the effect of the forced mechanical removal of the external layers.
Raman and XP spectroscopies revealed that the strengthening of the structure is related to the
spontaneous peeling due to a slow oxidation process [P2].
12 PhD Thesis

7. Publications

Publications related to the dissertation

P1. Farah, S.; Farkas, A.; Madarász, J.; László, K.

Comparison of thermally and chemically reduced graphene oxides by thermal analysis and
Raman spectroscopy.
J. Thermal Analysis and Calorimetry, 2020, 142, 331–337.
https://doi.org/10.1007/s10973-020-09719-3.
IF: 4.755 (Q2); Citations: 23, independent: 20
P2. Gyarmati, B.; Farah, S.; Farkas, A.; Sáfrán, G.; Voelker-Pop, M. L.; László, K.
Long-Term Aging of Concentrated Aqueous Graphene Oxide Suspensions Seen by Rheology
and Raman Spectroscopy.
Nanomaterials. 2022, 12:916.
https://doi.org/10.3390/nano12060916.
IF: 5.719 (Q1); Citation: 1, independent: 1
P3. Bertóti, I., Farah S., Bulátkó, A., Farkas, A., Madarász, J., Mohai, M., Sáfrán, G., László,
K.
Nitrogen implantation into graphene oxide and reduced graphene oxides using radio frequency
plasma treatment in microscale,
Carbon, 199, 2022, 415-423.
https://doi.org/10.1016/j.carbon.2022.08.024.
IF 11.307 (Q1).

Publications not related to the dissertation

P4. Paudics, A.; Farah, S.; Bertóti, I.; Faraks, A.; László, K.; Mohai, M.; Sáfrán, G.; Szilágyi,
A.; Kubinyi, M.
Fluorescence probing of binding sites on graphene oxide nanosheets with Oxazine 1 dye.
Appl. Surf. Sci. 2021, 541, 148451.
https://doi.org/10.1016/j.apsusc.2020.148451.
IF: 7.392 (Q1); Citations: 6, independent: 3
P5. Fekete-Kertész, I.; László, K.; Terebesi, C.; Gyarmati, B.; Farah, S.; Márton, R.; Molnár,
M.
Ecotoxicity Assessment of Graphene Oxide by Daphnia magna through a Multimarker
Approach from the Molecular to the Physiological Level including Behavioral Changes.
Nanomaterials 2020, 10, 2048.
https://doi.org/10.3390/nano10102048.
IF: 5.719 (Q1); Citations: 1, independent: 1

Conference presentations
Oral presentations

C1. Farah, S.; Farkas A.; Gyarmati, B.; László K.

Aging of concentrated aqueous graphene oxide suspensions, 2nd George Olah Doctoral
conference, BME, Budapest, Hungary; 28th September 2020.
C2. Farah, S.; Farkas, A.; Gyarmati B.; László, K.
Aging of concentrated aqueous graphene oxide suspension seen by Raman spectroscopy, 3rd
George Olah Doctoral conference (XIX Conference of the George Olah Doctoral School),
BME, Budapest, Hungary; 15th September 2021. (Best oral presentation prize)
13 PhD Thesis

C3. Farah, S.; Farkas, A.; Gyarmati, B.; Mohai, M.; Móczó, J.; László, K.
Long-term aging of concentrated aqueous graphene oxide suspension seen by various
analytical techniques, Chemistry Physics and Biology of Colloids and Interfaces (CPBCI
2022), Eszterházy Károly University Eger, Hungary; 6-10 June 2022.

Poster presentations

C4. Farah S.; Farkas A.; Madarász J.; László K.

Thermal analysis of graphene oxide derivatives
Thermal analysis and calorimetry conference 2nd JTACC+V4 2019, Budapest, Hungary; 18-
21 June 2019.
C5. László K.; Gyarmati B.; Farah S.; Farkas A.; Mohai M.
Aging of Concentrated Aqueous Graphene Oxide Suspension
Carbon 2022, The World Conference on Carbon. London, UK, 3-8 July 2022.