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Advances in Subcritical Hydro-/Solvothermal Processing of

Review

Graphene Materials
Suchithra Padmajan Sasikala, Philippe Poulin,* and Cyril Aymonier*

are far from commercial realities due to

Many promising graphene-based materials are kept away from mainstream the unscalable and expensive nature of the
applications due to problems of scalability and environmental concerns existing graphene synthesis processes.
in their processing. Hydro-/solvothermal techniques overwhelmingly sat- The clean and accurate epitaxial and CVD
(chemical vapor deposition) growth tech-
isfy both the aforementioned criteria, and have matured as alternatives to niques for bottom up synthesis of gra-
wet-chemical methods with advances made over the past few decades. The phene are very important for the graphene
insolubility of graphene in many solvents poses considerable difficulties in research and exploration of its properties.
their processing. In this context hydro-/solvothermal techniques present an Nevertheless these methods suffer from
ideal opportunity for processing of graphenic materials with their versatility high energy requirements and scalability
issues and thus fail to meet industrial
in manipulating the physical and thermodynamic properties of the solvent.
demands.[3,4] More over transfer procedure
The flexibility in hydro-/solvothermal techniques for manipulation of sol- of graphene sheets is also challenging and
vent composition, temperature and pressure provides numerous handles to face potential contamination from metal
manipulate graphene-based materials during synthesis. This review provides or polymer substrates.[4,5] On the other
a comprehensive look at the subcritical hydro-/solvothermal synthesis of gra- side, graphite liquid exfoliation, a widely
phene-based functional materials and their applications. Several key synthetic employed solution based top down syn-
thesis of graphene, involves long process
strategies governing the morphology and properties of the products such as time, harsh chemicals, controlled atmos-
temperature, pressure, and solvent effects are elaborated. Advances in the phere, surfactants, or high temperature
synthesis, doping, and functionalization of graphene in hydro-/solvothermal annealing treatments, which can damage
media are highlighted together with our perspectives in the field. the graphene sheets.[6–8]
Among all the established graphene
synthesis process, the most promising
1. Introduction method in terms of scalability and processability is the reduc-
tion of graphene oxide (GO). The GO is obtained by oxidation
Since its discovery a decade ago, graphene and its associated of graphite followed by ultrasonication and purification.[9] Nev-
materials have been continually investigated for diverse poten- ertheless, GO is electrically insulative due to the disruption of
tial applications in electronics, optics, energy, environmental the honeycomb hexagonal lattice of C atoms. In order to recover
and biomedical fields mainly due to its remarkable properties the disrupted sp2 bonding networks and to regain its electrical
such as high electrical and thermal conductivity, high stiffness, conductivity, GO should be reduced by removing oxygen groups
mechanical strength, high specific surface area, chemical, envi- from its crystal lattice. The main issue in this process is that
ronmental and biological stability.[1] Notably, graphene shows once most of the oxygen groups are removed, the reduced GO
exceptional compatibility with dissimilar functional materials tends to get aggregated. Thus it has been very difficult by this
such as polymers, metals and metal oxides and also with sim- method to obtain graphene sheets of the same quality as pris-
ilar layered materials such as transition metal dichalcogenides, tine graphene or like the ones obtained by mechanical exfolia-
and layered double hydroxides, thereby perpetually widening its tion. Nonetheless, the reduction of GO is undoubtedly regarded
spectrum of applications.[2] However graphene-based devices as the most suitable method for mass production of graphene
monolayer.
The thermal reduction is generally carried out at tempera-
Dr. S. P. Sasikala, Dr. C. Aymonier tures above 200 °C to temperatures as high as 2000 °C under
CNRS inert or reducing atmosphere. The inevitable structural damage
Univ. Bordeaux
ICMCB, UPR9048 F-33600, Pessac, France by released gas during thermal annealing is severe being
E-mail: cyril.aymonier@icmcb.cnrs.fr the limiting point of this process.[10] Chemical reduction on
Dr. P. Poulin the other hand is generally carried out at low temperatures
CNRS (≈100  °C ). Complete removal of oxygen functionalities is not
Univ. Bordeaux possible via this method, which results in agglomerated gra-
CRPP, UPR8641 F-33600, Pessac, France
E-mail: poulin@crpp-bordeaux.cnrs.fr
phene sheets, unless the sheets are stabilized by chemical addi-
tives.[11] Many of the chemical reductants such as hydrazine,
DOI: 10.1002/adma.201605473 phenyl hydrazine, dimethyl hydrazine, metal hydrides such

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as NaBH4 and LiAlH4, hydrogen halides, and boranes etc., are

Review
toxic and not environmentally friendly.[12] It is to be noted that Suchithra Padmajan Sasikala
reductants such as vitamin C and urea are nontoxic and equally received her PhD degree in
effective as hydrazine in reducing GO. In cases where GO is chemistry from University of
used with substrates that cannot sustain high temperatures or Kerala (India) in 2011 working
which are chemically reactive with the reductants in an unde- on layered natural materials.
sirably way, the existing chemical/thermal reduction techniques She carried out a csir-nehru
become unsuitable. Alternatively, hydro-/solvothermal syn- science postdoctoral Fellowship
at the National Institute of
thesis provides a scalable, efficient and low temperature route
Science and Technology (India)
to reduction of GO. The solvothermal atmosphere can promote
from 2011–2013 on engineered
graphitization of amorphous carbon, intiate dehydroxylation of
photocatalytic layered materials.
GO and induce π conjugation recovery.[13,14]In addition, hydro-/
She also worked as a visiting
solvothermal synthesis offers low temperature bottom up syn- scientist at UHasselt (Belgium)
thesis of graphene and exfoliation of graphite. in 2012. She joined Dr. Cyril Aymonier and Dr. Philippe Poulin
A solvothermal reaction can be considered as a reaction in a under the ‘Initiative of Excellence (IdEx) programme’ (University
close system using a solvent (mainly non-aqueous) at a temper- of Bordeaux, France) in 2013, working on sub-and supercritical
ature higher than its boiling temperature; consequently pres- processing of graphene based materials. Her current research
sure is involved.[15] When water is used as solvent, the same interests include physical chemistry of two dimensional mate-
is known as hydrothermal reaction. An autogenous pressure rials and their heterostructures.
develops due to the solvent heating in a constrained volume,
dramatically changing the microenvironment of the reaction Philippe Poulin is a senior
chamber. The facile manipulation of solvent properties in CNRS researcher at the Centre
hydro-/solvothermal synthesis affords this technique an oppor- de Recherche Paul Pascal in
tunity to have control over solubility, reactivity and selectivity Bordeaux-France. His fields of
which is hardly possible with conventional methods. Note that, interest include soft condensed
solvothermal reaction can be either subcritical or supercritical. matter, nanostructured and
If the temperature and/or the pressure of the system are below functional materials, nanotubes,
the critical temperature and pressure of the considered sol- graphene and composites.
vent, the process is operating in subcritical conditions, and if He obtained a PhD degree in
temperature and pressure are above the critical temperature Physical Chemistry from the
and pressure of the considered solvent, the process is oper- University of Bordeaux in 1995.
ating in supercritical conditions. Notably, hydro-/solvothermal Then he undertook postdoctoral
methods including both subcritical and supercritical methods research at the University of
have the flexibility to be stretched for commercial exploitation. Pennsylvania, USA before taking up his current CNRS posi-
Hydro-/solvothermal processes are well explored for the syn- tion in 1998 at the Centre de Recherche Paul Pascal. His main
thesis of inorganic nanocrystals with controlled morphology.[16] achievements include the study of novel colloidal interactions
and structures in liquid crystals, the development of functional
As a result of recent developments in reactor design, the cur-
carbon nanotube fibers and shape memory nanocomposites.
rent focus is to manufacture 100 tons/annum of formulated
P. Poulin is currently working on the physical chemistry of carbon
nanomaterials as developed in the European Commission
nanotubes and graphene and of their behavior in complex fluids.
7th Framework funded project named SHYMAN (sustainable
hydrothermal manufacturing of nanomaterials).[17] Commer-
Cyril Aymonier is currently
cial interest on this method is expanding with the interest of
a CNRS researcher at the
many companies such as Sawyer Technical Materials (Ohio),
“Institut de Chimie de la
Sakai Chemical Company (Japan), Cabot Corporation (Boston),
Matière Condensée de
Hanwha Chemical (Korea) and Murata Industries (Japan)
Bordeaux (ICMCB)”. He
among many others over the past 50 years.[18] However syn- obtained his PhD in chemical
thesis of graphene and of its related materials is still in infancy engineering from University
despite many promising reports which convincingly illustrate of Bordeaux (2000) where he
the great potential of solvothermally synthesized/exfoliated focused on supercritical water
graphene sheets, heteroatom doped/reduced graphene sheets, oxidation of wastewater. He did
graphene quantum dots, and graphene composites/aerogels/ a postdoctoral stay in Freiburg
fibers (Scheme 1).[19] Very recently, we have reviewed the super- (2000–2002, Germany) where
critical fluids methods for the processing of graphene and gra- he developed novel approaches
phene-based materials in detail.[20] While, supercritical fluids to design hybrid organic/inorganic nanoparticles. Now he
methods require high temperature and high pressure stable is the head of the Supercritical Fluids department of ICMCB
reactors, subcritical hydro-/solvothermal synthesis provides a (about 25 people). His current research interests are in the
low temperature alternative. Beyond the complementarity, it is chemistry and processes in supercritical fluids applied to
more accessible than supercritical fluid treatments as it can be materials science and environment.
carried out in an ordinary autoclave (Figure 1).

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Review
Scheme 1.  An overview of graphene-based materials obtained by sub-
critical hydro-/solvothermal processing.
Here we propose an in-depth review specifically focused
on subcritical hydro-/solvothermal processing of graphene-
based materials, considering the sustainability, versatility and
scalability of this process. The progress of subcritical hydro-/
solvothermal method in attaining graphene-based functional
materials is analyzed and discussed, with emphasizes on the
general physico-chemical aspects of hydro-/solvothermal pro-
cesses. Further we give the readers an insight into the potential
developments in the field by providing an overview on subcrit-
ical hydro-/solvothermal reactions for obtaining functional gra-
phene-based materials. Those include bottom up synthesis of
graphene, exfoliation of graphite, reduction of graphene oxide,
synthesis of graphene quantum dots, heteroatom doping, com-
posite formation of graphene sheets and graphene-based aero-
gels and fibers etc. Further we compare the performances of
graphene materials processed through different subcritical
hydro-/solvothermal methods for different applications. We
close the review by highlighting the open challenges and our
perspectives in the field.
Figure 1.  a) Schematic of an autoclave required for conducting hydro-/solvothermal reaction at lab scale. b) Increase in pressure as function of tem-
perature for different volumes of water in an autoclave of fixed volume capacity. The low pressure region is magnified in the inset. Plots were drawn
using data from NIST standard Reference Database version 9.0.
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2. Hydro-/Solvothermal Process: General Aspects
In general, laboratory scale hydro-/solvothermal processes
are carried out in a sealed container typically called autoclave,
which contains a stainless steel Teflon lined reaction chamber.
An autoclave could withstand a temperature as high as 250 °C
and a pressure of 15 MPa, depending on the specifications of
manufacturers (Figure 1a). A typical autoclave for routine sub-
critical solvothermal reactions like the ones that are covered
in this review is cost effective compared to conventional wet-
chemical lab wares considering its incomparable durability
with that of the later. In addition, now it is possible to monitor
the reaction progress inside the autoclave on the course of the
reaction by advances in the equipment design. There are many
more advantages such as environmental benignity arising from
limited pollution from the closed system process, and opportu-
nity to synthesize dimension, morphology and phase controlled
nanoparticles. Hydrothermal process is the most widely inves-
tigated solvothermal process because of its close relation to the
geological phenomena, ability to synthesize hydroxylated mate-
rials, low temperature conditions, and green chemistry. Hydro-/
solvothermal reactions are governed by the physico-chemical
properties of solvent associated to the precursor nature. At
the same time, solvent properties are directly associated to the
thermodynamic characteristics such as temperature and pres-
sure, and thus have a key reaction controlling role. Figure 1b
shows the variations of pressure inside an autoclave as function
of temperature with respect to the percentage fill of water in
the reaction chamber inside the autoclave. The graph explains
how one can control the pressure of the reaction by manipu-
lating the temperature and the solvent volume. A low solvent
volume, or in other words a low percentage fill, results in a
low pressure even at high temperatures. On the other hand,
a high solvent volume can create a high pressure even at low
temperature in the same reactor. Thus chemical reactivity of a
substance can be hugely modified under hydro-/solvothermal
conditions depending on the temperature and pressure condi-
tions and percentage fill of the reactor. Majority of the hydro-/
solvothermal reactions reported in the literature are related
to the synthesis of inorganic nanocrystals and are already
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reviewed in details in the literature.[21] This review is intended
to give an outlook on the low temperature hydro-/solvothermal
processing of graphene and of its related materials. Notably, in
subcritical hydro-/solvothermal processes concerning graphene
and its associated materials, water is mainly used as solvent,
even though other organic solvents are also investigated. The
popularity of water is also based on its drastic improvement of
ionic product under subcritical conditions. Water has an ionic
product of about 10–11 at 250 °C . Hence water in a temperature
range of 100–250 °C acts as a source of H+ and as analogues
to acids in catalyzed dehydration of alcohols, protonation of
hydroxyl/carboxyl groups of GO, followed by dehydration of GO
to result in highly reduced GO.[14] The following section covers
all the synthetic strategies adopted in the subcritical hydro-/
solvothermal processing of graphene-based materials, and their
effects on the resulting materials properties and applications.
3. Graphene-based Materials from Subcritical
Hydro-/Solvothermal Processes
Comprehensive discussion of the available literature on gra-
phene materials from subcritical hydro-/solvothermal process
constitutes the core frame of this review and is the main focus
of this section. This section is divided into a number of subsec-
tions, which are categorized based on the graphene products
obtained through subcritical hydro-/solvothermal process. They
include graphene sheets, graphene quantum dots, graphene
composites, graphene fibers and graphene-based 3-dimen-
sional structures.
3.1. Graphene Sheets/Ribbons
Historically solvothermal reactions using organic solvents have
been reported for the synthesis of carbon structures of graphitic
nature. For instance, Kuang et al.[13] in 2004 used tetrachlo-
romethane as both solvent and carbon source and potassium as
the reductant at a very low temperature (60–100 °C ) to obtain
crumbled carbon nanosheets (Figure 2a,b). Shen et al.[22] in
2008 used ferrocene and carbon disulfide (solvent) at 800 °C to
achieve carbon sheets aggregated into flower like morphology
(Figure 2c,d). Despite having graphene signature in these
sheets, these authors did not seem to identify these sheets as
graphene. Later, Stride et al.[19] in 2009 improved the method by
considering the product from solvothermal treatment (220 °C
for 72 h) of ethanol (solvent and carbon source) and sodium
metal (reductant) as graphene precursors, which they rapidly
pyrolysed and ultrasonicated to yield highly graphitic indi-
vidual graphene sheets (Figure 2e–g). The authors claimed the
achievement of 0.1 g graphene per 1 mL of ethanol with a bulk
conductivity of 0.05 S m–1. In 2013, Eftekhari et al.[23] reported
the synthesis of graphene sheets from a solvothermal reaction
between dichloromethane (solvent and carbon source), cobalt
chloride and sodium metal (reductant) at 200 °C for 16 h.
At high temperature and at autonomous pressure (developed
because of sealed reaction chamber), the organic solvents act
as carbon feed stock to get reduced by the metallic reductants
and to transform to graphitic sheets. Close enough to previous
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works on solvothermal synthesis of graphitic carbon, Pradip
Review
et al.[24] have very recently (in 2016) prepared rod shaped zinc
based metal organic frameworks (MOF) from solvothermal
synthesis using 2,5-dihydroxyterephthalic acid and zinc nitrate
with DMF and water as solvents at 120 °C for 24 h. Pyrolysis
of this MOF followed by an alkali assisted sonochemical unzip-
ping rendered graphene ribbons (Figure 2h–j). In this work,
the authors have controlled the morphology of the resulting
graphene products by controlling the organic linked MOF mor-
phology into rod shape. All these works advocated the trans-
formation of sp3 hybridized carbon source to sp2 hybridized
carbon nanostructures under solvothermal conditions. Our
recent work on the synthesis of graphene ribbons by treating
anthracite coal in ethanol at 250 °C and 20 MPa pressure, is
also in agreement with this observation of solvothermal gra-
phitization (Figure 2k,l).[25]
While the synthesis of graphene by dissociation of carbon
containing solvents/molecules at high temperature in a con-
fined volume (like the ones discussed above) can be consid-
ered as bottom-up solvothermal synthesis of graphene, the top
down approach, i.e., exfoliation of graphite using solvents at
solvothermal conditions is also in practice. The supercritical
exfoliation of graphite using supercritical fluids (which are
solvents at pressure and temperature higher than its critical
point) exceeds in number among solvothermal graphite exfo-
liation reports. This was reviewed in details previously.[20] Nev-
ertheless, the solvothermal subcritical exfoliation of graphite
(using solvents below their critical point and above the
boiling point in a confined volume) is also shown comparably
efficient.
The very first solvent phase exfoliation of graphite was
reported by Hernandez et al.[26] They stated that solvents like
N-methyl-pyrrolidone (NMP) which has nearly zero enthalpy
of mixing with graphite, under ultrasonication can exfoliate
graphite at concentrations of up to 0.01 mg mL–1 with a mono­
layer yield of 1 wt%. Tang et al.[27] reported that the variation
of enthalpy of mixing (ΔGmix = ΔHmix − TΔSmix) is mainly
influenced by ΔSmix since ΔHmix is small for most mixtures.
At high temperature ΔSmix increases and ΔGmix would be nega-
tive, consequently graphite exfoliation will be more prominant
than in ambient conditions. According to the authors, NMP at
a temperature of 200 °C was found to exfoliate the graphite
more than in ambient conditions.[27] Qian et al.[28] exfoliated
expanded graphite (EG) using acetonitrile (ACN) at a tempera-
ture of 180 °C and a pressure of 1.1 MPa. They obtained mono­
layer and bilayers graphene with a total yield of 10–12 wt%, as
opposed to no/insignificant exfoliation by ultrasonication in
ACN under ambient conditions. Such a high graphene yield is
exceptional and can be attributed to the fact that solvothermal
conditions increase the interaction of solvent molecules and
graphitic basal planes. They decrease thereby the potential
energy barrier for solvent molecules to effectively diffuse
into the interlayers to exfoliate and subsequently disperse the
layers.[28]
Zheng et al.[29] used another strategy of acid-intercalation
of graphite prior to the solvothermal treatment which was
then followed by ultrasonication as schematically shown in
Figure 3a. The authors accounted the strong ionic interactions
between intercalated acid molecules with oleylamine under
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Figure 2. a) TEM image of crumbled carbon sheets and its (b) Raman spectra showing graphitic peaks, Reproduced with permission.[13]
Copyright 2004, Elsevier B.V. c) SEM and (d) TEM image of carbon nanosheets aggregated into a flower-like morphology, Reproduced with permis-
sion.[22] Copyright 2008, American Chemical Society. e) SEM image of graphene obtained after the pyrolysis of solvothermal product from ethanol and
sodium reaction. f) TEM image of graphene sheets obtained after the ultrasonication of pyrolysis product as shown in (e) and (g) its selected area
diffraction pattern with integrated intensities of the in-plane h0 (√3d/n) reflections labeled with the Miller indices of hexagonal lattice, Reproduced
with permission.[19] Copyright 2009, Macmillan Publishers Limited. TEM images of (h) carbon nanorods and (i) graphene ribbons obtained from the
unzipping of carbon rods, (j) AFM image showing an average thickness of 3.5 nm for the graphene ribbons. Reproduced with permission.[24] Copyright
2016, Macmillan Publishers Limited. k) TEM and (l) AFM images of graphene ribbons obtained by the exfoliation of anthracite coal. The average thick-
ness of a graphene ribbon ranged from 0.9–2.4 nm. Reproduced with permission.[25] Copyright 2016, American Chemical Society.

solvothermal conditions (170 °C, 72 h) as the main driving
force for the exfoliation and subsequent dispersion upon
mild ultrasonication (30 min). In normal liquid phase exfo-
liation where the graphite is straightly ultrasonicated without
providing chemical assistance, drastic reduction in flake size
occurs as a result of the high acoustic energy needed for exfo-
liation (Figure 3b). Here, the authors combined many strate-
gies such as acid intercalation-solvothermal exfoliation-ultra-
sonication dispersion to achieve relatively high concentration of
graphene (0.15 mg mL–1) with large flake size (lateral dimen-
sion ≈4 µm and areal dimension ≈300 µm2) of which 80% were
single layers (Figure 3c–f). The Raman spectra showed small
traces of D peaks for larger graphene flakes, reflecting a low
density of structural defects. This is surprising since one could
anticipate some degree of defect in the graphene lattice after
the acid and ultrasonication treatments. However the authors
did indicate that the fast acid treatment imparted oxide defects
only in the edges and contamination from oleyl amine could
easily be removed by annealing. They achieved smaller gra-
phene flakes also together with larger flakes which showed a
rather defective crystal lattice due to the increased number of
edges (Figure 3g). Al Hazmi et al.[30] also reported the achieve-
ment of non-defective graphene sheets through solvothermal
exfoliation of graphite using isopropanol at 400 °C for 2 h
(Figure 3h). In this work, the authors preferred to pre-inter-
calate the graphite with tartaric acid. The material was then
thermally expanded at 750 °C for 60s before the solvothermal
exfoliation. Even though, the authors claimed and provide evi-
dence that the obtained graphene sheets were 95% monolayers
through AFM and TEM measurements with lateral dimension
of 240–400 nm, they did not provide the total product yield for
direct comparisons with other approaches.

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Review
Figure 3.  Schematic representation of (a) graphite exfoliation through combined intercalation, solvothermal exfoliation and ultrasonic dispersion
route leading to large flakes, as opposed to (b) conventional liquid phase exfoliation which ruptures the graphite flakes resulting in small graphene
flakes, (c) SEM, (d) AFM and (e)TEM images of a large graphene flake. f) Photograph of graphene-oleylamine dispersion(A) as obtained and (B) after
one month displaying the dispersion stability, (h) Raman spectra of small and large graphene flakes compared to single layer graphene. Reproduced
with permission.[29] Copyright 2010, The Royal Society of Chemistry. h) Raman spectra comparing the graphite after tartaric acid intercalation, thermal
expansion and after solvothermal exfoliation. Reproduced with permission.[30] Copyright 2015, Elsevier Ltd.

Table 1 compares the selected properties of graphene syn-
thesized by subcritical solvothermal exfoliation methods with
that of CVD processes and other exfoliation methods such as
liquid phase, electrochemical and supercritical fluids exfo-
liation methods. There are promising indications that solvo-
thermal exfoliation may be beneficial to achieve defect limited
graphene sheets and could be improved if explored further in
combination with suitable techniques like high-shear or micro-
wave exfoliation which were recently found to provide a very
high yield of graphene.[31,32] Despite the enormous amount of
research on graphene synthesis from all around the world, a
successful graphene production by direct graphite exfoliation,
which can meet the graphene market requirements, is yet to be
developed .
Despite the above mentioned works, majority of reported
solvothermal subcritical works on the production of graphene
involved the reduction of GO either with subcritical water
(known as hydrothermal reduction) or with other subcritical
polar solvents like alcohols, DMF etc. (known as solvothermal
reduction).
3.1.1. Reduced Graphene Oxide Sheets (rGO)
In a typical experiment to produce rGO sheets, acid oxidation
of graphite to graphite oxide is performed first. The material
is then exfoliated in water or other suitable solvents with the
aid of ultrasonication into GO single layers. Next, this aqueous
dispersion is chemically reduced using reagents such as hydra-
zine and hydrogen iodide to get rGO. Subcritical hydro-/
solvothermal reduction of GO is considered as a green alter-
native to hydrazine based reduction methods. In this method,
GO dispersion is transferred to a Teflon lined autoclave and
reacted under high temperature for several hours to produce
rGO sheets. Hydrothermal reduction, exceptionally, is advanta-
geous not only because it is a water solitary reaction, but also
because the ionic product of water is high. Thus hydrothermal
conditions cause the protonation of OH functionalities
which bring about dehydration on the edges or basal planes of
GO followed by the π-bonding restoration (Figure 4a,b).[14,37,38]
After hydrothermal reduction, oxygenated carbon such as
epoxide, hydroxyl, and carboxyl group signals were seen

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Table 1.  Comparison of properties of graphene synthesized by different exfoliation methods and CVD.

Procedurea) Graphene yield/ Lateral size of D/G ratiob) C:O ratioc) Electrical Ref
concentration graphene sheet conductivity
Solvothermal exfoliation (Acetonitrile) 10–12 wt% 800 nm Invisible D peak (Ratio not given) Not given 1 kΩ sq−1 [28]
Solvothermal exfoliation (Oleyl amine) 0.15 mg mL−1 4 µm Invisible D peak 97.4:2.0 Not given [29]
Solvothermal exfoliation Not given 400 nm 0.06 94.0:6.0 Not given [30]
(Isopropanol & tartaric acid)
Supercritical exfoliation (scCO2, 51.8 wt%, 3–5 µm 0.04 93.3:6.4 Not given [33]
pyrene polymers) 0.5 mg mL−1
Supercritical exfoliation (scCO2) 16.7 wt% 5 µm Invisible D peak for ≈5 layers which Not given 2.8 × 107 S m−1 [34]
increases with decreasing layer number
Liquid phase exfoliation 1 wt% 0.01 mg mL−1 2 µm Invisible D peak Not given 6500 S m−1 [26]
(N-methyl-2-pyrrolidone [NMP])
Liquid phase exfoliation <0.1–3 wt% 300–800 nm 0.27 Not given 4 × 104 S m−1 [31]
(NMP, sodium cholate)
Electrochemical exfoliation (Inorganic salts) 85 wt% 5–44 µm 0.25 94.5:5.5 1.96 kΩ sq−1 [35]
Microwave exfoliation (Ionic liquids) 93 wt%, 100 mg mL−1 1–5 µm 0.14 96.8:3.2 2.1  ±  0.9 kΩ sq−1 [32]
CVD 1–20 µm 0.05-3.0 Not given 0.7–1 kΩ sq−1 [36]

a)
Graphite exfoliation in solvents (given in bracket) except for CVD; b)Raman peak analysis; c)XPS data.

Figure 4.  Schematic representation of hydrothermal reduction mechanism through (a) intramolecular and (b) intermolecular dehydration. c) XPS,
and (d) solid state13C NMR spectra of the GO and rGO (blue line) after hydrothermal treatment at 180 °C for 6 h. Reproduced with permission.[14]
Copyright 2009, American Chemical Society. High resolution C1s XPS spectra of (e) GO and (f) rGO after reduction by DMF(g) Schematic of probable
mechanism of GO reduction and functionalization by solvothermal-DMF, Reproduced with permission.[39] Copyright 2011, Elsevier Ltd.

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radically shrunk in NMR experiments (Figure 4c,d). Diverse
reduction effects can be realized by controlling the hydro-
thermal conditions such as temperature, reaction time, and
physical parameters of GO suspensions such as concentration
and pH. For instance, complete reduction of GO is not always
desirable when considering device applications, because super
hydrophobic graphene sheets restack and aggregate together
to precipitate out. This phenomenon makes further transfer
difficult. Instead a stable dispersion of rGO sheets is prefer-
able for device fabrication.
Ding et al.[40] suggested that in order to get a stable rGO
dispersion after hydrothermal reduction, the initial concen-
tration of GO should be greater than 0.3 mg mL–1, the tem-
perature below 160 °C, and maximum reaction time should be
4 h. In these conditions, the rGO has enough residual oxygen
functionalities to be stable in water. Also alkaline water hydro-
thermal reduction is reported to have better reduction effect,
hence does not make stable dispersion, where as acidic water
is not as effective in reducing but makes stable rGO disper-
sions in water after hydrothermal reduction. The residual
oxygen functionalities which are left unprotonated make the
resulting rGO solutions to be very stable. Zhou et al.[14] sug-
gested that in alkaline water, the surface charge of GO is
negative with large zeta potential (>–43 mV) resulting in well
dispersed sheets due to electrostatic repulsion provided by
the carboxyl groups. At this point, under hydrothermal condi-
tions, intramolecular dehydration predominates, and almost a
complete recovery of π-conjugation is possible. On the other
hand, in acidic water, GO has a low zeta potential, and carboxyl
functionalities are protonated. This can result in aggregated
states due to less effective electrostatic repulsion between
the sheets. Intermolecular dehydration between adjacent GO
sheets is more prominent at this stage, leading to covalent
ether linkages between the sheets. Complete restoration of
π-conjugation becomes impossible in such conditions. Nav-
arro et al.[41] indicated that the pH of GO solution greatly alters
the morphology of resultant rGO sheets. The authors reported
that in acidic conditions, small rGO sheets of 1 µm are seen
together with multiwall nanotubes (around 25 nm at pH = 3,
100 nm to µm of length at pH = 5–7) and other carbon nano-
forms. They have used acidic water at 200 °C for more than 6 h
to reduce GO. Their results indicate that even initially mildly
acidic water during a long hydrothermal treatment creates
extreme acidic conditions, resulting in rupture of large GO
sheets into smaller ones. In contrast, flake size of rGO ranged
up to10 µm at higher pH, but seemed contaminated with salt
impurities all over the sheets.
In addition to water, other organic solvents such as eth-
anol, isopropanol, 1-butanol, ethylene glycol, dimethyl-
formamide, tetraethylene glycol, n-hexylamine and ethyl
acetate under subcritical conditions are reported as effec-
tive for reduction of GO.[35,39,42–46] The effect of reduction
procedure is reflected in C/O ratios of resulting rGO, and
are listed in Table 2. In the case of reduction by DMF along
with decarboxylation reactions, 3.1 at% N incorporation was
also reported. DMF in presence of water is hydrolyzed into
NH(CH3)2 under solvothermal conditions, which, as the
reaction progressed, is protonated to [NH2(CH3)2]+. This
cation then readily interacts with –COO− leading to edge
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functionalization of rGO sheets with alkyl groups. This func-
Review
tionalization stabilizes the dispersion also(Figure 4e–g).[39]
Similarly solvothermal reduction of aqueous GO with amino
propyl trimethoxy silane also resulted in edge functionaliza-
tion of rGO, providing a high concentration stable rGO dis-
persion (4 g L–1).[47] Nevertheless, the extent of restoration of
π conjugation would be inferior with such functionalization.
Even when we admit that hydrothermal/solvothermal treat-
ment is an environmentally friendly route for the controlled
reduction of GO, the long reaction time is a disadvantage.
The use of microwave heating instead of conventional oven
heating allowed the reaction time to be shortened from sev-
eral hours to a few minutes.[45] The temperature inside the
reactor increases very fast due to microwave absorbing polar
solvents. As a result autogenous pressure would be gener-
ated, similar to that of a heated conventional autoclave, but
with greater energy efficiency.[45]
There are enormous number of scientific research studies
dedicated to the reduction of GO, since it is believed to be
the most successful method to obtain scalable amount of
graphene, even though with compromised properties com-
pared to pristine graphene. Note that many of the chemical
reduction methods of GO using reducing agents involve tem-
perature, and are referred as solvothermal by the authors.[48]
However, as described in the introduction section, a reac-
tion can be considered solvothermal when carried out in a
closed system using a solvent at a temperature higher than
its boiling temperature. As a consequence of closed system,
a high pressure will also be involved in the reaction. In this
review, we consider only such reactions which were done in
an autoclave. The status of hydro-/solvothermal reduction is
not in the front stage considering the extent of deoxygenation
it could achieve. For instance, hydrothermal reduction of GO
at 200  °C during 16 h lead to a C/O ratio of 14.1.[42] This
ratio is inferior to that of chemical reduction by Al/HCl,[49]
Zn/H2SO4,[50] NH3BH3,[51] and supercritical ethanol[52] which
led to C/O ratios of 18.6, 21.2, 14.2 and 14.4, respectively.
Nevertheless, this C/O ratio for hydrothermal reduction is
better than the ratio chemically obtained with NaBH4,[53]
HI,[54] hydrazine,[55] glycine,[56] vitamin C[57] and urea[58]
which are of 8.6, 12.0, 10.3, 11.2, 12.5 and 4.8, respectively.
To summarize this section, graphite exfoliation in subcrit-
ical solvothermal conditions is still in a primitive stage, and
has not been reported as providing any significant advances
compared to liquid phase exfoliation and/or CVD methods.
Surprisingly, due to the unavailability of reported electrocon-
ductivity values we could not directly compare the electronic
quality of graphene sheets from hydro-/solvothermally exfo-
liation/reduction with that of other established methods such
as liquid phase exfoliation, CVD, chemical and thermal reduc-
tion. Nonetheless, solution phase bottom-up synthesis of gra-
phene sheets on solvothermal conditions would be a prom-
ising research area, and potential cost effective alternative
to gas phase CVD if explored further. Even though, hydro-/
solvothermal conditions put forward a very successful green
reduction strategy for GO, the research so far in this direction
is not at all exhaustive, and new approaches should be con-
stantly explored to get this environmentally benign process to
its full potential.
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Table 2.  Comparison of different hydro-/solvothermal reduction conditions for synthesis of rGO.

Solvent Temp, Time, pH C/Oa) (GO) C/Oa) (rGO) IC-C/IC-Ob) (GO) IC-C/IC-Ob) (rGO) Concentration Ref
(rGO)
Water 180 °C, 6 h …… ……. 1.8 5.6 0.5 mg mL−1 [14]
Water 160 °C, 4 h …… ……. …… …… 0.3 mg mL−1 [40]
Water 180 °C, 6 h, pH 3 …… ……. 1.1 7.8 …… [41]
Water 180 °C, 6 h, pH 5 …… …… 1.1 9.4 …… [41]
Water 180 °C, 6 h, pH 7 …… …… 1.1 9.8 …… [41]
Water 180 °C, 6 h, pH 9 …… …… 1.1 11.4 …… [41]
Water 180 °C, 6 h, pH 11 …… …… 1.1 14.1 …… [41]
Water 180 °C, 6 h, pH 11 0.36 1.5 …… …… …… [38]
Water 180 °C, 16 h …… 8.4 …… …… …… [42]
Water 200 °C, 16 h …… 14.1 …… …… …… [42]
Water 180 °C, 20 h 1.8 5.9 …… …… …… [43]
Ethanol 180 °C, 16 h …… 10.3 …… …… …… [42]
Ethanol 120 °C, 16 h …… 7.0 …… …… …… [42]
Ethanol 180 °C, 20 h 1.8 7.2 …… …… …… [43]
Butanol 160 °C, 16 h …… 6.4 …… …… …… [42]
Tetraethylene glycol 300 °C, 15 min 2.3 11.4 …… …… …… [45]
Ethylene glycol 120 °C, 16 h …… 8.3 …… …… …… [42]
Ethylene glycol 180 °C, 16 h …… 11.3 …… …… …… [42]
Ethylene glycol 140 °C, 16 h 1.42 3.03 ……. ……. ……. [46]
Ethylene glycol 160 °C, 16 h 1.42 3.57 ……. …….. …….. [46]
Ethylene glycol 180 °C, 16 h 1.42 3.84 ……. …….. …….. [46]
Dimethylformamide 180 °C, 12 h 2.0 5.5 …… …… 0.3 mg mL−1 [39]
Water+3-Amino propyltriethoxysilane 200 °C, 12 h 2.3 3.6 …… …… 4.0 mg mL−1 [47]

a)Ratio of total carbon to total oxygen; b)Ratio of carbon bonded to carbon (CC) and carbon bonded to oxygen (CO).

3.2. Heteroatom Doped Graphene Sheets
Methods to achieve nitrogen (N) doping of graphene gen-
erally include high-power electrical Joule heating, thermal
annealing or chemical vapor deposition with ammonia/N2 gas
as nitrogen source. However the high temperature require-
ment of these methods adversely affects the realization of their
device applications.[59] On the other hand, hydro-/solvothermal
methods can be used to achieve effective N doping, at compa-
rably much lower temperature. These methods are based on
the use of N containing precursors like ammonia, hydrazine,
urea, hexamethylene tetramine and/or ammonia with aqueous
GO. Simultaneous reduction of GO and N doping can be real-
ized in each case. An instance is given by Long et al.[60] who
reported nitrogen doping up to 4.5 wt% when aqueous GO is
hydrothermally treated with 0.3 wt% hydrazine and 30 wt%
ammonia at 120  °C . The oxygen content of GO decreased
from 48 to 13.5 wt%, indicating a simultaneous reduction. The
authors reported that without hydrothermal atmosphere, N
doping is impossible. Considerable morphology changes can be
observed by varying the hydrothermal temperature from 120 to
200 °C (Figure 5a–c). It is difficult to draw a general conclusion
whether the type of the nitrogen precursors or hydrothermal
conditions bring about enhanced N doping level. For instance,
N doping level of 7.2 and 9.6 wt% are reported using ammonia
solution as N-precursor with GO at 180  °C (for 12 h) and
110  °C (for 6 h), respectively.[61,62] On the other hand, using
urea and hexamethylenetetramine, 8.6 and 11.3 wt% N doping
are achieved at 180 °C for 12 h.[63,64] In all cases, N content is
a cumulative contribution of pyridinic, pyrrolic and quaternary-
N and each contribution varies with increasing hydrothermal
treatment time (Figure 5d–f), the quaternary contribution dom-
inating as reaction progress. It has been hypothesized that in
high temperature-pressure solvothermal conditions, ammonia
gas is released by precursors like urea or hexamethylenetet-
ramine. The gas then reacts with carboxylic acid and hydroxyl
species of GO to form intermediates like amide/amine, which
then undergo either dehydration to form pyridine/pyridone or
decarbonylation to form pyrrole/quaternary-N structures on the
course of time (Figure 5g–h).[65] However, no evidence is given
for this hypothetical mechanism by the authors.
While the above discussed hydrothermal methods used
GO as graphene precursor, a direct bottom-up synthesis of N
doped graphene by a solvothermal reaction between lithium
nitride and CCl4 at 250  °C for 10 h, in nitrogen atmosphere
was reported by Deng et al.[66] The authors speculated that sp3
hybridized carbon in CCl4 likely reacts with lithium nitride
to form dichlorocarbene, CC and CN groups as

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Review

Figure 5.  TEM images of N doped rGO reduced at (a) 80, (b) 120 and (c) 160 °C . Sheet wrinkling can be observed with increasing reduction tempera-
ture. Reproduced with permission.[60] Copyright 2010, American Chemical Society. (d–f) XPS N1s spectrum of the N doped graphene sheets prepared
with different hydrothermal reaction times: (d) 4 h, (e) 8 h, and (f) 16 h. Here N1, N2 and N3 denotes pyridinic-N (398.1 eV), pyrrolic-N (399.5 eV)
and quaternary-N (401.6 eV), respectively. N1 and N2 are the main species during the initial stage of the hydrothermal process (up to 8 h). N3 compo-
nents become more obvious when hydrothermal time is increased to 16 h, (g, h) Schematic of hypothetical mechanism showing (g) Nitrogen insertion
routes in GO; (h) Routes for the formation of a hypothetical structure of quaternary-N in GO. Reproduced with permission.[65] Copyright 2012, The
Royal Society of Chemistry.

intermediates and subsequently followed by dechlorination to
form small domains of sp2 hybridized carbon containing N,
which then grew into N-doped graphene sheets, as schemati-
cally proposed (Figure 6a–c). Through this method, N doping
in the range of 4.5–16.4 wt% can be obtained.
3.3. Graphene Quantum Dots (GQDs)
Graphene quantum dots (GQDs) are emissive nanographene
sheets, from one to several tens of layers with diameters mainly
distributed in a range of 3–20 nm. GQDs are biocompatible,

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cutting chemically oxidized graphene sheets

Review

put forward by Pan et al.[67] has been vali-

dated by many other researchers who used
the same procedure to obtain GQDs for dif-
ferent applications such as combination with
fluorescent polymers for organic photo­voltaic
devices or combination with europium ions
for phosphate sensing.[69,70] Kim et al.[71]
studied the anomalous PL behavior of size-
dependent shape/edge-state variations of
GQDs. By controlling the dialysis process,
GQDs of various size ranging from 5 to
35 nm, and circular/elliptical-to-polygonal-
shapes are obtained (Figure 7c).
Unlike above discussed works where pre-
cursors of GO are subjected to acid oxidation
to synthesize GQDs, Zhu et al.[72] reported a
new solvothermal synthesis route for GQDs
using DMF without any strong acid oxidation
steps. Briefly, the synthesis process includes
mixing of GO in DMF under ultrasonica-
tion followed by treatment at 200  °C for
5 h. The yield of separated GQDs was 1.6 wt%,
Figure 6.  (a) Schematic representation of SbCFs synthesis of N-doped graphene through the and displayed a size distribution in the range
reaction of CCl4 and Li3N, where gray balls represent C atoms, blue for N, green for Cl, and
purple for Li, (b) High resolution STM images of isolated bilayer N-doped graphene, revealing
3.0–7.0 nm, major fraction coming around
perturbed electronic structure with defects caused through N doping (c) Simulated STM image 5 nm and 1–2 layers. The as-prepared GQDs
of (b), the inset is a schematic of N-doped graphene, with the hexagons in gray balls high- contained many chemical groups such as
lighting the atomic network of graphene and deep blue balls labeling N atoms. Reproduced OH, epoxy/ether, CO and CONR2
with permission.[66] Copyright 2011, American Chemical Society. (originated from decomposition of DMF) and
displayed excellent solubility (15 mg mL–1) in
nontoxic, and chemically inert and thus attractive for nano­ many polar organic solvents such as tetrahydrofuran, acetone,
device applications replacing toxic Cd based semiconductor DMF, dimethyl sulfoxide, ethanol and water with different pH
counterparts. Among several approaches, including top down levels. The GQDs showed strong green fluorescence with PL
and bottom up strategies developed for GQDs, lithography quantum yield as high as 11.4% using 9,10-bis (phenylethynyl)
techniques, electrochemical oxidation, chemical ablation, anthracene as a reference. Blue PL emitting GQDs with a
oxygen plasma treatment, chemical oxidation methods, and quantum yield of 15% was prepared very recently by Tian
carbonizing organics are the dominating procedures. However et al.,[59] by solvothermal treatment of expanded graphite in
they suffer from one or many of disadvantages like expensive DMF and H2O2 at 170 °C for 5 h. It is noteworthy that among
equipment/high temperature/multistep process requirements, the existing reports on synthesis of GQDs, hydro-/solvothermal
and heterogeneous size distribution of resulting GQDs. Hydro- treatment has a dominating role on the preparation of GQDs
thermal breaking down of GO was first reported in 2010 by with high quantum yield and uniform size distribution. In
Pan et al.[67] and GQDs with strong blue emission were achieved addition, surface functionalization and doping of GQDs are
(Figure 7a). The method includes several steps including initial also feasible in one step in hydro-/solvothermal atmosphere.
thermal reduction of GO at 200–300 °C for 2 h under nitrogen
atmosphere followed by controlled oxidation in a mixture of
sulfuric and nitric acid under mild ultrasonication. A hydro- 3.3.1. Doping and Surface Functionalization of GQDs
thermal treatment at 200  °C for 10 h under alkaline pH and
a subsequent dialysis process are also required to obtain GQDs N doped GQDs are reported to show better quantum yield of
which still suffer from a non-homogenous size distribution in 24.6% compared to undoped particles. They can be prepared by
the range of 5–13 nm and 1–3 layers of graphene. However, this direct hydrothermal treatment of GO suspensions at 180 °C in
method bears the advantage of scalability, and produces GQDs the presence of ammonia.[73] They exhibited a relatively narrow
with a quantum yield of 6.9% (using quinine sulfate as a refer- size distribution between 2–6 nm and 1–3 graphene layers.
ence) (Figure 7b). The same synthesis process when repeated Inspired by this work, Liu et al.[74] prepared N-GQDs of average
with small modifications such as slightly higher thermal reduc- size 3 nm adsorbed at the surface of larger N-GQDs of average
tion of GO at 600 °C and strong alkaline hydrothermal condi- size 35 nm with the aid of a hydrothermal treatment at 200 °C
tions (pH>12) resulted in ultra-small GQDs with a lateral size for different times with ammonia solutions. Like N doping,
of 1.5–5 nm and a number of layers of 2–3.[68] The well crystal- chemical modifications using molecules with strong electron-
lized GQDs exhibited bright and stable green PL with a slightly donating or -accepting ability like primary amines, can also
better quantum yield of 7.5%. The hydrothermal procedure of make drastic changes of electronic and optical characteristics

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The photoluminescence quantum yield was

Review
found to be ≈29–19% (quinine sulphate as
a standard sample), which decreased with
increasing the degree of amine functionaliza-
tion. Sun et al.[76] introduced a prior chemical
oxidative cutting down of GO sheets to GQDs
followed by hydrothermal treatment with
ammonia at 200  °C for 10 h. The obtained
GQDs showed bright blue fluorescence, and
their quantum yield was also increased from
2.5 to 16.4%, after amino functionalization.
Just like GO, due to its surface oxygen func-
tionalities, GQDs are also vulnerable for
functionalization. Shen et al.,[77] reported an
example of surface functionalization of GQDs
by polyethylene glycol (PEG). GO suspen-
sion was cut down into small pieces using an
ultrasonic cell crusher for 60 min and mixed
with PEG 10 before hydrothermal treatment
at 200  °C for 24 h. Simultaneous reduction
and surface functionalization with PEG were
achieved. The PEG passivated GQDs exhib-
ited a PL quantum yield of 28.0% (using
rhodamine B as reference). In addition, they
showed up conversion PL properties and
higher photocurrent generation capability.
Graphene sheets decorated with- N doped
GQDs (N-GQD/graphene) heterostuctures
were reported to be prepared by hydrothermal
treatment (180  °C for 2 h) of a suspension
of well-dispersed GO with electrochemically
prepared N-GQDs. The hydrothermal pro-
cess ensured the formation of heterostruc-
ture assembly without changing the intrinsic
chemical nature of the components. The gra-
phene film thus formed was demonstrated to
exhibit a good conductivity of ca. 40 S cm–1
and superior electrocatalytic ability for oxygen
reduction reaction in fuel cells.[78]
Figure 7. (a) Schematic representation of hydrothermal synthesis of GQDs from oxidized
graphene sheets. During hydrothermal treatment, epoxy chain composed of epoxy and car-
bonyl pair groups inserted onto graphene sheet, through which graphene sheets cut down into 3.4. Graphene Composites
smaller GQDs (b) Models of the GQDs in alkali (left) and acidic (right) pH, which is reversible
depending on pH. Reproduced with permission.[67] Copyright 2010, WILEY-VCH Verlag GmbH 3.4.1. Graphene/GO- Polymer Nanocomposites
& Co. KGaA, Weinheim. (c) HRTEM images of GQDs. As shown, they have different shapes
and percentage populations for a given size. Reproduced with permission.[71] Copyright 2012,
American Chemical Society. Hydrothermal and solvothermal treatments
have been used in the field of graphene
of GQDs. The high concentration of ammonia in hydrothermal polymer nanocomposites with diverse objectives. As discussed
atmosphere leads to the amino functionalization of GQDs above, and from a general point of view, such treatments can
in contrast to low concentration of ammonia which leads to be used for the reduction of GO and the functionalization of
N doping of GQDs. Tetsuka et al.[75] prepared single layer graphenic materials. This in turn can directly affect the physical
amino-functionalized GQDs of diameter of 2.5 nm by amino- properties of composites in which the modified particles are
hydrothermal treatment of GO at 70–150  °C using ammonia embedded. Hydrothermally treated GO has also been used as
solution, followed by thermal annealing at 100 °C (Figure 8a). adhesive agent for fiber reinforced polymers. GO was grafted
The fluorescence of amino functionalized GQDs can be onto chemically inert poly (phenylene benzobisoxazole) (PBO)
tuned from the violet to the yellow region through adjusting fiber surface via sbcDMF treatment.[79] Strong interfacial adhe-
the degree of the functionalization of the primary amine, by sion between oxidized PBO fibers and carboxyl functionalities
changing the initial concentration of ammonia, and the tem- of GO with the aid of ethylenediamine, guaranteed efficient
perature of the amino-hydrothermal treatment (Figure 8b). load transfer from the soft organic matrix to the stiff fibers

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Figure 8.  (a) Schematic illustration of the synthesis of amino-functionalized GQDs from GO, (b) Photoluminescence and selected UV/VIS absorption
spectra of amino-functionalized GQDs. Continuous and broken lines denote the spectra of amino-functionalized-GQDs prepared at 120 and 90 °C,
respectively, (c) Photographs of emission of amino-functionalized GQDs dispersed in water (prepared under the following conditions: 150, 120, 70,
90, and 90 °C in ×2 conc. ammonia solution, respectively from the left) under irradiation from a 365 nm UV lamp. Reproduced with permission.[75]
Copyright 2012, WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

with high strength and modulus. In this work, the effective use
of solvothermal strategy using sbcDMF which not only helped
in the exfoliation of GO sheets, but also in the effective dis-
persion of GO to ensure maximum contact with PBO fibers.
This in turn helps to reduce internal stress concentration and
improves overall mechanical properties and tensile strength of
the composites.
3.4.2. Graphene/GO- Semiconductors Composites
Hydro-/solvothermal processes have been used extensively for
the preparation of graphene composites with semiconductors,
as evidenced by a large number of publications. The increasing
interest in coupling graphene with semiconductors is based on
the electronic properties of graphene which can be utilized to
increase the lifetime of photo generated charge carriers from
semiconductors.[80] However, in order to achieve the desired
activity, one should consider how to fully and intimately cover
the individual graphene sheets with semiconductor particles
with a better interfacial contact. In fact, solvothermal synthesis
due to its versatility offers more possibilities for composite for-
mation compared to conventional wet chemistry process. A
variety of reaction strategies employing different solvothermal
reactions parameters, have been established which resulted in
graphene semiconductor composites with different morpholo-
gies and properties (Table 3, Figure 9 and 10). The composite
formation can be either a one step process comprised of in
situ crystallization of semiconductor nanoparticles in pres-
ence of graphene oxide or a two steps process comprised of
a prior ex situ crystallization of semiconductors followed by
composite formation with graphene oxide. However, in both
processes, semiconductor nanoparticles (ex situ) or their pre-
cursors (in situ) are mixed with GO and loaded to the reactor.
GO sheets are then reduced to rGO in the hydro-/solvothermal
environment. Simultaneously crystallization of semiconductor
nanoparticles ensued. Most of such semiconductor graphene
composites were successfully tested for photocatalysis applica-
tions, solar energy conversion, environmental protection, and
energy storage applications such as supercapacitors or lithium
ion batteries as listed in Table 3. Among which TiO2-graphene
is extensively investigated. In the case of ex situ crystalliza-
tion process, many authors have used commercial P25 (TiO2
containing 20% of rutile and 80% of anatase phase)[80,81] or
chemically synthesized anatase TiO2 nanocrystals.[82] The car-
boxylic acid groups of GO and surface hydroxyl groups of TiO2
nanoparticles would interact together and make a homogenous
composite. Simultaneously, the reduction of GO to rGO and
the deposition of TiO2 can be achieved. The TiO2 -graphene
composites prepared by hydrothermal approach presented
good coverage of nanoparticles on graphene surface compared
to random integration of the same through conventional wet-
chemical methods (Figure 9a,b). Thus they tended to show
better photocurrent density and better active visible light pho-
tocatalytic activity than that of materials made by random
integration of TiO2 with CNT/graphene.[80–83] Such materials
have demonstrated different applications such as photocata-
lytic dye/phenol/benzene degradation,[82,84,85] H2 evolution,[86]
and optical limiting.[87] The morphology of P25 changed from
particle to nanowire when the hydrothermal treatment was
done in alkaline conditions.[88] According to Pan et al.,[88] TiO2
nanowires (NWs) have more chance of uniform coverage on

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Table 3.  Typical examples of graphene-semiconductor composites and hydro-/solvothermal conditions for their synthesis.

Review
Sample Precursors Solventsa) Temp, Timeb) Morphologyc) Applicationd) Ref
TiO2-graphene GO, TiF4 Water 120 °C, 12 h Particles, 100 nm Photocatalyst [80]
TiO2-graphene GO, P25 Water: Ethanol (2:1) 120 °C, 3 h Particles, 30–40 nm Photodegradation [81]
TiO2-graphene GO, TiO2 Water: Ethanol (4:1) 130 °C, 4 h Particles, 10–15 nm Photodegradation [82]
TiO2-graphene GO, P25 Water: Ethanol (3:1) 120 °C, 3 h Wires, d: 20–200 nm and Photodegradation [88]
Particles, 10 –15 nm
TiO2-graphene GO, TiO2 Water: Ethanol (2:1) 120 °C, 12 h Particles, 100–200 nm Supercapacitor [17]
Belts,d: 150–200 nm
TiO2-graphene GO, P25 Water: Ethanol (2:1) 120 °C, 24 h Particles, 40 nm Photodegradation [83]
TiO2-graphene GO, P25 Water 120  °C, 3 h Particles, 5–15 nm Photodegradation [84]
TiO2-graphene GO, P25 Water 150 °C, 6 h Particles, 30–40 nm Photodegradation [85]
TiO2-graphene GO, P25 Water 180 °C, 6 h Particles, 20–30 nm H2-Production [86]
TiO2-graphene GO, Ti(OBu)4 Water: Ethanol (2:1) 160 °C, 72 h Particles, 5 nm Optical limiting [87]
TiO2-graphene GO, P90, NaOH Water 120 °C, 24 h Nanotubes, (d: 9 nm) Photodegradation [89]
TiO2-graphene GO, Ti(SO4)2 Water: Ethanol (1:1) 180 °C, 9 h Particles, 10 nm Photodegradation [90]
TiO2-graphene GO, TiCl4 Water 180 °C, 8 h Particles, 12–16 nm Photodegradation [91]
TiO2-graphene GO, Ti(OBu)4, Glucose, Water: Ethanol (10:1) 160 °C, 4 h Particles, 9 nm H2-Production [92]
NH4Cl, NH4OH
TiO2-graphene GO, Ti(OPr)4, Diethylenetriamine Isopropyl alcohol 200 °C, 24 h Sheets, ≈ 100 nm Li ion Batteries [93]
TiO2-graphene GO, Ti(OPr)4, H2SO4 Water 170 °C, 24 h Particles, 50–100 nm Sensor [94]
TiO2-graphene GO, TiO2 Water: DMF 200 °C, 20 h Crystals, 15–30 nm Photodegradation [95]
TiO2-graphene GO, Ti(OH)4, Acetic acid, HNO3 Ethyleneglycol 200 °C, 24 h Rods(d: 5 nm, l: 20–30 nm) Solar cell [96]
Ag-TiO2-graphene GO, AgNO3, TiO2 Water: Ethanol (2:1) 130 °C, 3 h Particles, TiO2: 100 nm Antibacterial [97]
Ag: 4–6 nm Photodegradation
Mn-TiO2-graphene GO, MnCl2, Ti(OBu)4,Acetic acid Ethanol: Water (20:1) 180 °C, 10 h Particles, 6–14 nm Photodegradation [98]
C- TiO2-graphene GO,Titanocene dichloride, H2O2 Tetrahydrofuran 210 °C, 12 h Particles, 9 nm Li ion Batteries
[99]
Cu- TiO2-graphene GO, Cu-TiO2 Water: Ethanol (2:1) 120 °C, 3 h Particles,9–12 nm Photodegradation [100]
N- TiO2-graphene GO, N-TiO2 Water: Ethanol (2:1) 120 °C, 3 h Particles, 8–12 nm Photodegradation [101]
V-doped-graphene GO, V-TiO2, NaOH Water 120 °C, 24 h Rods(d: 11 nm, l: 40–75 nm) H2 Evolution Reaction
Catalyst [102]
Pt- TiO2-graphene GO, TiO2 (post Pt doping) Water: Ethanol (1:1) 150 °C, 3 h Particles, 30 nm Photodegradation [103]
YF3:Yb3+, Tm3+-TiO2-graphene GO,(YF3:Yb3+,Tm3+ ), P25 Water: Ethanol (2:1) 200 °C, 6 h Particles, 30–50 nm Photodegradation [104]
ZnO-graphene GO, Zn(OH)2, NaOH Water 180 °C, 24 h Rods, d: 90 nm, l: 3 µm ………………….. [105]
ZnO-graphene GO, Zn(NO3)2·6H2O, NH4OH Water 180 °C, 10 h Particles, 200–300 nm and Photodegradation [106]
Rods, d: 100 nm, l: 600 nm
ZnO-graphene GO, Zn(OAc)2·2 H2O, NaOH Ethanol 160 °C, 24 h Rods, d: 15 nm, l: 180 nm Photodegradation [36]
Bi2WO6-graphene GO, Bi2WO6 Water: Ethanol (2:1) 160 °C, 24 h Nanoplates, 5.5–15.7 nm Photodegradation [107]
ZnFe2O4-graphene GO, Zn(NO3)2·6H2O, Ethanol 180 °C, 12 h Particles, 7–10 nm Photodegradation [108]
Fe(NO3)3·9H2O
CoFe2O4-graphene GO, Co(NO3)2·6 H2O, Water 180 °C, 10 h Particles, 15–25 nm Photodegradation [109]
Fe(NO3)3·9H2O, NaOH
CoFe2O4-graphene GO, Co(NO3)2·6 H2O, 1-Hexanol 200 °C, 16 h Particles, 19–27 nm Microwave absorption [110]
Fe(NO3)3·9H2O, NaOH
NiFe2O4-graphene GO, Ni(NO3)2·6 H2O, Water 180 °C, 10 h Particles, 10–20 nm Microwave absorption [111]
Fe(NO3)3·9H2O, NaOH
NiCo2O4-graphene GO,Ni(NO3)2.6H2O, Water: Ethanol (1:1) 180 °C, 8 h Nanoarrays Supercapacitor [112]
Co(NO3)2.6H2O,Urea

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Table 3. Continued.

Sample Precursors Solventsa) Temp, Timeb) Morphologyc) Applicationd) Ref

Li4Ti5O12-graphene GO, Li4Ti5O12 Ethanol 120 °C, 16 h Particles, 100–200 nm Li ion Batteries [33]
NiMoO4-graphene GO, Ni(CH3COO)2·4H2O, Water 160 °C, 10 h Sheets, ≈100 nm Supercapacitor [113]
(NH4)6Mo7O2·4H2O,Urea
CdFe2O4-graphene RGO,Fe(NO3)3·9H2O, Water 180 °C, 12 h Particles, 10–20 nm Sensor [114]
Cd(NO3)2·4H2O, NaOH
CuFe2O4-graphene GO, FeCl3·6H2O,NaAc, PVP Ethylene glycol 180 °C, 20 h Spheres, 100 nm Supercapacitor [115]
CuCl2·2H2O
Co3O4-graphene Graphene, Co(NO3)2·6H2O Water 180 °C, 1.5 h Particles, 5.8 nm Supercapacitor [116]
Co3O4-graphene GO, Co(NO3)2·6H2O, NH4OH Ethanol 190 °C, 24 h Polyhedron, 100–250 nm Li ion Batteries [117]
Co3O4-graphene GO, CoCl2 6H2O, Na2CO3 Water: Isopropanol (1:2) 80 °C, 4 h Particles, 5 nm Supercapacitor [118]
Co3O4-graphene GO, (Co(C2H3O2)2·4H2O), Water 180 °C, 12 h Particles, 33 nm Photodegradation [119]
NH4OH
Co3O4-graphene GO, CoCl2.6H2O, H2O2 Water 170 °C, 12 h Particles, 5–15 nm Microwave absorption [120]
Co3O4-graphene GO, CoSO4·7H2O,Urea, NH4OH Water: Ethanol (1:1.5) 120 °C, 12 h Rods, d: 30 nm, l: 1–2 µm Li ion Batteries [121]
MoO3-graphene GO, MoO3, H2O2 Water 180 °C, 0.5 Belts, d: 200–500 nm Li ion Batteries [122]
h(MW)b
MoO3-graphene GO, Na2MoO4·2H2O, NaCl, HCl Water 180 °C, 24 h Belts, d: 200–300 nm ………………. [123]
SnO2-graphene GO, SnCl2·2H2O, Na2CO3 Water: Ethanol (1:1) 120 °C, 6 h Particles, 5 nm Li ion Batteries [124]
SnO2-graphene GO, SnCl2·2H2O, Ethanol 180 °C, 24 h Particles, 5 nm Supercapacitor [125]
SnO2-graphene GO, SnCl4.5H2O, NaOH Water 200 °C, 8 h Flower, 500 nm ………………. [126]
SnO2-graphene GO, SnCl2·2H2O, NaOH Water 200 °C, 24 h Particles, 5.1 nm Li ion Batteries [127]
MnO2-graphene GO, MnSO4·H2O, KMnO4, Water: Ethanol (3:2) 90 °C, 15 h Rods, d: 20–40 nm, l: 0.3 µm Supercapacitor [32]
Mn3O4-graphene rGO, KMnO4, Ethylene glycol Water 120 °C, 4 h Rods, d: 100 nm, l: 1 µm Supercapacitor [128]
VO2-graphene GO, NH4VO3,HCOOH Water 180 °C, 48 h Nanotubes, d: 100 nm Li ion Batteries [129]
VO2-N-graphene GO, NH4VO3,HCOOH Water 180 °C, 72 h Flower, 500 nm–1 µm Li ion Batteries [130]
RuO2-graphene GO/rGO, RuCl3·nH2O Water 200 °C,10 Particles, 2–3 nm Supercapacitor [131]
min(MW)b)
RuO2-graphene GO/ RuCl3·nH2O Water 180 °C, 4 h Particles, 3 nm Supercapacitor [132]
RuO2-graphene GO, PDDA, RuCl3·nH2O Water 180-200 °C, 4–8 h Particles, 5–10 nm Supercapacitor [133]
Fe3O4-graphene GO, Fe(acac)3, NH4Ac Ethylene glycol 200 °C, 24 h Flower, 50–70 nm Li ion Batteries [134]
Drug delivery
Cu2O-graphene GO, CuCl2·2H2O, Na(Acetate) Ethylene glycol 160 °C, 20 h Flower, 150 nm Supercapacitor [34]
Bi2O3-graphene GO, Bi2O3@GO, Urea Water 120 °C, 6 h Particles, 250 nm Li ion Batteries [135]
Cr2O3-graphene GO, Cr(NO3)3·9H2O, Urea Water 120 °C, 5 h Particles, 2–10 nm Li ion Batteries [136]
WO3-graphene Graphene, Na2WO4·2H2O, HCl Water 180 °C, 24 h Sheets and Rods, 1–3 µm Gas sensor [137]
ZnS-graphene GO, Zn(Ac)2, Na2S·9H2O, Water 140 °C, 10 h Particles, 4.5 nm ……………… [138]
NH4OH
ZnS-graphene rGO, ZnCl2,Thiourea Ethanol 180 °C, 12–16 h Particles, 10 nm and Photovoltaics [139]
Flakes, 50–80 nm
ZnS-graphene GO, Zn(NO3)2·6H2O, CS2, Water: Ethylene 180 °C, 12 h Particles, 6 nm Supercapacitor [140]
C2H4(NH2)2 glycol (1:1)
NiS-graphene GO, NiCl2·4H2O, Thiourea Water 180 °C, 24 h Flakes, t: 5 nm Li ion Batteries [141]
Na3C6H5O7·2H2O, NH4OH
NiS-graphene GO, NiCl2·4H2O, L-cystein Water 200 °C, 24 h Particles, 10–80 nm Li ion Batteries [142]
NiS-graphene GO, NiCl2, Thioacet- Ethanol: Water (3:2) 180 °C, 24 h Spheres, 100 nm H2-Evolution Reaction [143]
amide, Ethylenediamine, Catalyst
Poly(vinylpyrrolidone)
CuS-graphene GO, CuCl2, L-cysteine Water 160 °C, 12 h Particles, 18 nm Photodegradation [144]

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Table 3. Continued.

Review
Sample Precursors Solventsa) Temp, Timeb) Morphologyc) Applicationd) Ref
CdS-graphene rGO, Cd(NO3)2·4H2O, Water 180 °C, 3.5 h Particles, 10 nm …………………. [145]
Na2S·9H2O
CdS-graphene rGO, CdCl2.(2.5)H2O, Water 180 °C, 3.5 h Flower, 10 µm ……………. [145]
Na2S·9H2O
CdS-graphene rGO, Cd(Ac)2. 2H2O, Na2S·9H2O Water 180 °C, 3.5 h Particles, 100 nm ……………. [145]
CdS-graphene GO, CdCl2·2.5H2O, Water 160 °C, 10 h Flower, 620 nm ……………. [146]
Na2S2O3·5H2O
CdS-graphene GO, Cd(Ac)2. 2H2O, DMSO 180 °C, 12 h Particles, 3 nm H2-Production [147]
CdS-graphene GO, Cd(Ac)2. 2H2O,Thiourea Ethyleneglycol 120 °C, 12 h Particles, 100 nm …………. [148]
VS2-graphene RGO, NH4VO3, NH4OH, CTAB, Water 180 °C, 20 h Sheets, 200 nm Li ion Batteries [149]
CH3CSNH2
Ni3S2-graphene GO, Ni(S2COC6H11)2 Ethyleneglycol 180 °C, 20 h Particles, 8–28 nm Supercapacitor [150]
Adsorbent
MoS2-graphene GO, Na2MoO4, H2CSNH2 Water 210 °C, 24 h Sheet, 1–2 µm H2-Production [151]
TiO2- MoS2-graphene Ti(OC4H9)4, MoS2-graphene Water: Ethanol (2:1) 180 °C, 10 h Particles, 7–10 nm H2-Production [151]
Ce–SnS2-graphene GO,SnCl4·5H2O, CTAB Water: Ethanol (1:1) 180 °C, 36 h Flower, 1–2 µm Li ion Batteries [152]
Ce(NO3)3.6H2O, CH3CSNH2
CuInS2-graphene GO, Cu(Ac)2·H2O, In(Ac)3, Ethanol 160 °C, 12 h Particles, 2–5 nm Solar cell [153]
1-octadecylamine, CS(NH2)2
Co9S8-graphene GO, CoCl2·6H2O, CH4N2S Ethyleneglycol 180 °C, 12 h Particles, 80–90 nm Li ion Batteries [154]
Ni-graphene GO, Ni(NO3)2, NH4OH, Water 180 °C, 12 h Particles,10–50 nm H2-Production [155]
Hydrazine
CdS-ZnO-graphene GO, CdS, ZnO Water: Ethanol (2:1) 200 °C, 6 h Particles, 100–200 nm H2-Production [156]
ZnSe-graphene GO, ZnSe(diethylenetriamine)0.5 Water 180 °C, 12 h Belts,d: 150–200 nm Photodegradation [157]
l : 1–4 µm Oxygen Reduction
Reaction
ZnSe-graphene GO, EDTA,NaOH, Se Water 190 °C, 36 h Flower,Sphere (50–100 µm) [158]
Zn(CH3COO)2·2H2O,
ZnSe-N-graphene GO, Zn(AC)2·2H2O, Water 180 °C, 12 h Belt (Few µm) Photodegradation [159]
Na2SeO3·5H2O, N2H4·H2O
Zn2GeO4-graphene GO, Zn2GeO4 Water 250 °C, 8 h Rods d: 200 nm Li ion Batteries [160]
l:1.25 µm
ZnxCd1−xS-graphene GO, Cd(CH3COOH)2·2H2O, Ethylene glycol 180 °C, 12 h Particles, 20–30 nm Photodegradation [161]
Zn(CH3COO)2·2H2O, Thiourea
CdSxSe1−x-graphene GO, Se, Hydrazine, Water, Ethylene glycol 120 °C, 8 h Particles, 100–200 nm [162]
Cd(Ac)2. 2H2O
Thiourea,
Cd2Sb2O6.8-graphene GO, C4H6CdO4·2H2O, Water 180 °C, 24 h Particles, 5–10 nm Photodegradation [163]
N2H4, NH4OH, KSbO6H6
Co3Sn2@Co-graphene N-rGO, SnCl2·5H2O, Water 250 °C, 24 h Particles, 15.6 nm Li ion Batteries [164]
CoCl2·6H2O, CTAB
Ni3Sn2-graphene GO,NiCl2·6H2O, SnCl2·2H2O Ethylene glycol 190 °C, 8 h Spheres,300 nm Li ion Batteries [165]
ZnIn2S4-graphene GO, ZnCl2, InCl3.4H2O, DMF: Ethylene glycol 250 °C, 24 h Flakes, 200 nm H2-Production [166]
thioacetamide (1:1)
Water 120 °C, 10 h Spheres,10 nm H2-Production [167]
MIL-53(Fe)-graphene ribbon Graphene oxide ribbons, DMF 170 °C, 24 h Polyhedron, 2 µm Photodegradation [168]
FeCl3·6H2O, 1,4-Benzenedicar-
boxylic acid
Ag/AgCl-graphene GO, AgNO3, NH4OH Water 130 °C, 3 h Particles, 10–200 nm Photodegradation [169]
(Ag-rGO post treated with FeCl3)

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Review
Table 3. Continued.
Sample Precursors Solventsa)
CoMn(CoMn)2O4-graphene GO, Co(OAc)2·4H2O, DMF: Water (5 :1)
Mn(OAc)2·4H2O, NaOH
'' DMF: Water (3 :1)
'' DMF: Water (2 :1)
'' DMF: Water (1 :1)
BiOCOOH -graphene GO, Bi(NO3)3·5H2O Water: DMF (6 :1)
LiMn0.5Fe0.5PO4 –graphene Li3PO4/GO, FeCl2·4H2O, Ethyleneglycol
MnCl2·4H2O
LiFePO4-graphene Graphene, FeSO4⋅7H2O, H3PO4, Water
LiOH⋅H2O
a)
(V:V): volume ratio; b)MW: Microwave; c)morphology and d: diameter, l: length of resultant semiconductors; d)application not demonstrated.
the graphene surface compared to TiO2 nanoparticles (NPs)
due to geometrical similarity (Figure 9c–e). When used as
photocatalyst, TiO2 NWs-graphene displayed better dye degra-
dation under sunlight compared to TiO2 NPs-graphene. This
is because, the NW structure provides a direct injection path
for photogenerated electrons into conductive graphene sheets,
while trapping photogenerated holes thus providing a longer
catalyst lifetime. In addition, the NW structure suppresses the
carrier scattering between NPs which is a common issue while
working with NPs.
Xiang et al.[17] also shared similar observation that one dimen-
sional TiO2 belts-graphene displayed better electrochemical
charge transfer performance compared to TiO2 NPs-graphene,
when tested as electrode for supercapacitor application. The spe-
cific capacitance of TiO2 belts-graphene was 225 F g–1 at 0.125 A g–1
which was 3.6 times higher than that of graphene-TiO2 NPs
(62.8 F g–1). Perera et al.[89] prepared TiO2 nanotube (≈9 nm)-
graphene composites by employing P90 (TiO2 containing >90%
of anatase phase) and an alkaline hydrothermal process which
simultaneously resulted in ≈70% reduction of GO (Figure 9f,g).
Alternatively, post hydrolysis of titanium precursors to (Ti (OH)4)
followed by hydrothermal treatment to crystallize TiO2 with
varying morphologies like particles/sheets (Figure 9h) is also
commonly employed.[90–94] Ti (OH) 4 has more affinity towards
carboxyl functionalities of GO compared to TiO2, and thus
enhanced interfacial contact is warranted. Subsequent dehydra-
tion and crystallization of TiO2 together with reduction of GO
would follow as hydrothermal reaction progresses. In either
cases, TiO2 nanoparticles in the graphene composites obtained
from solvothermal processes were predominantly anatase phase
due to the low temperature synthesis conditions.
Globally, all the reported works on solvothermal synthesis of
TiO2-rGO guaranty controlled crystal growth and homogenous
distribution. Another advantage of solvothermal methods over
conventional methods is that a calcination treatment at >500 °C
for TiO2 anatase phase crystallization is not needed. The reduc-
tion of GO at the same time would require slightly higher tem-
perature annealing treatment under inert atmosphere. In this
aspect, solvothermal methods put forward a one-step solution
to both problems. In order to achieve more efficient reduction
of GO, extra reducing agents such as glucose were employed.[92]
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Temp, Timeb) Morphologyc) Applicationd) Ref
200 °C, 6 h Plates, 80 nm Supercapacitor [170]
'' Fibers & Plates ''
'' Fibers & Plates ''
'' Fibers, 1 µm ''
120 °C, 12 h Flower, 5–6 µm Photodegradation [171]
180 °C, 12 h Particles, 20 nm Li ion Batteries [172]
170 °C, 5 h Particles, 60 nm Li ion Batteries [173]
Another strategy is to include GO during the post hydrolysis
of titanium precursors followed by a hydrothermal treatment
in which simultaneous crystallization and reduction could be
achieved.[80,95] Colloidal form of TiO2-graphene composites,
which could be very appropriate for device fabrication were
reported by Zhao et al.[96] who used ethylene glycol as solvent
instead of water/ethanol. A direct comparison of P25-graphene
composites with that from in situ hydrothermal crystallization
of titanium precursors provided clear demonstration of better
interfacial contact between graphene sheets and TiO2 for the
latter. The titanium precursors could sufficiently interact with
the functional groups of well-dispersed GO in an aqueous phase,
thereby leading to the intimate integration of the graphene and
TiO2 ingredients. A major drawback of TiO2 photocatalysts is
that they are active only in the UV region which is just 4% of
the solar spectrum. Metal doping of TiO2 and composite forma-
tion with graphene is found to enhance the visible light photo­
catalytic efficiency. Especially in environmental photocatalysis
application, where the degradation of organic contaminants is
the main role of the photocatalyst, the metal doped sites act as
trap sites for photo excited electrons. This reduces electron–
hole recombination which frees up the oxidative valence hole of
the photocatalyst for the degradation of organics.[112,174] In situ
one step hydrothermal doping of TiO2 with Ag/Mn and gra-
phene composite formation[97,98] or solvothermal (using THF)
carbon coating of TiO2 and graphene composite formation have
been reported.[99] Similarly, ex situ metal doping of semiconduc-
tors followed by composite formation with GO in hydrothermal
environment has been reported. For instance, Cu-doped TiO2,
N-doped TiO2, V-doped, YF3:Yb3+, Tm3+-doped TiO2 graphene
composite have been reported.[100–102,104] It is also possible to
post dope TiO2-rGO composites. For instance, Pt-TiO2-rGO
composite was prepared by post doping TiO2-rGO obtained
from hydrothermal synthesis with Pt nanoparticles.[103] Equally
important but not yet well explored as TiO2, other environ-
mental semiconductor photocatalysts such as ZnO,[36,105,106]
and Bi2WO6,[107]-graphene composites or complex oxides such
as ZnFe2O4,[108] CoFe2O4,[110] NiFe2O4, and NiCo2O4 -graphene
composite[112,109,111] were also obtained using in situ solvo-
thermal crystallization route. Many of those materials were
demonstrated to be very effective for water purification by
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Review
Figure 9. TiO2-rGO composite synthesized from different reaction conditions showing different morphologies. TEM images of P25-rGO composite
(a) by hydrothermal route showing a uniform dispersion of spherical TiO2 nanoparticles over rGO surface and (b) by conventional synthesis using
hydrazine as reductant displaying non-homogenous and aggregated particle dispersion. Reproduced with permission.[86] Copyright 2011, American
Chemical Society. (c) TEM images of the graphene-TiO2 nanowire (GNW) composite. Inset is TiO2 nanowire made by alkaline hydrothermal treat-
ment. (d) Comparison of Raman spectrum of graphene-TiO2 nanowire (GNW) with graphene-TiO2 particles (GNP), TiO2 nanoparticles (NP) and TiO2
nanowires (NW). As shown, in both spectra of GNP and GNW graphene 2D peak is visible indicating effective reduction of GO under hydrothermal
treatment. (e) Cyclic voltammograms of GNW, GNP, NP and NW displaying higher current density for GNW. The test was carried out on thinfilm of
samples on FTO glass acting as anode. Reproduced with permission.[88] Copyright 2012, American Chemical Society. (e) TiO2 nanosheets uniformly
distributed on rGO surface, Reproduced with permission.[93] Copyright 2012, American Chemical Society. (f) SEM and (g) TEM images of TiO2
nanotube-graphene composite. Inset of (f) is high resolution TEM showing nanotube of 9 nm diameter. Reproduced with permission.[89] Copyright
2012, American Chemical Society.

photo degrading organic contaminants. Especially, the coupling
of magnetic nanoparticles to the photocatalysts has an added
advantage of easy magnetic separation. Other complex oxides
which have high electrochemical activity such as Li4Ti5O12,[33]
NiMoO4,[113,175] CdFe2O4,[114] and CuFe2O4[115] were also cou-
pled with graphene through solvothermal crystallization route.
Similarly metal oxide semiconductors such as Co3O4,[116–121]
MoO3[122,123] SnO2,[124–127] MnO2,[32] Mn3O4,[128] VO2,[129,130]
RuO2,[131–133] Fe3O4,[134] Cu2O,[34] Bi2O3,[135] Cr2O3,[136] and
WO3,[137] V2O5,[176] metal sulfides such as ZnS,[177,138,139,178,140]
NiS,[141–143] CuS,[144] CdS,[145–148] Ni3S2,[150] MoS2,[151,179]
VS2,[149]Ce doped SnS2,[152] CuInS2,[153] and Co9S8,[154] metal
nanoparticles such as Ni,[155] were successfully integrated into
graphene through solvothermal routes. The combination of

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Figure 10.  (a)TEM of Co3O4-graphene composite prepared hydrothermally at 180  °C for 1.5 h. Reproduced with permission.[116] Copyright 2012,
Elsevier B.V. (b) SEM images of the Co3O4-graphene composite prepared hydrothermally using ethanol-water solvent at 190 °C for 24 h. Reproduced
with permission.[117] Copyright 2013, Elsevier B.V. (c) TEM image of Co3O4 nanorods graphene composite prepared hydrothermally using ethanol-
water solvent at 120 °C for 12 h, the insert is the diffraction pattern. (d) High resolution TEM image of single Co3O4 nanorod displaying many Co3O4
nanoparticles self-assembled to form the rod. Reproduced with permission.[121] Copyright 2011, Elsevier B.V. TEM image of SnO2-graphene composite
prepared solvothermally (e) using ethanol at 180 °C for 24 h displaying homogenous distribution of SnO2 nanoparticles on the graphene surface.
Reproduced with permission.[125] Copyright 2013, Elsevier B.V. (f and g) using water at 200 °C for 8 h displaying SnO2 nanorods self-assembled to flower
morphology and dispersed on the graphene surface. Reproduced with permission.[126] Copyright 2012, Elsevier B.V. (h) TEM image of CdS-graphene
composite prepared using water at 180 °C for 3.5 h, Reproduced with permission.[145] Copyright 2013, Elsevier B.V. (i) SEM and (j) TEM image of
CdS-graphene composite synthesized using water at 160 °C for 10 h, Reproduced with permission.[146] Copyright 2012, The Royal Society of Chemistry.
(k) TEM image of VO2-graphene displaying nanotube morphology of VO2 synthesized using water at 180 °C for 48 h, Reproduced with permission.[129]
Copyright 2012, Elsevier B.V. (l) SEM and (m) TEM image of VO2-graphene displaying a nanosheet-built 3D flower hybrid structure of VO2 synthesized
using water at 180 °C for 72 h, Reproduced with permission.[130] Copyright 2013, American Chemical Society.

metal oxide or metal sulfides with graphene resulted in the
excellent capacitance activity and long cycling stability of the
resultant composites. Table 3 summarizes the typical exam-
ples of these composites, their precursors and employed solvo-
thermal conditions together with a brief description of resultant
morphologies. Figure 10a–m represents some of rGO-semicon-
ductor composites and how their morphology differs by tuning
solvothermal reaction parameters.
Two or more semiconductors hybridized with graphene can
be obtained by following a two steps in situ solvothermal crys-
tallization process. Xiang et al.[151] for example reported ternary
composite materials consisting of TiO2 nanocrystals grown in
the presence of a layered MoS2-graphene hybrid. This composite
material was prepared by a two-step hydrothermal process. In
the first step, the layered MoS2-graphene hybrid was prepared
by crystallization of TiO2 resulting in the final MoS2-graphene-
TiO2 composite. This composite (composed of 99.5 wt%
TiO2, 0.45 wt% MoS2 and 0.05 wt% rGO) showed excellent
photocatalytic H2 production activity. A ternary combination
of CdS-ZnO-graphene composite,[156,180] Fe3O4-TiO2-graphene
composite,[181] and quaternary combination of Fe3O4-polyani-
line-TiO2-graphene composite were also synthesized solvother-
mally.[182] The coupling of metal oxide and metal sulfide would
benefit to improve the charge separation and result in longer
lifetime of the charge carriers, while graphene would act as
an acceptor of the photo generated electrons from both semi-
conductors to ensure fast charge transportation. Metal sele-
nide semiconductors like ZnSe,[157–159] and other novel hetero-
structures such as Zn2GeO4,[160] ZnxCd1−xS,[161] CdSxSe1−x,[162]
Cd2Sb2O6.8,[163] Co3Sn2@Co,[164] Ni3Sn2,[165] Ag/AgCl,[169]
CoMn(CoMn)2O4,[170] BiOCOOH,[171] ZnIn2S4,[166,167] and Fe
based Metal organic frame work (MOF),[168] LiMn0.5Fe0.5PO4,[172]
LiFePO4,[173] Li4Ti5O12,[183] –graphene composites were also
reported as photocatalysts/Li-battery materials. All these studies
strongly support that the hydro-/solvothermal approach brings
about favorable reduction of GO and homogenous deposition
of semiconductor nanoparticles simultaneously. In fact, hydro-
thermal medium offers opportunity for multiple chemical

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transformations such as in the case of composite like Li4Ti5O12
(LTO)-polyethyleneimine-GO.[184] Hydrothermal treatment
of this ternary composite in presence of diethylenetriamine
at 180  °C for 4 h transformed LTO to LTO–TiN and GO to N
doped reduced graphene oxide. Here, diethylenetriamine under
hydrothermal conditions played dual roles: as a phase modi-
fier and N source to achieve the unique LTO–TiN-graphene
composite.
3.4.3. Other Inorganic Nanostructures- Graphene Composites
Layered double hydroxides (LDHs) have been recently used for
composite formation with graphene in order to make super-
capacitor electrode materials. Some instances from hydro-
thermal synthesis are Ni(II)Fe(III)-,[185] Ni(II)Al(III)-,[186,187]
Ni(II)Co(III)-,[188] and Co(II)Al(III)-LDHs.[189] As in the case of
other graphene composites, hydrothermal reaction conditions
and the precursors used were inevitably related to the final
LDH-graphene composite. Considering the case of Ni(II)Al(III)
LDH-graphene composite, Xu et al.[186] used an in situ growth
process by coating AlOOH colloids prepared by hydrolyzing
aluminum isopropoxide onto both sides of exfoliated GO sheets
and then mixing with Ni(NO3)2.6H2O and subsequent hydro-
thermal treatment at 100 °C for 24 h. A hierarchical 3D com-
posite composed of graphene layers sandwiched between LDH
nanosheet arrays was reported. LDH nanosheets were grown
perpendicularly and uniformly on both sides of the graphene
sheets, and showed a large specific surface area (184.7 m2 g–1)
and typical mesoporous characteristics. This material showed
very high pseudo capacitance performance (1329 F g–1 at a
current density of 3.57 A g–1). Unlike the above described two-
steps synthesis procedures, Gao et al.[187] used a one-step in situ
hydrothermal procedure to synthesize the same. The authors
used the chemically reduced GO as graphene precursors and
Ni(NO3)26H2O, Al(NO3)3 9H2O, and urea as Ni2+Al3+LDH
precursors and hydrothermally treated the mixture at around
100  °C for 24 h. The obtained Ni2+Al3+LDH-graphene com-
posite showed a decreased specific surface area of 87.2 m2 g–1
and a specific capacitance of 781.5 F g–1 at 5 mV s–1. Similarly
by fine tuning the reaction parameters, Huang et al.[189] dem-
onstrated the hydrothermal preparation of Co2+Al3+LDHs-
graphene composites in which the LDH sheets were size
controlled. The authors reported that the one-step direct
hydrothermal synthesis involving all the precursors (aqueous
GO, CoCl2·6H2O, AlCl3·6H2O, and urea) at 100 °C for 24 h
resulted in micro-sized Co2+Al3+LDHs-graphene composites.
On the contrary, a two-steps process involving the prepara-
tion of LDHs nuclei suspension at first, and then subsequent
hydrothermal treatment at 100 °C for 24 h with GO suspen-
sion resulted in nanosized Co2+Al3+LDHs-graphene compos-
ites. One step in situ hydrothermal synthesis could be useful
to achieve ternary composites like Ni2+A3+LDH-CNT-graphene
composite also, which synergically combined the conductive
matrix with electroactive moities and resulted in very high
capacitance performance (1869 F g–1 at a current density of 1.0
mA cm–2).[190] In situ solvothermal synthesis of Ni2+Fe3+-LDH
-graphene composite followed by ex situ thermal decomposi-
tion of LDH to form NiO/NiFe2O4-graphene composite were
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also reported.[191] Another set of inorganic nanostructures-
Review
graphene composites obtained from hydrothermal synthesis
include Mn2+,[192] carbon nanocages,[193] Pt3Ni-carbon,[194] N
doped carbon-rGO composites.[195] Nitrogen rich carbohydrates
under hydrothermal conditions with subcritical ammonia water
transformed to amorphous carbon containing nitrogen syn-
chronized with the dehydroxylation/ decarboxylation of GO.
As discussed in this section, hydro-/solvothermal synthesis
strategy is advantageous when compared to conventional syn-
thesis procedures for composites for several reasons such as
in situ reduction of GO, retardation of the aggregation of gra-
phene sheets, and homogenous dispersion of the inorganic/
organic counter parts on the surface of rGO sheets. Recently,
the number of scientific reports on hydro-/solvothermal syn-
thesis of graphene-composites is dominaty increasing over
conventional wet-chemical methods, and the approaches or
material compositions or types discussed in this section are not
all-inclusive as new approaches are constantly being explored.
3.5. Graphene-based Aerogels /Hydrogels
When the concentration of GO is typically greater than 1 mg mL-1,
under hydrothermal conditions, the flakes get spontaneously
reduced to rGO and self-assemble to form hydrogels.[196] How-
ever, at low GO concentration, the probability of interactions
through π–π stacking is rather difficult. Consequently, rGO
sheets precipitate as a powder. rGO hydrogels containing about
2.6 wt% of graphene sheets and 97.4 wt% water were reported
to show an electrical conductivity of 5 × 10−5 S m–1, a storage
modulus of 450−490 kPa that is 1 to 3 orders of magnitude
higher than those of conventional self-assembled hydrogels.[196]
Bi et al.[197] reported a hydrothermal reduction (solution with
controlled pH) to fabricate high density 3D compact graphene
structures. According to the authors, when concentration of the
GO dispersions is above 0.5 mg mL−1, hydrothermal reduction
results in hydrogels which can cast into any complicated mac-
roscopic shapes (Figure 11a–g). The pH of water plays a critical
role during the hydrothermal process. At alkaline pH (pH 10),
the GO sheets tend to be negatively charged and repel each
other. As the reduction reaction progresses, most of the carbox-
ylic acid groups from GO were removed. At this point, van der
Waals forces would exceed the electrostatic repulsion forces and
hence rGO sheets agglomerate together in a compact manner.
This contributed to the enhancement of conductivity, density,
and strength of resultant compact 3D graphene nanostructures
(Figure 11h). On the other hand, an excess alkaline medium
(pH>10) led to a decrease in ionization degree, resulting in
the tendency of the sample surface to become rough and in
the deterioration of the electrical conductivity and compressive
strength.[197,198] Carbohydrates such as glucose, β-cyclodextrin,
and chitosan if included with GO during the hydrothermal
process, get carbonized, and act as spacers to separate and
support the neighboring sheets in the hydrogel structure.[199]
Similarly, if N-containing precursors such as urea or ethylen-
ediamine are used, N doped rGO hydrogels could be achieved
with a N doping level of 3.95–6.6 wt% and specific surface areas
as high as >1300 m2 g–1 in the wet state.[200,201] Instead if HF
is used with GO in hydrothermal treatment, fluorine doped
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Figure 11.  Graphene hydrogels casted into different shapes (a) triangular prism, (b) quadrangular prism, (c) joint ring, (d) crucible, (e) screw stem,
(f) gear. The insets are their concept maps. (g) Castings steps- plastic containers of designed structures were used for the final casting of rGO gel,
which were then dried at 30 °C for 15 h in air to achieve the densified structure. (h) Schematic representation of graphene agglomeration in water
with and without ammonia. In pure water (the pathway indicated by black arrows), as the reaction progresses, due to the removal of carboxyl groups,
the large GO sheets finally lost charges and agglomerated easily. The green arrows represent the process of agglomeration at pH10, by the addition
of ammonia. At this pH, the carboxyl groups ionize into COO−, which reduce the partial agglomeration of the GO sheets. The GO sheets become
hydrophobic and COO− groups are removed gradually, resulting in a uniform agglomeration of GO sheets in a compact manner. Reproduced with
permission.[197] Copyright 2012, WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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(4.52 at%) graphene hydrogels are obtained.[202] Interestingly,
a temperature higher than 150  °C is not ideal for its hydro-
thermal synthesis, since fluorine tends to dissociate from gra-
phene sheets at high temperature. A high amount of dissolved
O2 during solvothermal treatment of GO with ethylene glycol
and water is found to oxidize the defective carbon atoms of GO
sheets. This oxidation creates numerous holes on GO sheets
which in turn increases the surface area of the resulting gra-
phene hydrogel.[203]
Owing to the high dispersion ability of hydro-/solvothermal
media, rGO hydrogels hybridized with materials such as
MoS2,[179] Sn,[204] Pd,[205] SnO2,[206] MnCO3,[207] AgVO3 nanowire
s,[208]polypyrrole,[209] Fe2O3,[210] and CoMn2O4,[211] were reported
to show better capacitance/photocatalytic performances which
will be discussed further in section 4. The hydrogel mor-
phology provides 3D porous structures which act as open chan-
nels for the electrolytes to freely move around. Wang et al.[212]
reported that solvents in solvothermal reactions play a key role
in determining the final products. For example, under same
solvothermal conditions (180  °C and 6 h) and same precur-
sors (Ni(OAc)2·4H2O and GO), different products have been
obtained with different solvents. Accordingly with DMF and
water, the hydrogels obtained are Ni-graphene and Ni(OH)2-
graphene, respectively. On the other hand when DMF/water
mixture is used as solvent, NiOOH-graphene hydrogel is
obtained. At high DMF/water ratio, NiOOH nanocrystals were
found better dispersed in hydrogel and the strength of hydrogel
increased significantly. Ma et al.[18] reported that in situ solvo-
thermal synthesis using ethanol as solvent at 180 °C for 12 h
has increased interfacial interaction between graphene sheets
and Fe2O3 in the hydrogel network compared to in situ hydro-
thermal (water at 180  °C for 12 h) or ex situ solvothermal
methods (ethanol at 180  °C for 12 h, using pre-synthesised
Fe2O3 nanoparticles). The authors stated that in situ solvo-
thermal synthesis (IS) resulted in homogenous distribution of
Fe2O3 nanoparticles in the graphene hydrogel network com-
pared to in situ hydrothermal (IH) or ex situ solvothermal syn-
thesis (ES). This has been reflected in the excellent cycling and
lithium ion storage rate performance of IS routed Fe2O3-gra-
phene hydrogel compared to that of IH and ES. The increased
interfacial interaction through Fe–O–C bonds in IS routed
Fe2O3-graphene hydrogel has enable to buffer the volume
change during charge/discharge process and to decrease the
aggregation and pulverization of the Fe2O3 particles.
3.6. Graphene Fibers
A fused silica column or glass pipe can replace an autoclave
and act as a micro-hydrothermal reactor to fabricate graphene
fibers.[213] GO suspensions of desired concentration are first
injected into the column/pipe which was then sealed to create
a one dimensional confinement similar to that of autoclave,
followed by baking at 90–230  °C for several hours. Fibers,
matching the pipe geometry were then recovered by flowing
N2. Continuous production of functional graphene fibers could
be achieved by scaling up of this method (Figure 12a–d). The
hydrothermal synthesis strategies generally adopted for syn-
thesis of N doped graphene, hybridization of graphene with
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CNT and polymers have been recently integrated into fiber
Review
fabrication. Thus neat graphene fibers, graphene-Fe3O4, gra-
phene-TiO2, N-graphene-CNT and graphene-poly(3,4-ethylene
dioxythiophene) fibers were achieved. Hybridization enhanced
the functionalities of graphene fibers such as CNT improved
the electrical conductivity (as high as 102 S cm–1 as opposed
to 10 S cm–1 for graphene fibers) and capacitive performance
of graphene fibers. Incorporation of Fe3O4 and TiO2 enabled
graphene fibers to be used for magnetic actuation and photo­
detector applications, respectively (Figure 12e–k).[214,215]
Very recently, Qu et al.[215] reported hybridization of poly(3,4-
ethylene dioxythiophene) with GO fibers through hydrothermal
methods as described before for rGO/PEDOT fibers with a
large interior hollow part as shown in Figure 13a–e. During the
hydrothermal reduction of GO inside a closed tube, gases such
as CO2 were released from the deoxygenation process. The gases
flowed from the solution interior to the void ends of the sealed
tube in response to the pressure difference, pushing away the
graphene sheets towards the walls of the tube. The hollow part
imparts a greater surface area, and thus an improved electro-
chemical capacitance to the fibers. The fibers were strong and
flexible to tie a knot (Figure 13f,g). While the bare rGO fibers
showed a high electrical conductivity of 4200 S m–1, the rGO/
PEDOT fibers showed an exponential increase of conductivity
with increasing PEDOT weight percentage and showed a con-
ductivity of 4700 S m–1 at 25% weight percentage incorporation
of PEDOT (Figure 13h).
4. Applications of Graphene-based Materials
Synthesized from Hydro-/Solvothermal Method
The extraordinary characteristics of graphene and of its asso-
ciated materials stem a wide range of high end applications
which have the potential to touch all the domains of our eve-
ryday life. In this section, we focus only on the performance
of hydro-/solvothermally synthesized graphene materials for
different applications ranging from energy-storage to biological
and environmental fields.
4.1. Electrochemical Energy Storage-Batteries and
Supercapacitors
Over the past few years, large numbers of publications have
investigated the use of graphene in electrochemical energy-
storage devices such as batteries and supercapacitors.[82] These
studies have advocated graphene as a good active material to
host ions such as Li+/Na+ in metal ion batteries, either as such
or as composite with other active materials capable of storing
Li+/Na+. Outstandingly, due to the intrinsic ultrathin and low
density characteristics, graphene may be a potential active
material of choice for flexible lithium ion batteries (LIB). Nev-
ertheless, bare graphene suffers from low cycling efficiency
due to the high initial Li+ consumption and restacking ten-
dency over repeated cycling.[88] In this regard, many studies
have found that the inclusion of electroactive materials
such as metals or metal oxides into the graphene provides
higher storage capacities than bare graphene or graphite.[82]
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Figure 12.  Photographs displaying the flexibility and elasticity of graphene fiber: (a) graphene fibers coiled around a glass rod, (b) hand-knitted gra-
phene textile, (c) fiber network embedded in PDMS matrix and (d) graphene spring, (e) Fe3O4 /graphene fiber attracted to the magnet and (f) photo­
electric response of TiO2/graphene hybrid fibers. The inset is the enlarged view of the photocurrent response curve. Reproduced with permission.[213]
Copyright 2012, WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim. (g–i) SEM image of graphene/CNT hybrid fibers, (h) surface and (i) fractured end
showing CNTs attached to the edges, (j) schematic of ultraviolet photodetector incorporating graphene/CNT fiber microsupercapacitors. Inset: SEM
image (scale bar, 1 mm) of an aligned TiO2 nanorod array grown on a FTO substrate and photograph of the three supercapacitors connected in series,
and its (k) current response. Reproduced with permission.[214] Copyright 2014, Nature publishing group.

Table 4 includes some hydro-/solvothermally synthesized
graphene-based composites/hydrogels which were proposed as
Li+/Na+ storage electrodes with promising reversible capacities
and life cycle.
Similarly graphene and graphene composites have been
explored for electrochemical capacitors (supercapacitors)
including both electrochemical double layer capacitors and
pseudocapacitors. Particularly, graphene hydrogels due to their
porous 3D structure, conductivity and mechanical strength
are better electrode materials for supercapacitors and can be
used without binding agent and/or conducting additive, unlike
materials in the powder/flakes form.[196,199] Schematics of such
a graphene hydrogel based supercapacitor and corresponding
cyclic voltagrams are given in Figure 14a–c. They show a spe-
cific capacitance of 175 F g–1, which is 50% higher than that
of the powder form.[196] Comparable capacitance (178 F g–1
at 0.2 A g–1) was reported for holey graphene hydrogel which
was synthesized in a high oxygen rich solvothermal condi-
tions.[203] Hydrothermal routed Nitrogen-doped graphene
sheets have also good performances as supercapacitor elec-
trode materials. As previously discussed, hydrothermal reac-
tion conditions and N-precursors have a direct influence on
the N-content and N-type doping. For instance, hydrothermal
reduction of GO with ammonia, hexamethylenetetramine
and urea resulted in 7.2, 8.6 and 10.1 at% of N doping.[62,65,63]
Their respective capacitance was reported to be 144.6, 161.0
and 326 F g–1 at 0.2, 0.5 and 0.2 A g–1, respectively. Another
study of graphene hydrogel containing 9.64 at% of N showed
a capacitance of 113.8 F g–1 and a high power density of
205.0 kW kg–1 at an ultrafast charge/discharge rate of

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Review
Figure 13.  (a) Schematic representation of fabrication of graphene/PEDOT hybrid fibers and formation of hollow structures, SEM images of a fiber
(b–c) fractured end displaying unique hollow structure, (d–e) surface at low and high magnifications. (f) SEM images of knotted fibers. Inset is a
cross-sectional SEM image, (g) Photographs displaying the high mechanical strength of the fiber. The fiber could carry objects with increasing weights
as high as 120 g, (h) The electrical conductivity of the fiber with increasing weight percentage of PEDOT:PSS. Inset is the photograph showing an
electrical resistance of fiber with a length of 1 cm and outer diameter of 112 µm as 216.6 Ω. Reproduced with permission.[215] Copyright 2016, WILEY-
VCH Verlag GmbH & Co. KGaA, Weinheim.

185.0 A g–1.[201] Hybrid graphene hydrogels such as manganese
carbonate (MnCO3), polypyrrole and NiOOH- incorporated
graphene hydrogels were also reported to show high specific
capacitance of 645.5 F g–1 (at 0.5 A g–1), 375 F g–1 (at 10 mV s–1),
and 1162 F g–1 (at 1 A g–1), respectively.[207,209,212] Solid state
supercapacitors made from N-graphene-CNT fibers were
reported to show a specific volumetric capacitance of 300 F cm–3
at 26.7 mA cm–3, and an energy density as high as 6.3 mWh cm–3
(Figure 14d–f).[214] Similarly, graphene-poly(3,4-ethylene dioxy-
thiophene) fibers were also reported for their good capaci-
tance performance, with a capacitance of 304.5 mF cm–2 at
0.08 mA cm–2 and an energy density as high as 27.1 µWh cm–2
at a power density of 66.5 µW cm–2 (Figure 14g–i).[215] Hydro-
thermally synthesized graphene-based composites were also
shown to meet the requirements for energy storage in superca-
pacitors. To list some of them (specific capacitance, current den-
sity, electrolyte are listed in bracket): TiO2-graphene composite
(225 F g–1 at 0.125 A g–1 in 1.0 M Na2SO4),[17] Co3O4-graphene
composite (415 F g–1 at 3 A g–1 in 6 M KOH),[116] SnO2-gra-
phene composite (364.3 F g–1 at 1.0 A g–1 in 1.0 M Na2SO4),[125]
MnO2-graphene composite (380 F g–1 at 0.3 A g–1 in 1.0 M
KOH),[32] Mn3O4-graphene composite (121 F g–1 at 0.5 A g–1
in 1.0 M Na2SO4),[128] RuO2-graphene composite (497 F g–1 at
0.5 A g–1,[131] 521.2 F g–1 at 0.5 A g–1,[133] and 219 F g–1 at 1.0 A
g–1[132] in 1.0 M H2SO4), Cu2O-graphene composite (215 F g–1
at 1.4 A g–1 in 6.0 M KOH),[34] ZnS-graphene composite
(191 F g–1 at 0.5 A g–1 in 6.0 M KOH),[140] Ni3S2-graphene com-
posite (281.2 F g–1 at 0.5 A g–1 in 3.0 M KOH),[150] NiCo2O4-
graphene composite (698 F g–1 at 0.5 A g–1 in 2.0 M KOH),[112]
NiMoO4-graphene composite (1888 F g–1 at 1.0 A g–1 in
2.0 M KOH),[113] CuFe2O4-graphene (576.6 F g–1 at 1.0 A g–1
in 3.0 M KOH),[115] CoMn(CoMn)2O4-graphene composite
(571 F g–1 at 1.0 A g–1 in 1.0 M KOH),[170] NiAl-LDH-
graphene composites (1329 F g–1 at 3.56 A g–1 in 6.0 M

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polymer. The GQDs provided an effective interface for charge

Review

Table 4. Performance details of hydro-/solvothermal routed graphene

composites for lithium ion (LIB)/sodium ion batteries (SIB). separation and an electron transport channel. The reported
J–V characteristics curves and corresponding energy band dia-
Composite Type Cycle Current density Capacity Ref gram are shown in Figure 15d,e. GQDs surface passivated by
number [mA/g] [mAh/g]
PEG were reported to exhibit upconversion photoluminescence
TiO2-graphene LIB 120 161 161 [93] properties and higher photocurrent generation capability under
C-TiO2-graphene LIB 100 20 110 [99] near-infrared light.[77] The GQDs-PEG spin-coated onto an ITO
Li4Ti5O12-graphene LIB 50 15.8 158 [216] substrate showed higher photon-to-electron conversion capability
compared with GQDs on ITO and was considered as a good
Co3O4 –graphene LIB 50 50 840 [117]
dopant material for solar cells. Recently CuInS2-QDs hybridized
Co3O4 –graphene LIB 40 100 1310 [121]
with graphene through solvothermal route applied for poly(1-
Co3O4 -graphene LIB 40 1000 1090 [121] methoxy-4-(2-ethylhexyloxy)-p-phenylenevinylene) based solar
MoO3-graphene LIB 100 100 172 [122] cell exhibited an efficiency of 1.5%.[153]
VO2-graphene LIB 20 40 320 [129]
VO2-N-graphene LIB 50 50 251 [130]
4.3. Fuel Cells
Fe3O4-graphene LIB 50 92.5 605 [134]
Fe2O3-graphene LIB 80 1600 1071 [217] Methanol offers several advantages over hydrogen as a fuel
Bi2O3-graphene LIB 100 200 417 [135] including the ease of transportation and storage and high theo-
C-Cr2O3-graphene LIB 100 45 650 [136] retical energy density. Thus direct methanol fuel cells (DMFCs)
are an attractive power source with high energy-conversion effi-
SnO2-graphene LIB 100 200 808 [127]
ciency and low operating temperatures. Highly dispersed Pt NPs
Zn2GeO4-graphene LIB 50 80 768 [160]
supported on nitrogen doped graphene synthesized by the urea
SnO2-graphene aerogel LIB 1000 2000 905 [206] assisted hydrothermal method were used in DMFCs.[64] The
NiS-graphene LIB 50 400 394 [141] electrochemical reduction of O2 (ORR) in fuel cells has two main
NiS-graphene LIB 1000 500 810 [142] possible pathways: one is the transfer of two electrons to produce
H2O2, and the other is a direct four-electron pathway to produce
VS2-graphene LIB 100 200 528 [149]
water. It is highly desirable to have ORR through four-electron
Co9S8-graphene LIB 50 50 841 [154]
pathway to obtain maximum energy capacity in fuel cells, as
Ce–SnS2-graphene LIB 50 353 707 [152] observed for example in N-GQDs supported by 2D graphene
Co3Sn2@Co-N-graphene LIB 100 250 1615 [164] sheets,[74,78] ZnSe-N-graphene composite,[157] CoMn2O4-N-gra-
Ni3Sn2-graphene LIB 200 100 554 [165] phene hydrogel,[211] and Pt3Ni–Carbon-graphene composite,[194]
as electrocatalysts prepared by hydrothermal routes.
LiMn0.5Fe0.5PO4 -graphene LIB 500 125 112.5 [172]
LiFePO4-graphene LIB 45 31 157 [173]
NiO/NiFe2O4-graphene LIB 100 10 670 [191] 4.4. Bioimaging
SnO2-graphene SIB 150 100 330 [124]
Sn-graphene hydrogel SIB 50 50 323 [204] Due to their stable photo-luminescence, low cytotoxicity, excel-
lent solubility, eco-friendliness and bio-compatibility, GQDs
are particularly attractive as bioimaging probes. Zhu et al.[72]
KOH)[186] and (781.5 F g–1 at 0.5 A g–1 in 6.0 M KOH),[187] reported no adverse effect of green photoluminescent GQDs on
NiCo-LDH-graphene composite (1911 F g–1 at 2.0 A g–1 in human osteosarcoma (MG-63) cell viability at a concentration
3.0 M KOH),[188] CoAl-LDH-graphene composite (581.5 F g–1 as high as 400 µg/150 µL. Confocal fluorescence microscopy
at 2.0 A g–1 in 1.0 M KOH),[189] NiAl-LDH-CNT-graphene com- results showed excellent bioimaging capability of GQDs with an
posite (1869 F g–1 at 1.0 mA cm–2 in 6.0 M KOH),[190] N rich excitation-dependent PL behavior (Figure 16a–d). Another study
carbon-graphene composite (300.0 F g–1 at 0.1 A g–1 in 6.0 M utilized N-doped GQDs for bio imaging of HeLa cells, with an
KOH).[195] excitation dependent PL behavior. Bright green luminescence
was observed inside the cells, indicating that the N-GQDs had
been internalized by the HeLa cells and were mainly localized
4.2. Solar Cells in the cytoplasm region (Figure 16e–h).[73] The low cytotoxicity
and bioimaging properties of GQDs could be advantageous in
Gupta et al.[69] demonstrated the use of hydrothermally prepared applications such as drug delivery, disease diagnosis and as bio-
GQDs for application in solar cells in combination with ani- sensors, if coupled with right counterparts.
line, which acted as an electron acceptor material in conjugated
polymer poly(3-hexylthiophene-2,5-diyl) (P3HT) based thin film
solar cells which showed an efficiency of 1.14% (Figure 15a–c). 4.5. Environmental Applications
Further they have demonstrated the organic light emitting diode
(OLED) application of GQDs with methylene blue dye and poly(2- The large surface area of graphene which can absorb the
methoxy-5-(2-ethylhexyloxy)-1,4phenylenevinylene) (MEH-PPV) target environmental toxic elements and thus concentrate

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Review
Figure 14.  (a) Schematic of a graphene hydrogel-based supercapacitor device; the graphene hydrogel can be cut into slices with a knife, and can be
used as electrode. (b) Cyclic voltammograms of the graphene hydrogel-based supercapacitor at two different scan rates displaying nearly rectangular
shape implying a good charge transport within the hydrogel electrodes and (c) respective galvanostatic charge/discharge curves at a constant current
of 1 A g–1. Reproduced with permission.[196] Copyright 2010, American Chemical Society. (d) Schematic of a micro-fiber supercapacitor constructed
with two rGO-CNT hybrid fiber electrodes on a polyester substrate, (e) Galvanostatic charge/discharge curves of micro-fiber supercapacitor at various
current densities from 66.7 to 133.3 mA cm–3, (f) comparison of volumetric device capacitance at different current densities for the micro-fiber super-
capacitor compared to commercial activated carbon supercapacitor. Reproduced with permission.[214] Copyright 2014, Nature publishing group. (g)
Figure displaying the long-term cyclic stability of the microfiber supercapacitors made from rGO-PEDOT hybrid fiber compared to that from bare rGO
fiber at a current density of 0.48 mA cm–2. Inset is photograph displaying serially connected three fiber supercapacitors which are then pasted onto
clothes to power LEDs, (h) Photographs showing rGO-PEDOT fiber supercapacitor of length 3.0 cm and connected in series to power 15 LEDs, (i)
The fiber supercapacitor is very flexible and retent their capacitance under different bending states. Reproduced with permission.[215] Copyright 2016,
WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

them in the viscinity of semiconductors like TiO2 to be
photodegraded is one of the main attraction of graphene when
used for environmental applications. However if the semicon-
ductors are not uniformly distributed on the surface of gra-
phene sheets, the advantage of using graphene is null. The
photogenerated holes from the semiconductors cannot reach
the adsorbed targets to oxidize. Thus homogenous disper-
sion with minimal agglomeration of semiconductors is critical
in graphene-semiconductor composites, an advantage pro-
jected by solvothermal synthesis. Photo degradation efficiency
of hydrothermal routed TiO2-graphene composites was well
demonstrated by different research groups for organics such
as gas phase benzene,[82,83] aqueous phenol,[85] chromium,[98]
and dyes such as methylene blue (MB),[81,84,88,97,218] reac-
tive black5,[84] malachite green,[89] rhodamine B (RhB),[90,91,95]
methyl orange (MO),[100,101,104] Orange-II,[36] surfactant (dode-
cylbenzenesulfonate)[103] in aqueous solutions. Similarly photo
degradation of organics is reported with other composites
such as ZnO-graphene for MB,[106] Bi2WO6-graphene for MB
and RhB,[107] ZnFe2O4–graphene for MB,[108] Co3O4-graphene

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Review

Figure 15. AFM images of composites (a) P3HT modified aniline (ANI) functionalized graphene sheets displaying large-scale phase separation.
b) P3HT/ANI-GQDs (c) MEH-PPV/MB-GQDs, showing uniform and fine features, suggesting nanoscale phase separation. This results in enhance-
ment of the exciton migration to the donor/acceptor interface, resulting in a decrease in the resistance and hence an improved performance of the solar
cell/OLED. (d) Current density versus voltage (J–V) characteristics of the photovoltaic devices based on ANI-GQDs with different GQDs content and
ANI-Graphene. The corresponding band diagram is given in the inset, (e) Measured current density of MEH-PPV with MB-GQDs 0–3% as function of
the applied voltage. The inset plots the electroluminescence spectrum of the MEH-PPV (red) and MEH-PPV/MB-GQDs (1%) (black). The inset also
shows the band diagram of the MEH-PPV/MB-GQDs and the recorded brightness of MEH-PPV LED and MEH-PPV/MB-GQDs (1%) LED. Reproduced
with permission.[69] Copyright 2011, American Chemical Society.

for phenol,[119] CuS-graphene for MB,[144] MoS2-graphene for
MB,[179] ZnSe-N-and ZnxCd1−xS- graphene for MO,[157,161] and
MB,[159] Cd2Sb2O6.8-graphene for RhB and MB,[163] BiOCOOH-
graphene for RhB,[171] Fe-based MOF-graphene ribbon for
benzyl alcohol,[168] and Ag-AgCl-rGO composites for MO.[169]
H2 production is another well demonstrated application of
hydrothermally synthesized graphene composites. Some of
them are TiO2-graphene,[86,92] CdS-graphene with 0.5 wt% Pt
as a co-catalyst,[147] TiO2-MoS2 –graphene,[151] Ni-graphene
composite,[155] and ZnIn2S4-graphene [166]composites which
have a H2 production rate of 4.0 µmol h–1, 1.12 mmol h–1, and
165.3 µmol h–1, 27.4 mmol min–1, 40.8 µmol h–1, respectively.
Similar observations were reported with ZnO-CdS-graphene
composites also.[156]
4.6. Sensors
Bai et al.[70] presented a new photoluminescent sensor for phos-
phate detection with the use of hydrothermally prepared GQDs
as an effective sensing platform. Initially, Eu3+ ions were coor-
dinated to the carboxylate groups on the surface of the GQDs,
where they acted as a bridge for the induction of GQDs aggrega-
tion. As a consequence, the PL of GQDs was quenched through
electron-transfer processes. When phosphate was introduced
into the system, Eu3+ ions which have a higher affinity for the
oxygen-donor atoms in phosphate, detached from carboxy-
late functionalities of GQDs to combine with phosphate. This
resulted in the dissociation of GQDs aggregates, as schemati-
cally presented in Figure 16i,j and as a consequence the PL
of the GQDs was restored. The restoration of PL was taken
as detection of phosphate in water. Hydrothermally prepared
GQDs and their amino functionalized forms were compared
by Sun et al.[76] for sensing metal ions. The sensor made of
GQDs could induce significant fluorescence decreases for Cu2+,
Al3+, Co2+, Cd2+, Mn2+, Pb2+, Fe2+, and Fe3+ at a concentration
of 10 µM. Amino functionalized GQDs induced a significant
fluorescence response for Cu2+ in the living cells because of
the high chelating affinity of Cu2+ ion to N and O functional
groups. Hydrothermally prepared graphene sheets were used
for chemiluminescent immuno assay of C-reactive proteins.[219]
TiO2-graphene composites were used for electrochemical detec-
tion of dopamine, one of the most important neurotransmitter,
with a detection limit of 2 µM.[94] Similarly, WO3-and CdFe2O4-
graphene composites were reported to show good selectivity
and response to acetaldehyde[137] and acetone vapor,[114] respec-
tively. Carbon nanocages-graphene composites were reported
for electrochemical detection of catechol and hydroquinone
which have poor degradation in the ecological environment and
are toxic.[193]
4.7. Electromagnetic Wave (EM) Absorption
There were few reports on hydrothermally synthesized gra-
phene composites with CoFe2O4,[109–111] NiFe2O4[111] and

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Review
Figure 16.  (a) TEM image showing a homogenous size (5.3 nm) distribution of GQDs, (b) PL behavior of GQDs in different solvents at 375 nm excita-
tion. Inset shows the corresponding photographs, (c) Imaging of MG-63 cells by GQDs at 405 nm excitation, (d) MG-63 cells viability with GQDs of
different concentrations. Reproduced with permission.[72] Copyright 2011, The Royal Society of Chemistry. (e) PL spectra of N-GQDs in water at different
excitation wavelengths from 280 to 480 nm. Inset is the photograph of the sample excited by a 365 nm UV lamp. (f) HeLa cells imaging by confocal
fluorescence microphotograph incubated with N-GQDs at 405 nm excitation (g) Bright-field microphotographs of HeLa cells, and (h) Image displaying
overlay of (f) and (g). Reproduced with permission.[73] Copyright 2013, The Royal Society of Chemistry. (i) The PL recovery of GQD–Eu3+aggregates in
the presence of different concentrations of phosphate (Pi). The concentrations of Pi were 0 to 190 mM for curves 1 to 13. The inset shows the change
of PL intensity (I/I0) at 450 nm of GQD -Eu3+ titrated with Pi. (GQDs, 10 µg mL–1; Eu3+, 216 mm; tris-HCl buffer, pH 7.8; excitation, 310 nm) and
(j) Schematic illustration of Pi detection based on the competition of Pi with carboxylate groups on the GQDs surface for Eu3+ions, Reproduced with
permission.[70] Copyright 2013, Wiley-VCH Verlag GmbH&Co. KGaA, Weinheim.

Co3O4[120] as microwave absorption materials. The residual
oxygen groups in rGO were supposed to act as polarized
centers, which promoted electromagnetic energy absorption.
Maximum reflection loss of at −47.9 dB at 12.4 GHz, −39.7 dB
at 9.2 GHz and −43.7 dB at 13.8 GHz was reported for CoFe2O4,
NiFe2O4 and Co3O4-graphene composites, respectively. A qua-
ternary composite consisted of graphene, Fe3O4, PANI, TiO2
showed superparamagnetic behavior and a reflection loss of
−41.8 dB at 14.4 GHz.[182] Such hierarchical structures induce
extra interfacial polarization for attenuation of EM waves while
the void space existing between different components such as
Fe3O4 and TiO2 result in relatively large specific surfaces area
providing more active sites for reflection and scattering of EM
waves effectively.
To conclude this section, graphene materials are attrac-
tive candidates in different energy, environmental and biolog-
ical applications. Particular attention is directed towards the
optimization of its properties through adopting right synthetic
methodologies. The graphene materials prepared through
hydro-/solvothermal routes are demonstrated to show enhanced
performances for many applications including solar cells, photo­
catalysis, Li ion batteries, supercapacitors, fuel cells, sensors
and bioimaging among many others. Future research in the
field should focus on the scale up, robustness, consistency and
study of commercial viability of these promising technologies.
5. Conclusion
Ever since the starting of graphene era, the potential application
window of graphene and of its associated materials is growing
day by day. It already includes flexible touchscreens, ultraca-
pacitors, lithium ion batteries, high frequency transistors, solar
cells, sensors, desalination membranes and biomicrorobotics

Adv. Mater. 2017, 29, 1605473 © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim wileyonlinelibrary.com (28 of 32)  1605473
 www.advmat.de
among others. However the synthetic methodologies of gra-
Review
phene struggle to cope with its growing demands. Although
the hydro-/solvothermal processes have been in practice since
the nineteenth century, it has only been recently recognized
as a versatile and powerful approach in the field of graphene-
based materials and applications. At the current state of gra-
phene research, hydro-/solvothermal methods have several
advantages over conventional wet-chemistry methods, in par-
ticular, because of its industrial compatibility and opportu-
nity to modify the physico-chemical properties of the solvent.
Given the current worldwide concern about a greener chem-
istry, hydro-/solvothermal methods could replace many existing
environmentally unfriendly wet-chemical synthesis methods
for graphene-based materials. The associated temperature and
pressure environment can replace toxic-reducing agents such
as hydrazine and hydrogen iodide to reduce the graphene
oxide with green solvents such as water and/or ethanol. The
use of strong acid mixtures such as nitrating mixture to syn-
thesize graphene quantum dots is not necessary with hydro-/
solvothermal methods. The methods like CVD, hydrazine, and
high temperature annealing processes for N doping of gra-
phene sheets can be replaced by hydro-/solvothermal methods,
as well. In particular, hydro-/solvothermal routes are advanta-
geous in realizing homogenous graphene composites with
polymers, metals, metal oxides, metal sulphides etc., with con-
trollable crystal growth. Hydro-/solvothermal process could
result in versatile interfacial interactions between graphene
and counter components. Significantly, the use of this method
could offer the access to metastable phases of metals, and to
complex hybrid inorganic materials, which combined with gra-
phene could bring new exciting properties and applications.
More specifically, the hydro-/solvothermal route has some
surprising graphitization effect on amorphous carbon, which
would potentially open new routes towards the bottom up syn-
thesis of graphene, even if substantial research has still to be
done in this direction.
Synergic efforts both from the hydro-/solvothermal and
graphene communities are prominent to ensure growth of
this field. This is utmost important since optimization of con-
cepts, improvement of techniques and introduction of new
approaches are necessary for this process to be recognized as
an alternative manufacturing process for graphene. While
understanding of synthetic mechanisms remains challenging
because of sampling difficulty on the course of the reaction, the
new trend of hydro-/solvothermal device designs to temporally
monitor reaction processes is encouraging. Especially such a
monitoring would bring new knowledge and understanding
for the synthesis of graphene-based systems involving graphiti-
zation of carbon, cutting of large graphene sheets down to a
few nanometres dimension, dehydration/deoxygenation of GO
and inorganic crystal growth, etc., which would substantially
enhance its method-optimization and further development. Use
of additional external factors such as high shear mixing, ultra-
sonication, microwave, electrochemical and mechanochemical
are already found advantageous in conventional wet-chemical
solution method. Combining these factors with existing hydro-/
solvothermal techniques would provide an extra hand to con-
trol and vary the reaction conditions during the synthesis pro-
cess. Many of these may seem just hypothetical at this point,
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www.advancedsciencenews.com
but by improving the basic knowledge and setting up new pro-
cesses, they can potentially realize unanticipated results in the
not so distant future. We believe this review will contribute to
this vision, which in fact is valid for two dimensional materials
beyond graphene also.
Acknowledgments
SPS is thankful to University of Bordeaux and the IdEx postdoctoral
fellowship programme. This work has received financial support from
the French State in the frame of the “Investments for the future”
Programme IdEx Bordeaux, reference ANR-10-IDEX-03-02”. The authors
declare no competing financial interest.
Received: October 10, 2016
Revised: November 28, 2016
Published online: February 28, 2017
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