Diamond & Related Materials 85 (2018) 23–36

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Diamond & Related Materials

journal homepage: www.elsevier.com/locate/diamond

Synthesis of graphene-based nanostructures by the combined method T

comprising sol-gel and sonochemistry techniques
⁎
Elena A. Trusovaa, , Klara V. Kotsarevaa, Alex N. Kirichenkob, Sergey S. Abramchukc,
Artem A. Ashmarina,d, Igor A. Perezhoginb,c,e
a
Baikov Institute of Metallurgy and Materials Science, RAS, 49 Leninsky pr., Moscow 119334, Russia
b
Technological Institute for Superhard and Novel Carbon Materials, 7a Tsentralnaya street, Troitsk, Moscow 142190, Russia
c
Lomonosov Moscow State University, GSP-1, Leninskie Gory, Moscow 119991, Russia
d
Keldych Research Center, 8, Onezhskaya str., Moscow 125438, Russia
e
Moscow Institute of Physics and Technology State University, 141700, Institutskiy per. 9, Dolgoprudny, Moscow Region 141701, Russia

A R T I C LE I N FO A B S T R A C T

Keywords: Nanocomposites based on graphene and Co3O4, MoO3, NiO and WO3 have been synthesized by a combination of
Graphene sol-gel and sonochemical techniques. N,N-Dimethyloctylamine was used for the formation and stabilization of
Ultradispersed metal oxide powder metal-containing sols and for stabilization of graphene suspension. The structure, morphology and composition
Graphene-ceramics composites of graphene-based nanocomposites were investigated by means of transmission electron microscopy, X-ray
Sol-gel technique
diffraction, Raman and FT-IR spectroscopy. It has been shown that the proposed method allows obtaining the
Sonochemistry
hybrid nanoparticles with 10 to 200 nm size consisting of Co3O4, MoO3, NiO or WO3 crystallites coated with the
graphene layers. This method enables preparing chemically homogeneous composite nanopowders for the
production of high performance (photo)catalysts and fine-grained ceramics for the energy sector with uniform
distribution of components within a volume. It has beens proven experimentally that graphene sheets are in-
volved in the formation of hybrid nanoparticles based on metal oxides as structuring and texturing agents. These
results show promise in the synthesis and fabrication of well-defined graphene-based functional materials, in-
cluding graphene-ceramic hybrids, with a broad scope of applications.

1. Introduction
Over the past decade, a growing interest of researchers has been
focused on graphene-ceramic composites [1–3]. The composites con-
sisting of graphene or graphene oxide and metal oxide nanoparticles are
attractive as raw materials due to the fact that graphene improves their
specific strength, electrical and thermal properties [4–7]. Specific
properties of such composites are related to the formation of the che-
mically bonded graphene–metal oxide interface [1,8]. Composites
based on graphene, graphene oxide or reduced graphene oxide and
nanopowders of metal oxides are promising raw products for designing
new high-purity materials with a wide range of end use: anodes for Li-
ion batteries, supercapacitors, transistors, (photo)catalysts, solar cells,
sensor materials, fuel cells, electrochromic devices, etc. [1,5,7,9–12].
As known, beneficial effects of graphene addition on the physico-
chemical properties are sometimes contradictory, which has been at-
tributed to the inhomogeneous dispersion of carbon species in a ma-
terial volume [13,14].
Among chemical methods for preparing ultradispersed powders of
metals and their oxides, so-called wet methods are particularly attrac-
tive [15–22]. These methods use relatively low temperatures, they are
environment-friendly and technically easy to implement. Sol-gel tech-
nique is one of the most appropriate and promising method for the
synthesis of composite nanostructures based on metal oxides which are
important sources for the production of fine-grained ceramics with
versatile applications [3,23–26].
This method requires careful selection of synthesis and heat treat-
ment conditions. It is very important to detect a correlation between the
synthesis conditions and physicochemical properties of a prepared
product. Among chemical pathways of the graphene oxide preparation,
Hummers method is the most frequently used. It is based on oxidation
of graphite by potassium permanganate in sulfuric acid [27–30] re-
sulting in destruction of the delocalized π-electron system by oxygen-
containing groups. It is known that during reduction of graphene oxide
neither the structure nor the properties are restored [31].
Therefore, it is especially important to have methods for obtaining
graphene without oxygen functional groups. Many synthetics have been
devoted to solving this problem. Graphene exfoliation is carried out in

⁎
Corresponding author.
E-mail address: hibiny69@yandex.ru (E.A. Trusova).

https://doi.org/10.1016/j.diamond.2018.03.020
Received 25 August 2017; Received in revised form 1 January 2018; Accepted 18 March 2018
Available online 20 March 2018
0925-9635/ © 2018 Elsevier B.V. All rights reserved.
E.A. Trusova et al.
Fig. 1. Scheme of the graphene-metal oxide nanocomposite preparation.
liquid media, most often in water, in the presence of alkaline lignin,
sodium dodecyl sulfate or ionic liquids for stabilization of graphene
sheets and prevent their agglomeration [32–34]. Exfoliation is also
carried out in organic solutions of imidazole, dimethylformamide, a
mixture of benzene and hexafluorobenzene, as well as in heptane
[35–38]. As a rule, the yield of single-layer graphene is small and de-
pends on the nature of the stabilizer and/or solvent. Unfortunately, the
use of any of these compounds is problematic because of their toxicity,
therefore, the search for new liquid-phase systems for effective strati-
fication of graphite is topical.
As for graphene-ceramic hybrids, potential applications of gra-
phene-ceramic hybrids synthesized by traditional methods have been
reported in a great number of publications. Also, there are many pub-
lications related to hybrids based on graphene oxide and reduced gra-
phene oxide. However, quite scarce are communications focused on a
search of original rational methods for obtaining graphene-ceramic
hybrids which would be streamlined and cost-effective and at the same
time would ensure high product yields with satisfactory reproducibility
in terms of physicochemical properties [39]. Publications on Al2O3-
based hybrids are more frequent in comparison with those that discuss
TiO2 and the like.
A current trend in high technology development covers colloidal
processing, sol-gel, PDC route, and molecular level mixing. CVD and
sol-gel techniques are most commonly used for the synthesis of gra-
phene-containing hybrids and these are sol-gel methods that become
increasingly important due to the workability and ability to provide a
high quantitative yield and desired physicochemical properties [40].
Most of the prepared graphene-ceramic composites are based on
predispersion techniques where graphene is dispersed in a solvent and
then mixed with a ceramic material. Anionic sulfate surfactants were
shown to stabilize graphene in aqueous solutions and promote the self-
assembly of in situ grown nanocrystallite TiO2, rutile and anatase, with
graphene [41].
Alumina nanofibers were encapsulated into multi-layered graphene
shells using a one-step CVD process in a flow of two gases: ethylene and
hydrogen [42]. The ability to transform the insulating material Al2O3
into a highly conductive material by filling the matrix with alumina
nanofibers encapsulated by multi-layered graphene was demonstrated.
Fibers of 7 nm in diameter were covered by graphene by the catalyst-
free one-step CVD process for the first time [43].
Recently, the approach was proposed for the incorporation of gra-
phene into a ceramic composite using liquid phase exfoliation of gra-
phene and its dropwise dispersion in the Al2O3 matrix via the
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Diamond & Related Materials 85 (2018) 23–36
ultrasonication and powder processing route that resulted in the 40%
increment in fracture toughness with only 0.8 vol% graphene added
[44]. This processing route appeared advantageous as it let solve the
problem of producing good quality graphene without affecting its
properties as in the case of Hummers method.
A graphene/NiO hybrid was prepared by combining the chemical
bath deposition and graphene spin-coating; in this case the hybrid was a
porous film coated by graphene sheets [45]. Therefore, it is apparent
that the synthesis of hybrids based on oxygen-free graphene and WO3,
MoO3, NiO, and CoOx has been poorly studied and there is an urgent
need for their direct development.
Previously we had reported a modified sol-gel synthesis and char-
acterization of metal oxide nanoparticles (single and composite) along
with a study on some of their electron properties. The study covers a
wide range of metal oxides: Al2O3, Bi2O3, CeO2, Fe2O3, MoO3, NiO,
TiO2, WO3, Y2O3, ZnO, ZrO2, as well as SiO2 and Ag nanoparticles
(colloidal silver) [46–48]. A specific feature of the suggested method
was the use of N,N-dimethyloctylamine (DMOA) for the formation and
stabilization of a sol, as well as for subsequent oligomerization during
the 3D gel formation. The oligomeric intermediates were formed with
involving DMOA as a repeat unit in polymerization; both the structure
and composition of this 3D gel determined the morphology and phase
composition of the metal oxide powder or composite metal oxide na-
noparticles. In the paper [49], we reported a method for obtaining
oxygen-free graphene and its fixation at the DMAO-aqua interface.
The aim of this study was to synthesize hybrid composites based on
nanoscale metal oxides and oxygen-free graphene in mild conditions. In
the this work, we have combined sol-gel and sonochemical techniques
for the preparation of hybrid (nano)particles consisting of metal oxide
crystallites coated and bonded together with graphene sheets. A gra-
phene suspension was obtained by liquid phase exfoliation under ul-
trasonic treatment of synthetic graphite. Sonochemical exfoliation re-
sulted in the formation of 2D graphene sheets which further were mixed
with as-prepared Co-, Mo-, Ni- or W-containing sol.
The idea of this study was that, in a mixed emulsion, micro-droplets
of DMOA in water would act as nanoreactors where graphene and
metal-containing sol particles interact to form van der Waals systems. In
the beginning, DMOA was used as a stabilizer of sols and nanocarbon
particles. Then it played the role of a template in the formation of the
hybrid structure of a gel comprising the graphene sheets and a metal-
containing sol. We synthesized hybrid nanopellets consisting of metal
oxide crystallites and few-layer graphene sheets with the thickness up
to several tens of nanometers.
E.A. Trusova et al. Diamond & Related Materials 85 (2018) 23–36

A B

Fig. 2. Active components of the mixed sol: a – Me-containing particles (A) and graphene sheets (B) stabilized by DMOA, b – schematic model of the interaction
between sol particles and graphene inside the DMOA microdroplet.

A continuous graphene structure was found to be present on the
surface of metal oxide nanoparticles. The graphene sheets were struc-
turing particles in the formation of hybrid nanostructures. In the de-
veloped hybrid nanopellets, graphene layers fulfilled reinforcing and
texturing functions. Such nanopowders are promising sources for a
wide range of new materials with higher performance, for example
ceramics with improved mechanical characteristics [50–53]. Moreover,
graphene layers are also excellent electrical and thermal conductors as
a result of their unique intrinsic electron properties and structure,
which is important for the creation of ceramic materials with appro-
priate electrophysical properties [2,3,40,54,55].
The hybrid structure of (nano)particles provides chemical homo-
geneity of powders even with a minimum graphene content. A gra-
phene sheets in metal-oxide nanoparticles can inhibit grain growth
during sintering of ceramics and contribute to the formation of mate-
rials with a homogeneous microstructure [56]. Actually, the use of
graphene-containing nanostructured raw materials for the production
of fine-grained ceramics will allow obtaining materials with the fol-
lowing particular properties: increased thermal and electrical con-
ductivity, stiffness, toughness and flame retardance, improved barrier
properties and appearance, including scratch and mar resistance, re-
duced specific weight while maintaining or improving the properties.

25
E.A. Trusova et al.
a b
Fig. 3. TEM data of graphene sheets: (a) microphoto, (b) electron diffraction pattern.
Fig. 4. TEM microphoto of the Gr-MoO3 hybrid nanoparticle synthesized using
the graphene suspension obtained by ultrasonic treatment during 10 hs. The
oval shows the entrance to the channel between the MoO3 rods filled with
graphene sheets.
Fig. 5. Raman spectra measured from 3 spots of the Gr-MoO3 hybrid nano-
powder using 0.1 and 1.0 mW excitation energy laser irradiation. Laser ex-
citation is 514 nm.
The paper uses terminology and definitions recommended by IUPAC
[57] and the Editorial Board of Journal Carbon [58] as well as the
publication [59].
26
Diamond & Related Materials 85 (2018) 23–36
2. Experimental
The composites were synthesized by a combination of sol-gel and
sonochemical techniques from synthetic graphite in the aqueous
medium at pH 3. All reagents were of analytical grade and were used as
received without further purification. The choice of reagents was con-
ditioned by the challenge of developing a cost-effective laboratory
technology for large quantities of highly-dispersed metal oxide pow-
ders. So, available mineral salts Ni(NO3)2·6H2O, Со(NO3)2·6H2O,
(NH4)6Mo7O24·4H2O, and (NH4)10O5W12O36·10H2О were used as
sources of metals. The graphene suspension was obtained by ultrasonic
treatment of synthetic graphite (ultrasonic power 200 W) [49]. The
time of ultrasound varied from 15 min. to 10 hs. DMOA was used as a
stabilizer of sol and nanocarbon particles. The as-prepared Co-, Ni-, Mo-
or W-containing sol and graphene suspensions were combined at
mixing [47] to produce a hybrid gel during subsequent evaporation at
80–85 °C. Subsequently, the as-prepared gel was calcined at 320–340 °C
for 3 hs.
The morphology of graphene–metal oxide hybrid nanopowders was
investigated by transmission electron microscopy (TEM, LEO-912 AB
OMEGA LEO) and X-ray diffraction (XRD, DRON-3 M with the use of
CuKα radiation, Shimadzu XRD-6000 with CuKα radiation and a
Panalytical Empyrean X-ray diffractometer equipped with a Bragg-
BrentanoHD optical module and a Medipix-2 PIXel3D detector with
CuKα radiation). The Raman spectra were measured in approximately
back-scattering geometry using a TRIAX 552, Jobin Yvon spectrometer
equipped with CCD Spec-10, 2KBUV, a Princeton Instruments
2048 × 512 detector and razor edge filters. A 514.5 nm exciting laser
STABILITE 2017 was used. The FT-IR spectroscopic study of the pow-
ders was carried out on a HYPERION-2000 microscope paired with a
FT-IR IFS-66 v/s Bruker spectrometer. The elemental analysis of the
prepared nanoparticles was performed using a Perkin Elmer Optima
5300DV Inductively Coupled Plasma Optical Emission Spectrometer
and a Carbon/Sulfur Analyzer SC-400 from LECO Co. The carbon
content in the obtained metal oxides was 0.07–0.08 ( ± 0.01) wt% and
the carbon content in the hybrid nanoparticles was 0.2–12.0
( ± 0.0002) wt%.
3. Results and discussion
3.1. Synthesis of composite structures
We have combined sol-gel and sonochemical techniques for the
preparation of hybrid nanoparticles consisting of the metal oxide
crystallites coated with graphene sheets. Fig. 1 shows the scheme of the
synthesis of Gr-MeO hybrid nanoparticles wherein MeO is Co-, Mo-, Ni-
E.A. Trusova et al.
Fig. 6. XRD pattern of the Gr-MoO3 hybrid nanopowder (CoKα radiation).
or W-oxide, and Gr – graphene. The developed method is based on the
concept of the in situ formation of the 3D oligomeric templating agent
from the low molecular weight organic compound (DMOA), anions of
the starting salts and the co-solvents. This approach allows molecular
level control of the structure of future hybrid nanoparticles and their
dispersity with accuracy of 10–15 nm [48,56]. The synthesis of a hybrid
nanostructure involves six steps: the first – obtaining of a graphene
microsuspension using DMOA for its stabilization, the second – pre-
paration of starting salt aqua solutions, the third – formation of a sol
using DMOA, fourth – merging of the as-synthesized sol and graphene
suspension, the fifth – gelation of the mixed sol, and sixth – heat
treatment of an as-prepared mixed gel in a muffle furnace at 320–340 °C
for 3 hs in air.
The graphene suspension was obtained by ultrasonic treatment of
graphite in the aqua-DMOA liquid medium with pH 3. The exfoliation
resulted in the formation of graphene sheets which passed to the acidic
substrate. Their stabilization occurred through the fixation at the aqua-
DMOA boundary (Fig. 2a). Then the obtained graphene sheets were
used to synthesize hybrid nanoparticles based on metal oxides.
In the graphene suspensions in aqua-DMOA emulsion, amine not
only provided the surface of its drops to fix the graphene sheets, but
also contributed to the maintenance of a high dispersion of the gra-
phene sheets by preventing agglomeration. Next, the as-prepared Co-,
Mo-, Ni- or W-containing sol and graphene suspensions were mixed
under stirring. DMOA was also used for the sol formation and stabili-
zation. Organic components of the complex were removed during
subsequent heat treatment and the hybrid structure was formed. Four
series of composite nanoparticles were obtained and characterized: Gr-
Co3O4, Gr-MoO3, Gr-NiO, and Gr-WO3.
The self-assembly process of the interaction between the sol parti-
cles and the graphene sheets took place in DMOA droplets as in na-
noreactors (Fig. 2b). DMOA molecules were links between the graphene
sheets and the sol particles. The quaternary nitrogen atom was formed
by DMOA molecule protonation in the acidic medium. Namely, the
quaternary nitrogen atom is the center of sol particles accession via the
anion-ligand associated with the metal ion (Men+). As a result, the gel
was formed at 80–85 °C (Fig. 2b) which subsequently was calcined
(320–340 °C) to produce hybrid nanoparticles Gr-MeO.
The obtained graphene sheets had linear dimensions exceeding
1 μm (Fig. 3a). Upon drying on a polymer substrate of the TEM in-
strument, they attached from one side to the edge of the support grid
due to statics. The layer thickness measured at bends corresponded to
10–20 monolayers.
The film did not have a planar configuration and took the form of
randomly deformed layers, which increased their thermodynamic sta-
bility by minimizing the surface energy at room temperature. Random
bends of the film were probably caused by its variable thickness and
original graphite nanoparticles randomly distributed within the layers.
Electron diffraction showed the multidirectional orientation of the
layers and the absence of their preferred orientation in the film as well
as its variable thickness (Fig. 3b).
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Diamond & Related Materials 85 (2018) 23–36
3.2. Gr-MoO3 composite structures
In the series of Gr-MoO3 composites, it has been shown that the
thickness of the graphene layer on the surface of metal oxide nano-
particles depends on the graphene dispersion. Using of a heavier frac-
tion obtained after 10 hs of ultrasonic treatment, the graphene coating
thickness achieved several nanometers on the surface of hybrid parti-
cles (Fig. 4). According to the elemental analysis, the graphene content
in the hybrid nanoparticles was 7.27 ± 0.02 wt%.
The TEM microphoto clearly shows that the graphene interlayers
connect MoO3 rods together. The thickness of the carbon interlayer
between MoO3 rods can achieve several nm. Distances between the
graphene layers were approximately 0.35 nm. From the outside, the
composite particle is also coated by a curved carbon layer whose
thickness achieved 2 nm.
The bands in the Raman spectra of the Gr-MoO3 composite were
obtained from different points attributed to the multilayer graphene (D
(1350 cm−1) and G (1580 cm−1) bands at 1000–1800 cm−1 region)
and metal oxide (200–1000 cm−1 region) (Fig. 5). As known, the G
band appears due to the E2g phonon at the Brillouin zone center and
indicates stacking structures [60]. The D band is associated with the
graphene ordering degree. This band corresponds to the density of
structural defects on the graphene surface. The differences in D and G
bands intensities are due to the differences in the degree of structure
ordering and sizes of the graphene sheets. If D band intensity exceeds G
band intensity, graphene sheet sizes do not exceed 5 nm.
The luminescence background may emerge because of the presence
of hydrocarbons at high defectiveness of the graphene sheets due to
their bends on the MoO3 rod ribs. When increasing laser power from 0.1
to 1.0 mW, carbon is partially removed from the surface of MoO3
crystallites and, as a result, MoO3 crystallite bands become more in-
tense (curve 4 in Fig. 5).
The XRD pattern of the Gr-MoO3 hybrid nanopowder (Fig. 6) shows
weak reflexes from crystalline MoO3 and, in addition, several reflexes
(2Ɵ = 9.6, 19.3, 25.8) corresponding to crystalline nanocarbon, as well
as a halo due to the presence of amorphous carbon. The amorphous
carbon can accumulate at the inlet of channels between MoO3 crystal-
lites, and the crystalline one covers flat faces of the MoO3 rods, as
shown in Fig. 4. Some contribution to the formation of the halo can also
be made by MoO3 nanoparticles or clusters with sizes < 10 nm.
The obtained Gr-MoO3 nanoparticles had morphological features
related to the fact that the MoO3 rods coated with thin graphene layers
were grouped into micropellets (Fig. 7a and b). Interestingly, the MoO3
rods were packed into micropellets strictly parallel to each other. The
dark-field TEM microphoto in Fig. 7c shows moiré, which indicates the
presence of 2-layer graphene on the micropellets surface. Fig. 7d shows
the superposition of electron diffraction patterns for the cubic lattice of
MoO3 (bright reflections) and 1–2-layer graphene sheets (weak re-
flexes). In this case, all MoO3 rods in the microgranule have the same
crystallographic orientation. The analysis of the micrographs in
Figs. 7a–c shows that the synthesized hybrid micropellets include single
E.A. Trusova et al. Diamond & Related Materials 85 (2018) 23–36

a b

c d

1010
e f 0110
1210 2110

Fig. 7. TEM data for the Gr-MoO3 hybrid nanopowder: (a and b) microphotos in the light field, (c) microphoto in the dark field, (d) electron diffraction for
nanoparticles, including graphene sheets (corresponding weak reflexes are marked with arrows and ovals), (e) microphoto of the MoO3 nanoparticle curved by
graphene, (f) electron diffraction for the nanoparticle curved by 1–2-layered graphene sheets.

MoO3 crystals < 10 nm thick and 100 nm longer coated with 1–3-layer
graphene. According to the elemental analysis, a graphene content in
the hybrid nanoparticles was 2.53 ± 0.06 wt%.
Fig. 7d clearly shows that, in addition to the MoO3 crystal lattice,
there are reflexes corresponding to diffraction on few-layer graphene
[61–64]. The presence of doublets indicates a partial disordering of
graphene layers caused by stress and strain arising during the formation
of the interface layer in the Gr-MoO3 particles. Another electron dif-
fraction pattern was observed, if graphene dominated in the hybrid
particle. Fig. 7e shows the MoO3 crystallite inside of the graphene shell.
The electron diffraction pattern consists of intensive reflexes due to
graphene planes and weak reflexes caused by the MoO3 crystal lattice
(Fig. 7f). The I{0110}/I{1210} > 1 and I{1010}/I{2110} > 1 intensity ra-
tios of observable reflections are characteristic of 1–2-layed graphene
[65–67].
Fig. 8 shows HRTEM microphotos of edge regions of Gr-MoO3
particles where single- and multi-layered graphene sheets cover the
surface of MoO3 crystallites. Single-layer graphene is observed on the

28
E.A. Trusova et al.
Fig. 8. HRTEM images of the edge areas of Gr-MoO3 hybrid particles.
Fig. 9. FT-IR spectra of αMoO3 and Gr-αMoO3 composites synthesized from the graphene suspensions obtained by different duration ultrasonic treatment of
graphite.
exposed surface of the rods; the thickness of its sheets is < 1 (~0.35)
nm. The other species is multi-layered graphene located at the rod
joints. Graphene monolayers in Fig. 8 are randomly oriented and dif-
ferrentiate in geometric dimensions. At the same time, multi-layered
graphene interlayers play the role of a connecting component for the
hybrid nanostructure and orients the MoO3 rods parallel to each other.
The thickness of these graphene texturing layers is several nanometers,
which also corresponds to the TEM data in Figs. 4 and 7.
Fig. 9 shows the FT-IR spectra of the obtained αMoO3 and Gr-
αMoO3 hybrids synthesized using graphene suspensions with the dif-
ferent duration of ultrasonic treatment of graphite.
The spectrum for pure MoO3 shows the dominant peaks at 991, 870,
820, and 596 cm−1. The band at 991 cm−1 corresponds to the
stretching vibration from the O = Mo6+ bonds. The bands at 870 cm−1
originated from stretching vibrations within Mo-O-Mo groups com-
prising bridging oxygen.
The observed splitting of the 870 cm−1 band in the region of
stretching vibrations (870–930 cm−1) in the hybrids spectra (Fig. 9) is
likely to result from the van der Waals interaction of surface bonds with
the sp2-system of graphene sheets. The band of the stretching vibration
at 596 cm−1 is attributed to the oxygen atom surrounded by three
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Diamond & Related Materials 85 (2018) 23–36
Mo6+-atoms (OMo3 groups). There is no significant signal at the region
of 1600 cm−1 which is usually ascribed to the bending mode of hy-
droxyl groups on the MoO3 surface [68]. However, in this case, weak
bands at 1600 cm−1 are attributed to the skeletal vibration of CeC
bonds in graphene sheets of the Gr-MoO3 hybrids [69–71].
The rest of the bands in the spectra of Gr-MoO3 composites virtually
correspond to the spectrum of pure MoO3, although a small red shift of
the band from 991 cm−1 to 978 cm−1 is observed because of an in-
crement of suspending O = Mo6+ bonds on the surface of the nano-
particles. Furthermore, a band shape change was observed at 870 cm−1
(it became broader) and, in some spectra, band centers shifted to
910 cm−1, which indicates a change of symmetry within the Mo-O-Mo
group.
3.3. Synthesis of the Gr-WO3 nanocomposite
The morphology of the synthesized Gr-WO3 nanocomposites is
shown in Fig. 10. According to the elemental analysis, the carbon
content in the hybrid nanoparticles was 2.73 ± 0.07 wt%. The TEM
image of the synthesized powder shows that it consists of rod-like na-
noparticles, the so-called 1D species, with the cross section side equal to
E.A. Trusova et al.
а 30 nm
21 nm
50 nm
3 nm
с
Fig. 10. TEM images: (a) Gr-WO3 hybrid (circumferences denote several composite nanopellets), (b) pure WO3 nanopowder obtained under the same conditions, (c)
electron diffraction for the Gr-WO3 composite, (d) schematic representation of Gr-WO3 hybrid nanoparticles consisting of densely packed WO3 rods on the graphene
sheets surface.
2–3 nm and length equal to a few tens of nanometers (Fig. 10a). WO3
nanorods are grouped into pellets where they are packed parallel to
each other.
Fig. 10b shows a TEM micrograph of the pure WO3 nanopowder
obtained under the same conditions. It is clearly seen that this powder
consists of cube-like nanoparticles with the side size of about 20 nm
agglomerated into microgranules sized < 80 nm. The electron diffrac-
tion pattern for the hybrid nanoparticles (Fig. 10c) can be interpreted as
resulting from the superposition of the pure ultrafine WO3 crystallite
lattice and that of graphene.
Fig. 10d schematically shows the structure of hybrid Gr-WO3 na-
noparticles formed from densely packed and parallel-oriented WO3 rods
with the length up to 50 nm (Fig. 10a). Only graphene sheets or ribbons
could provide such orientation of crystallites in hybrid microgranules. A
hybrid nanoparticle is formed from the aggregate of 1D metal oxide
structures under control of the carbon mesh. As a result of the Van der
Waals interaction, sp2 electrons orient charged sol particles along the
chains of carbon cycles. Apparently, in colloid, graphene sheets act as
template particles and provide anisotropic growth of metal oxide
crystallites.
Fig. 10a shows that the thickness of the synthesized hybrid nano-
particles does not exceed 4 nm and their length is determined by the
length of graphene sheets (tapes) and can achieve several tens of nan-
ometers. However, in the formation of hybrid nanoparticles, graphene
sheets not only controlled the directed growth of crystallites, but also
oriented them relative to each other. Thus, inside the hybrid nano-
particles, the graphene sheets act as texturing components (Fig. 10d).
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Diamond & Related Materials 85 (2018) 23–36
b
d
The Fig. 11a and b show HRTEM micrographs of edge regions of the
Gr-WO3 hybrid particles where few- and multi-layer graphene sheets
are oriented perpendicular to each other. The sheets consisted of 5–10
layers and the distances between them were not < 0.35 nm. At the edge
of the carbon shell of the hybrid particle, the aggregation of a number
of differently oriented few- and multi-layered sheets is observed
(Fig. 11c) along with scarce few-layered graphene sheets near the
Gr–WO3 interface. Fig. 11d shows the graphene sheet (red) and the
deformed 2D WO3 layer (green) in the hybrid nanostructure.
In a thin graphene shell of hybrid particles, inclusions of WO3 na-
noparticles (clusters) with dimensions typical for quantum dots
(1–1.5 nm) are clearly observed. At the same time, they form small
associates somewhere within the graphene shell. Presumably, the pre-
sence of the accumulation of WO3 quantum dots and a network of few-
layered graphene on the hybrid structure surface causes intense lumi-
nescence in the Raman spectra (Fig. 12).
The Raman spectra of Gr-WO3 composite correspond to multilayer
graphene and metal oxide exhibit D (1350 cm−1) and G (1580 cm−1)
graphene broad bands of approximately equal intensity related to
multilayer graphene as well as the strong fluorescent (Fig. 12). It should
be noted that the spectrum obtained at 0.5 mW shows only graphene
broad bands (Fig. 12a), but the spectrum obtained at 5.0 mW shows
both graphene and metal oxide broad bands (Fig. 12b). It concerns with
removing of graphene from Gr-WO3 composite surface with increasing
laser energy. Apparently, with an electron energy increasing, a partial
removal of graphene from the WO3 crystallites surface occurs, and
electron diffraction on the WO3 crystal lattice becomes possible. The D
E.A. Trusova et al. Diamond & Related Materials 85 (2018) 23–36

Fig. 11. HRTEM images for edge regions of Gr-WO3 hybrid nanoparticles: (a, b) few-layered graphene sheets are oriented perpendicular to each other; (c) inclusions
of WO3 nanoparticles (clusters) in the graphene shell made up of differently oriented sheets, one of which is marked by a circle; (d) graphene sheet (red) and
deformed 2D WO3 layer (green). (For interpretation of the references to colour in this figure legend, the reader is referred to the web version of this article.)

Fig. 12. Raman spectra obtained using laser excitation with 514 nm wavelength at various power values and the XRD (CoKα radiation) pattern of the Gr-WO3 hybrid
(insert).

and G bands broading is due to the great amounts of defects at the edges
of sheets as well as different orientation of the graphene layers in the
sheets.
The increase of the laser power from 0.5 up to 5.0 mW leads to the
decrease of background fluorescence intensity and appearance of strong
bands: 178 and 254 cm−1 (deformation vibrations of OeWeO groups)
as well as 687 and 799 cm−1 (valence vibrations of OeWeO groups). In
this case, the appearance of WO3 bands with intensity many times
higher than that of D and G bands is likely to be associated with gra-
phene destruction and elimination of carbon from the WO3 crystallite
surface. The insert shows XRD data that corresponds to highly dispersed
or weakly crystallized WO3 and a small amount of highly dispersed
carbon phase that corresponds to TEM and HRTEM data (Figs. 10a and
11).

31
E.A. Trusova et al. Diamond & Related Materials 85 (2018) 23–36

Fig. 13. TEM images: (a) Gr-Co3O4 composite, the ovals show graphene-curved conglomerates; (b) pure Co2O3 powder.

Fig. 14. Raman spectrum for Gr-Co3O4 hybrid nanoparticles and the selected area of graphene bands (insert).

Fig. 16. FT-IR spectrum for the Gr-Co3O4 hybrid nanopowder.

3.4. Gr-Со3О4 hybrid nanostructure

The synthesized Gr-Со3О4 hybrid nanoparticles were studied by

Fig. 15. XRD patterns: (a) single Co3O4 nanopowder (DRON-3 M, CuKα ra-
diation),
(b) Gr-Co3O4 hybrid (Shimadzu XRD-6000, CuKα radiation).
TEM, XRD, Raman and FT-IR spectroscopy (Figs. 13–16). The nano-
powder consisted of conglomerates with sizes of 40–130 nm (Fig. 13a),
in which Co3O4 crystallites had sizes from 10 to 40 nm, while the
powder of pure Co3O4 had the crystallite size of 30–50 nm and smaller
crystallites were hardly observed (Fig. 13b). The cube-lake crystallites
of the pure Co3O4 powder did not undergo any agglomeration. The TEM
image of the composite depicts cage-like graphene, in which Co3O4
crystallites were placed.
Fig. 14 shows the Raman spectrum for the Gr-Со3О4 nanopowder

32
E.A. Trusova et al.
Fig. 17. TEM image of hybrid Gr-NiO nanoparticles.
with an increased allocated region of D and G bands of graphene. There
are two regions observed in it: the region of 400–800 cm−1 is char-
acteristic of the Co3O4 spinel structure [72,73] and the other covers an
interval of 1200–1600 cm−1 and corresponds to graphene. One can
distinguish active Raman modes located approximately at 478, 512,
620 and 675 cm−1 and attributed, as characteristic bands, to Co2+(3d7)
and Co3+(3d6) located at tetrahedral and octahedral sites, respectively.
The D (1351 cm−1) and G (1580 cm−1) bands correspond to graphene
inside of hybrid particles (Fig. 14, insert).
A comparison of the XRD patterns in Fig. 15a and b indicates that
the formation of Co3O4 crystallites on the surface of graphene sheets
not only leads to an increase in dispersion, but also affects the defec-
tiveness of its crystal lattice. In addition, weak reflexes are observed on
a • - Ni0
b c
Fig. 18. XRD pattern for hybrid Gr-NiO nanoparticles (a). Williamson-Hall plots for NiO and Ni0 nanoparticles in the hybrid nanostructure (b and c, respectively).
33
Diamond & Related Materials 85 (2018) 23–36
the XRD pattern of the hybrid (in the regions of 33.0–33.5 and 57.5
degrees) which cannot be reliably attributed to any of the Co-oxide
phases. However, the diffuse reflex at 42.4 degrees can presumably be
ascribed to the impurity phase of hexagonal close-packed Co0 (JCPDS
card no. 09–0402) which emerged as an interface in a place of the
contact of graphene and Co3O4 phase during the formation of the latter.
Meanwhile, the diffractogram features no reflex in the region of 26.7
degrees, which is characteristic of the graphite-like 3D phase [74,75].
Fig. 16 shows the FT-IR spectrum for the Gr-Co3O4 hybrid nano-
powder where two distinctive bands are observed. One is the band at
567 cm−1 associated with CoeO vibrations in an octahedral position
(Co3+) and the other at 663 cm−1 is associated with CoeO vibrations in
tetrahedral sites (Co2+) of the spinal lattice [76–78]. In the spectrum,
there are no stripes indicating the formation of new chemical bonds in
the hybrid. Only the bands characteristic of Co3O4 are observed in the
spectrum.
3.5. Gr-NiO hybrid nanostructure
Fig. 17 shows a typical TEM image for the synthesized hybrid Gr-
NiO nanoparticles afforded from the sol mixed and then calcined at
340 °C: there are clearly visible NiO crystallites coated with graphene
layers. One can see several species of the graphene sheets in composite
particles. The first type is plane graphene sheets not > 1 nm thick, to
which 15–25 nm NiO crystallites are attached on both sides. The second
type is curved graphene sheets not > 1 nm thick that are also attached
to NiO crystallite faces. The third type of graphene sheets is graphene or
graphene-like coating of NiO crystallites, the thickness of the formed
shell being 1–4 nm. While their shape replicated that of crystallites,
their sizes corresponded to those of crystallite faces.
Fig. 18 shows the XRD pattern and Williamson-Hall plots for the
hybrid Gr-NiO nanostructure. There are two species of reflexes that
correspond to NiO and Ni0 in the diffractogram (Fig. 18a). Crystallite
•
•
E.A. Trusova et al.
Fig. 19. Scheme of the formation of hybrid nanoparticles.
sizes and lattice strain on the peak broadening of the Gr-NiO powder
were studied using X-ray broadening supported by the Williamson-Hall
analysis and size-strain plots. In the case of NiO, the contribution of
homogeneous deformations is significant (Fig. 18b) apparently due to
the van der Waals interaction of charged metal-containing particles of
the sol with graphene sheets during the hybrid's synthesis.
The dispersion of reduced nickel (Ni0) is practically not affected by
the presence of graphene in the reaction medium during crystallization.
We have shown previously [47] that sizes of Ni0-impurity crystallites
(several percentages) are a few folds larger than of NiO crystallites in
the nanopowder synthesized by the proposed method. The size factor
only affects the broadening of reflexes of Ni0 (Fig. 18c) which is not
involved in the van der Waals interaction with graphene sheets; Ni0
crystallization occurs regardless of the graphene presence.
3.6. Double effect of DMOA in the synthesis of a hybrid nanostructure based
on graphene and metal oxides
Fig. 19 shows a schematic diagram for the formation of hybrid na-
nostructures based on graphene and metal oxides. The 3D oligomeric
gel formation occurs under the influence of graphene sheets from the
sol synthesized in the presence of DMOA. They establish both the or-
dering of sol particles on their surface due to the van der Waals inter-
action and the direction of growth of oligomeric gel chains of metal
oxide crystallites during subsequent heat treatment. Herewith, strict
orientation of the emerging crystallites on the surface of graphene
sheets is retained in the directions of the carbon cycles sequence in
graphene.
All hybrids were synthesized under the same conditions; in all
syntheses, DMOA was used to form and stabilize sols as well as to
stabilize the graphene suspension. In all cases, metal oxide crystallites
had sizes many fold smaller than in pure powders. During the formation
of hybrids, crystallization occurred on graphene sheets. Oxides of VIB
group metals (MoO3 and WO3) were formed as rods oriented in parallel
to each other and assembled by graphene sheets into a common
structure. In contrast, oxides of VIII group metals (NiO, Co2O3) were
formed as highly defective crystallites assembled by graphene sheets
into a hybrid nanostructure.
4. Conclusion
In summary, an original approach to the synthesis of hybrid gra-
phene-metal oxide nanostructures was developed by combining sol-gel
and sonochemical techniques. Co3O4, MoO3, NiO or WO3 crystallites
were uniformly distributed between graphene sheets in the volume of
34
Diamond & Related Materials 85 (2018) 23–36
these particles without chemical bonds. DMOA was used both for the
formation and for the stabilization of metal-containing sols and for the
stabilization of the graphene suspension. The structure, morphology
and composition of graphene-based nanocomposites were investigated
using methods of TEM, HRTEM, XRD, Raman-, and FT-IR spectroscopy.
It has been shown that the proposed method allowed affording com-
posites with particle sizes from 10 to 200 nm that consist of Co3O4, NiO,
MoO3 and WO3 crystallites coated with graphene layers. In general, this
approach enables the preparation of chemically homogeneous compo-
site nanopowders with a uniform distribution of components within the
volume for the production of high performance (photo)catalysts and
fine-grained ceramics for the energy sector. It has been proven by ex-
periment that graphene sheets are involved in the formation of com-
posite nanoparticles based on metal oxides as structuring and texturing
agents. Taking in account the characteristics of the synthesized nano-
composites, the findings may be useful for the synthesis and fabrication
of well-defined functional graphene-based materials, including gra-
phene-ceramic hybrids, with a broad scope of applications. We believe
that this simple and cost-effective method will pave the way to various
functional graphene-metal oxide hybrid raw products and offer new
opportunities in design of such materials at the atomic and molecular
level.
Acknowledgement
The authors are thankful to Dr. S.N. Polyakov for the analysis of the
XRD results by Williamson-Hall method. E.A. Trusova, A.N. Kirichenko,
and I.A. Perezhogin gratefully acknowledge financial support from by
the Russian Foundation for Basic Research (RFBR, Grant No: 17-02-
00759_а).
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