Microchim Acta (2017) 184:1–44

DOI 10.1007/s00604-016-2007-0

REVIEW ARTICLE

Nanocomposites of graphene and graphene oxides: Synthesis,

molecular functionalization and application in electrochemical
sensors and biosensors. A review
Junhui Xu 1,3 & Yazhen Wang 1 & Shengshui Hu 2,3

Received: 29 July 2016 / Accepted: 31 October 2016 / Published online: 12 November 2016
# Springer-Verlag Wien 2016

Abstract Functionalized nanocomposites based on various
type of graphene nanomaterials including graphene, graphene
oxides (GOs), and doped graphene (oxides) are widely used as
materials for various sensors that can display high sensitivity,
selectivity and stability. This review with 347 references sum-
marizes advances in the preparation and functionalization of
graphene nanocomposites for the application of electrochemical
sensors and biosensors. Following a general introduction into the
field, the article is divided into subsections on (a) the synthesis
and functionalization of nanocomposites (made from graphene,
various kinds of GOs, heteroatom-doped GOs), (b) on methods
for functionalization of composites (with other carbon
nanomaterials, metal nanoparticles, metal oxide and metal
sulfide nanoparticles), (c) on functionalization with inorganic
materials including polyoxometalates, hexacyanoferrates,
minerals), (d) on functionalization with organic materials such
as amino acids, surfactants, organic dyes, ionic liquids,
macrocycles (including cyclodextrins, crown ethers and
calixarenes), and (e) on functionalization with organometallics
and with various other organic compounds, (f) on
functionalizations with polymers such as conventional polymers,
polyelectrolytes, conducting polymers, molecularly imprinted
* Shengshui Hu
sshu@whu.edu.cn
1
Key Laboratory of Optoelectronic Chemical Materials and Devices,
Ministry of Education, School of Chemical and Environmental
Engineering, Jianghan University, Wuhan 430056, China
2
College of Chemistry and Molecular Sciences, Wuhan University,
Wuhan 430072, China
3
Key Laboratory of Transducer Technology, Chinese Academy of
Sciences, Beijing 10080, China
polymers, (g) on functionalization with biomolecules including
proteins and nucleic acids. Other subsections cover flexible
graphene and GO based nanocomposites and 3D composites.
Application of graphene and GO nanocomposites are then
covered in a in large section that comprises electrochemical
sensors and biosensors (based on voltammetry, amperometry,
potentiometry, impedimetry, electrochemiluminescence,
photoelectrochemistry, field effect transistors, electrochemical
immunosensors) with specific subsections on gas sensors,
enzymatic biosensors and gene sensors. A concluding
section covers current challenges and perspectives of graphene
and GO based (bio)sensing.
Keywords Nanoparticles . Nanosheets . Sensing
nanocomposites . Quantum dot . Functionalized graphene .
Modified electrode
Introduction
Since Novoselov’s Bgroundbreaking experiments regarding
the two-dimensional material^ in 2004 [1], tremendous re-
search efforts have been devoted to the study and applications
of graphene and graphene-based materials. Graphene is an
indefinitely extended two-dimensional (2D) carbon crystal,
in which carbon atoms are packed in a hexagonal lattice re-
sembling a honeycomb [2]. Graphene exhibits a variety of
intriguing properties including large specific surface area,
high transparency, excellent mechanical strength and flexibil-
ity, strong ambipolar electric field effect, good thermal and
electrical conductivity as well as superior electronic properties
[3]. These outstanding properties have aroused growing
interest in touch screens, capacitors, spintronic devices, fuel
cells, batteries, sensors, transparent conductive films,
2 Microchim Acta (2017) 184:1–44
high-frequency circuits, toxic material removal, and flexible
electronics [4, 5].
According to the definition recommended by the
International Union of Pure and Applied Chemistry
(IUPAC), graphene is Ba single carbon layer of graphite struc-
ture, describing its nature by analogy to a polycyclic aromatic
hydrocarbon of quasi-infinite size^ [6]. However, such defini-
tion is not strictly adhered in the current research, the concept
of graphene has been extended to a series of graphite materials
that consisting of one or more graphene layers and large
amount of sp3-hybridized carbon defects or physical holes in
the structure [7]. Here, we follow this trend of referring all
pristine graphene-related materials as Bgraphene (GR)^ when
discussing the materials collectively and will attempt to be
more specific in the discussions of certain individual cases.
Graphene can be synthesized by either Btop-down^ or
Bbottom-up^ approaches [8–10]. Figure 1 gives an intuitive
comparison for the main possible approaches [9]. Generally,
the top-down approaches involve the exfoliation of graphite as
starting material through mechanical (e.g., Scotch tape),
chemical (e.g., solution-based exfoliation, graphite oxide ex-
foliation/reduction), or electrochemical processes (oxidation/
reduction and exfoliation), which aim at weakening the van
der Waals forces between the graphene layers. Preparation of
graphene by opening/unzipping carbon nanotubes can be
Fig. 1 Illustration of the main possible Btop-down^ or Bbottom-up^
approaches: (1) Oxidation of graphite to graphite oxide. (2) Step-wise
exfoliation of graphite oxide. (3) Reduction of graphene oxide. (4)
Mechanical exfoliation of graphite to give graphene. (5) Oxidation of
ascribed to a special category of process under the top-down
approach. On the other hand, the bottom-up approaches gen-
erate graphene by assembling small molecular building blocks
into single or few layer graphene structures by means of
catalytic (e.g., chemical vapor deposition (CVD)), thermal
(e.g., SiC decomposition), or chemical (organic synthesis)
processes [7, 9]. Among all these methods, the solution-
based chemical exfoliation of graphite stands out as the pri-
mary strategy that can yield large amounts of graphene suit-
able for further molecular functionalization. Graphene oxide
(GO), the most common product obtained through graphite
oxide exfoliation-chemical route, possesses plentiful defects
and oxygen-containing groups (epoxy, carboxyl, and hydrox-
yl groups), which can not only act as catalytical active centers
in electrochemical process but also provide anchoring sites for
covalent or non-covalent functionalization [10]. However, GO
tends to be insulating due to the disruption of the sp2 bonding
networks. The reduction of GO to reduced-GO (rGO) is a
required deoxygenation treatment in order to recover the orig-
inal properties and attain materials that resembles pristine
graphene to certain extent, which can be easily realized before
or after functionalization via thermal, chemical or electro-
chemical procedures [11].
Despite the great application potential, it is broad consen-
sus that graphene needs to be functionalized by functional
graphene sheets to graphene oxide. (6) Thermal decomposition of an
SiC wafer. (7) Growth of graphene films by chemical-vapor deposition.
Reprinted with permission from Ref [9]. Copyright (2012) Elsevier
Microchim Acta (2017) 184:1–44
materials. Functional materials are generally characterized as
those materials which possess particular native properties and
functions of their own. Functional materials are found in all
classes of materials such as metal and metal oxide nanoparti-
cles, polymers, organic and biological molecules. These func-
tional materials or functional molecules are often used in the
application of chemically modified electrode to improve or
even gain sensing capabilities for special electroanalytical pur-
pose. Molecular functionalization of graphene with different
functional materials provides the possibility to finely tune the
material’s chemical and physical properties, resulting in a com-
bination of the individual properties of the each component
material. For example, introduction of water soluble additives
can bring better aqueous dispersibility that favorable for the
preparation of film modified electrode [12]; decoration with
polyelectrolyte can greatly enhance the adsorption capacity to
oppositely charged species [13]; combination with metal nano-
particles (NPs) can endow graphene nanocomposite selective
catalytical activity to special small molecules [14]; conjunction
with biologic recognition elements can help capture the targets
and assist in signal transduction [15]; integration with transpar-
ent plastics may result in wearable photosensitive electrochem-
ical sensors [16], and so on. As a promising electrode material,
graphene nanocomposite possesses the virtue of good stability,
low over potential, wide potential window, negligible residual
current as well as excellent electrocatalytic activity, which is
favorable for the rational design of high-performance electro-
chemical sensors and biosensors [3–5, 7–10].
In the past several years, many reviews covering graphene-
based electroanalytical applications have been published
[17–23]. For example, our group has reviewed the electrochem-
ical sensors based on graphene materials, highlighting the im-
portant applications of graphene and its nanocomposites in
electroanalytical chemistry [21]. We also summarized the main
electrochemical applications of graphene in the field of diagno-
sis analysis, drug analysis, food analysis and environmental
analysis [22, 23]. In this article, we will survey the recent im-
portant advances on graphene nanocomposite based electro-
chemical sensors and biosensors. Firstly, the functional mate-
rials and operational procedures employed for the synthesis and
molecular functionalization of graphene nanocomposite are
summarized. Then, some new significant developments in their
analytical practice based on various electrochemical techniques
are discussed. Finally, we conclude with a look at the current
challenges and future prospects of graphene nanocomposite
based electrochemical sensors and biosensors.
Synthesis and molecular functionalization of graphene
nanocomposite
GO is the preferred starting materials for the design of graphene
nanocomposite based electrochemical sensors and biosensors
owing to its good water solubility and a large number of
3
oxygen-containing groups, which makes it easy to modulate
the electrode’s structural architecture and intrinsic properties
by either covalent or non-covalent functionalization of GO
[10]. Generally, the covalent functionalization involves the for-
mation of covalent bonds, including: substitute of carbon atoms
in the basal plane of graphene by heteroatoms, addition of free
radicals to C = C bonds of graphene and reaction between or-
ganic functional groups and the oxygen-containing functional
groups of GO [4]. On the other hand, non-covalent
functionalization is often realized by intermolecular interactions
such as π-π stacking, anion-π interaction, hydrophobic interac-
tion and hydrogen bond. Compared with covalent
functionalization, non-covalent functionalization has the advan-
tage that functional groups could be introduced into graphene
without affecting its structure and electronic network, so that the
novel properties of graphene are retained [5]. In most cases, the
stable binding of functional material with graphene comes from
the synergistic effect of several above driving forces [3–5].
Based on the aforementioned bonding or interaction,
graphene nanocomposite can be obtained via several techniques.
Among all techniques, mechanically mixing is the simplest one.
Functional materials can combine with graphene by hand grind-
ing [24], electromagnetic stirring or ultrasonic mixing in solu-
tions [25], and sometimes with the aid of refluxing or heating
[26]. A more controllable strategy is to synthesize functional
materials in the presence of graphene. During the reaction, pro-
duction of functional materials can occur at the active sites on
the surface of graphene with designable features and distribu-
tion, which is often described as in-situ functionalization meth-
od. Electrodeposition is a special synthetic method to obtain
graphene nanocomposite. Functional materials can be electro-
chemically deposited on to graphene [27] or co-deposited with
graphene [28] from solution containing precursors. Since the
graphene nanocomposite is directly deposited onto the electrode
surface, no further transfer steps are needed for the preparation
of modified electrode. In the case of covalent functionalization,
pretreatment of graphene oxide is usually necessary in order to
enhance the abundance of reactive oxygen containing groups
[29]. If amidation reaction is expected, carboxyl groups on
graphene are routinely activated by N-hydroxysuccinimide
(NHS) –ethyl (dimethylaminopropyl)carbodiimide (EDC) pro-
cedure [30].
According to the architectures, the graphene based nano-
composites can be mainly classified into two types as illustrat-
ed in Fig. 2: graphene supported functional materials and
graphene dispersed in functional materials. Most graphene
based nanocomposites belong to the former type, including
various materials decorated, grafted or wrapped graphene. If
polymerization, electrodeposition and sol-gel process is
employed, the resulting nanocomposites often show a feature
of the latter. Prior to electroanalytical applications, the
graphene based nanocomposites are always characterized to
fully understand the structural and chemical properties. More
4 Microchim Acta (2017) 184:1–44
Fig. 2 Illustration of two types of
graphene based nanocomposites:
a graphene supported functional
materials and b graphene
dispersed in functional materials
specifically, atomic force microscopy (AFM) is most reliable
to quantify the thickness of graphene sheets. Scanning tunnel-
ing microscopy (STM) can be used to visualize the carbon
atoms in graphene structures, even allowing the identification
of defects. Scanning electron microscopy (SEM), transmission
electron microscopy (TEM) and High-resolution TEM
(HRTEM) are powerful imaging tools to characterize the mor-
phology and structural features. Energy dispersive X-ray
(EDX) spectroscopic measurement is often employed to ana-
lyze the elemental composition. X-ray photoelectron spectros-
copy (XPS) can be used to evaluate the atomic compositions
and oxidative states of the available elements. The crystal struc-
tures can be characterized by X-ray diffraction (XRD) spectros-
copy. Raman spectroscopy can give information on structural
features, density of defects, and the number of graphene layers.
Fourier transform infrared spectroscopy (FTIR) and UV-VIS
absorption spectroscopy are often applied to investigate the
functional groups and covalent bonding. Electrochemical im-
pedance spectroscopy (EIS) can be utilized to study the con-
ductivity and interfacial charge transfer characteristics.
Generally, these characterizations can provide sufficient infor-
mation about the nanocomposite, but in some cases, other tech-
niques are also employed to acquire special details as needed.
Numerous works have demonstrated that graphene is an ex-
cellent material for the immobilization of functional materials
due to its unique and advantageous physicochemical properties.
Combining the advantages of both graphene components and
the functional materials, the graphene based nanocomposites
possess enhanced stability, improved electrical conductivity
and electron mobility, as well as high available surface area for
analyte binding. These nanocomposites can significantly lower
the over-potentials and facilitate the electron transfer between
the analyte and the electrode surface, which play key roles in the
design of high performance electrochemical (bio)sensors. To
date, a broad range of functional materials have been reported
for the construction of graphene nanocomposite based electro-
chemical sensors. In this section, we will discuss six categories
of the functional materials involved in synthesis and molecular
functionalization of graphene nanocomposite, including hetero-
atoms, nanomaterials, inorganic materials, organic materials,
polymers and biomaterials. In addition, considering the growing
interest in flexible and three dimensional (3D) sensors, we will
give a brief description of the advances in flexible and 3D–
structured functionalized graphene nanocomposite.
Heteroatom-doped graphenes
Doping with heteroatoms is an effective way to adjust the elec-
tronic, mechanical properties and electrochemical activities of
graphene [31, 32]. Generally, the doped heteroatom should have
similar atomic structure and electronegative feature with carbon.
Therefore, nitrogen and boron are considered as the best candi-
dates for the doping of graphene. For example, Shi [33] prepared
N-doped graphene nanoribbons (N-GNRs) by unzipping carbon
nanotubes (CNTs) under strongly oxidizing conditions and sub-
sequent doping with nitrogen by a low-temperature hydrother-
mal method. Compared to common nitrogen plasma treatment
and chemical vapor deposition, this doping procedure was car-
ried out at a very low temperature (80 °C), and can be utilized to
adjust the electronic structure of graphene materials with en-
hanced electrochemical properties. Ma [34] synthesized N-
doped graphene (N-GR) through a one-step electrochemical
strategy at room temperature. In general, GO was dispersed in
NH4Cl-NH3 buffer solution and deposited on the working elec-
trode at a constant cathodic potential. The doping process oc-
curred at the active sites generated from the electrochemical
removal of oxygen containing groups, and the product mainly
contained pyridine- and pyrrole-like N atom. Since the electro-
negativity of nitrogen is larger than that of carbon, local charge
polarization on adjacent carbon atoms may formed, which can
facilitate the electrocatalytic reduction of oxygen.
Yeh [35] reported the preparation of B-doped graphene by
an atmospheric-pressure carbothermal reaction. Typically,
B2O3 was melted and vaporized, and B-doped graphene was
obtained when boron atoms replaced carbon atoms within
graphene structures at high temperature. The original defects
in the graphene framework may provide active sites for boron
doping. Boron dopant can create more defects, which not only
act as the electrocatalytic sites by transferring charges to neigh-
bor carbon atoms, but also facilitate the aqua electrolyte pene-
trating into the porous structure through the hydrophilic sur-
face. The resulting B-doped graphene exhibited outstanding
Microchim Acta (2017) 184:1–44
electrocatalytic ability for the reduction of H2O2 and can act as
a noble-metal free catalyst for its electrochemical detection.
Sulfur atom also has similar electronegative feature with
carbon and can be applied for the chemical modification of
graphene. Tian [36] introduced a simple procedure for the syn-
thesis of S-doped graphene. GO and benzyl disulfide was dis-
persed in ethanol, the mixture was first ultrasonicated and then
treated in a microwave oven. Raman spectroscopy results sug-
gested that the S-doping may lead to the lattice distortion and
produce additional defect sites in graphene networks. Though
S-doped graphene alone shows poor catalytic activity, the
doped sulfur heteroatoms strongly boost the electrocatalytic
activity of graphene nanocomposites by enhancing the interac-
tions between metal or metal oxide and S-doped graphene.
Heteroatom doping can endow graphene with various new
physicochemical and structural properties, greatly extends the
applications of graphene in electrochemical analysis field.
The heteroatom-doping of graphene with N, B and S can
create active sites, which can consequently enhance the adsorp-
tion and activation of analytes, promote charge transfer and
facilitate further modification with functional moieties, resulting
in improved performance when being used for the construction
of electrochemical sensors. However, since the doping status
significantly affects the properties, the synthesis parameters
should be strictly controlled to guarantee the doping efficiency
and minimum the influence of different doping structures.
Functionalization of graphene with nanomaterials
Few years ago, the association of nanomaterials such as noble
metal nanoparticles to graphene sheets was still an unexplored
area of research. Now, this kind of research has become a hot
topic and achieved remarkable results. The nanomaterial-
graphene composites have been tested very widely, here sev-
eral important nanocomposites of graphene and nanomaterials
(carbon nanomaterials, metal nanoparticle, metal oxide nano-
particle, magnetic nanoparticles, and metal sulfide nanoparti-
cle) are discussed.
Carbon nanomaterial-graphene nanocomposites
Carbon nanomaterials play an important role in the field of
electrochemical sensing, and combining between various car-
bon nanomaterials seems very attractive. Among all carbon
nanomaterials, CNTs have received the most considerable at-
tention during the first decade of twenty-first century due to
there overwhelming advantages in fabricating electrochemical
sensors [37]. The combining between one-dimensional CNTs
with two-dimensional has drawn the most attention. For ex-
ample, Han [38] prepared CNT-GO hybrids by treating the
mixture of pristine CNTs and GO suspension with the aid of
ultrasonication. Due to the strong π-interaction between the
surface of CNTs and π-conjugated multiple aromatic domains
5
of GO, CNTs were completely disentangled and adhered to
the surface of the GO. Compared with the acid-treated CNTs
and GO, the CNT-GO showed better electrocatalytic ability
for the oxidation of tryptophan. Zhu [39] described the syn-
thesis of GNR/CNT by partially unzipping of CNT and sub-
sequent chemical reduction with hydrazine. The GNR struc-
tures were appeared on the side of nanotubes, and the central
cores of nanotubes remained tube-like structure, indicating a
core-shell heterostructure. The synergistic effects of the CNT
and the GNR resulted in a distinctly improved redox current
towards p-dihydroxybenzene (DHB).
Fullerene C60 (C60) is a closed hollow cage made of 60
sp2-hybridized closely packed carbon atoms into fused hexa-
gons and pentagons without any edges. Due to its ability to act
as an electron acceptor, C60 has attracted numerous interests
for electrocatalytic analysis. Our group [24] presented a facial
way to prepared C60 functional graphene by simply grinding
the mixture of C60 and GO in an agate mortar. The resulting
black-brown colloidal powder was readily dissolved in water
under ultrasonication. Due to the stable π-interaction, C60
molecules can insert into GO, which can prevent the aggrega-
tion of both C60 and GO. As a result, the good dispersibility of
C60-GO nanocomposite in water was achieved. The water-
soluble nanocomposite was easy to be further functionalized
for sensing application. Taking into account the adsorption
and interaction of several kind of molecules on graphene with
different strength of surface molecule interaction, Merino
studied weakly interacting molecule C60 [40] and on the other
highly interacting ones, as atomic H atoms or covalent linked -
conjugated polymers of electron donor moieties [41].
Carbon dots are novel Bzero-dimensional^ carbon
nanomaterials with the advantage of biocompatibility, cyto-
toxicity and good oxidation-reduction performance.
Similarly to C60, carbon dots can also effectively prevent the
aggregating of graphene. Hu [26] placed the mixture suspen-
sion of carbon dot and GO into a Teflon-lined stainless steel
autoclave under heating. In this case, GO was reduced to rGO
by carbon dots and carbon dot-rGO composite was obtained.
The composite can provide abundant carboxyl groups at sur-
face as well as act as barriers to prevent the interferences from
other substances, which endows the carbon dot-rGO based
dopamine sensor with high sensitivity and good specificity.
Nanodiamonds are another kind of Bzero-dimensional^
carbon nanomaterials that exhibit most of the unique proper-
ties of bulk diamond with good chemical stability and huge
surface area. They are sometimes considered to have a core-
shell architecture based on a diamond core (sp3 carbon atoms),
a middle layer (sp2+x carbon atoms), and a graphitic outer shell
(sp2 carbon atoms) with dangling bonds terminated by func-
tional groups [42]. Dong [43] developed a procedure to pre-
pare core-shell-structured nanodiamond/N-doped-graphene
composite. The nanodiamond powder was annealed in vacu-
um at first, then refluxed in mixed concentrated sulfuric acid
6 Microchim Acta (2017) 184:1–44

and nitric acid, and finally treated with the N-doping process. Table 1 Relevant information dealing with the preparation and the
electroanalytical application of metal NP-graphene nanocomposites
Raman spectra and HRTEM suggested that a multi-layer epi-
taxial graphene was formed on the surface of nanodiamond, Materials Methods Analytes Ref.
leading to a nanodiamond core/graphene shell structure. The
nanodiamond/N-doped graphene composite showed similar Pt/GR chemical reduction H2O2 [14]
oxygen adsorption mechanism to Pt electrocatalysts and ex- Pt/rGO chemical reduction glucose [46]
hibited excellent catalytic activity for the electrochemical re- Au/rGO chemical reduction melamine [47]
duction of oxygen. Au/rGO chemical reduction glucose [48]
Decoration of graphene by other carbon nanomaterials has Au@Pt@Au/GO chemical reduction H2O2 [49]
given rise to new physical properties through cooperative and Pd/GO chemical reduction paracetamol [50]
synergetic effects, and the functionalized composites have Ag-Pd/GO chemical reduction vanillin [51]
found more applications in electrochemical sensing fields Ag/rGO chemical reduction H2O2 [52]
where they were previously less competitive. Bi/rGO chemical reduction Fe(III) [53]
Ni/PANI/rGO chemical reduction glucose [54]
Metal nanoparticle-graphene nanocomposites Ag/GO spontaneous redox reaction H2O2 [55]
Pt3Pd/rGO spontaneous redox reaction glucose [56]
Metal nanoparticles (NPs) are often employed in the construc- Au/rGO photochemical reduction trinitrotoluene [57]
tion of electrochemical sensors due to their special catalytical Pd/GO-CNT photochemical reduction glucose [58]
activity. Introduction of metal nanoparticles onto graphene Co/GO electrodeposition N2H4 [59]
can effectively exploit the unique virtues of both the two ma- Ag/GR electrodeposition guanine, adenine [60]
terials and has drawn increased interest in sensing field. Metal Bi/rGO electrodeposition glucose [61]
NPs functionalized graphene can not only exert the maximum Ni/rGO electrodeposition dopamine [62]
availability of the nanoscale surface area for electron transfer, Au-Pd/GO electrodeposition organophosphate [27]
but also facilitate mass transport of the reactants to the Pt-Au/rGO electrodeposition H2O2 [63]
electroactive centers on the electrode surface, leading to the Au/rGO mechanically mixing H2O2 [64]
significantly enhanced electrochemical response [5, 44, 45]. Pd/rGO mechanically mixing dopamine [65]
Metal NP-graphene nanocomposites can be obtained by Pt/GO-CNT covalently linking cTnI [66]
chemical [14, 46–56], photochemical [57, 58] or electrochem-
ical [27, 59–63] reduction of metal ions at the presence of GO,
as well as mechanically mixing [64, 65] or covalently linking sodium citrate and HAuCl4 solution were added by turn to
[66] metal NPs with graphene. Relevant information dealing obtain Au@Pt@Au/GO. EDX spectroscopy confirmed the
with the preparation of metal NP-graphene nanocomposites formation of Au@Pt@Au/GO bimetallic nanocomposites,
and their electroanalytical application is presented in Table 1. while XRD spectroscopy demonstrated that the Au@Pt@Au
In situ chemical growth is the primary method for the fab- had a face-centered cubic structure. The nanocomposite
rication of metal-graphene nanocomposites. For example, showed unusual bi-electrocatalytic activity toward the oxida-
Guo [14] described a PtNPs ensemble-on-graphene through tion and reduction of H2O2.
a one-step procedure. Typically, water/ethylene glycol (EG) Pd has drawn much more attention than Pt and Au due to
mixture of graphene oxide, Pt precursor and poly(methacrylic their higher abundance and lower cost. Li [50] slowly added
acid sodium salt) (PMAA) was placed for microwave oven for NaBH4 solution to the mixture suspension of GO and PdCl2
a certain time. Herein, EG was used as a reducing agent for the under vigorous stirring. Therefore, Pd/GO nanocomposite
production of both PtNPs and rGO. The PtNPs on rGO had was obtained. HRTEM images confirmed that highly dis-
small size, uniform distribution and controllable high-metal- persed PdNPs with the size of 5 ~ 10 nm were firmly anchored
loading level, and the resulting nanocomposites showed at- on the surface of GO. The Pd/GO nanocomposite exhibited
tractive electrocatalytic activities toward several organic and good electrocatalytic activity towards the oxidation of para-
inorganic electroactive compounds. Bimetallic NPs are attrac- cetamol and was applied for its sensitive electrochemical de-
tive because of their peculiar catalytic behavior with respect to termination. Li [51] also reported a green and inexpensive
monometallic systems. Li [49] illustrated the preparation of approach for the preparation of bimetallic Ag-Pd NPs deco-
bimetallic Au@Pt@Au core-shell NPs functionalized rated graphene. Here, polyethylene glycol was employed to
graphene. At first, AuNPs were grown on GO by the redox reduce the mixture solution of GO, Pd2+ and Ag+ in situ with-
reaction between HAuCl4 and GO at boiling point. Next, out employing any other surfactants and templates. EDX spec-
AgNO3 and sodium citrate solution were added by turn to tra showed that the loading of Ag-Pd on GO sheet surface was
obtain Ag@Au/GO. Then H2PtCl6 solution was added to get so high that the mass percent of Ag-Pd bimetal in nanocom-
Ag@Au/GO by a galvanic replacement. At last, AgNO3, posite was 45.77 %. Due to its large surface area, excellent
Microchim Acta (2017) 184:1–44
conductivity and catalytical activity, the nanocomposite pos-
sessed synergetic catalytic effect on the oxidation of vanillin.
Noor [55] described the synthesis of Ag/GO nanocompos-
ite without any additional reductant or surfactant, where Ag+
was reduced to Ag with the aid of strong ultrasonic irradiation
and GO provided a high surface area with large number of
functional groups for the stabilization of AgNPs. Zhao [56]
prepared Pt-Pd NPs supported on rGO spontaneous redox
reaction by using rGO as a reductant. The TEM and
HRTEM images revealed that dense and homogeneous metal
NPs with an atomic ratio of Pt:Pd at about 3:1 were well
dispersed on the rGO sheets, and it seemed that the PtNPs
were assembled around the PdNPs. The nanocomposite was
expected to exhibiting better catalytic activity than monometal
catalyst, resulting in an ultrasensitive approach for sensing
glucose even at near-neutral pH values.
Photochemical reduction is a Bgreen^ and reductant-free
technique for the reduction of graphene oxide. Wang [57]
reported a novel procedure for the synthesis of Au/rGO nano-
composite by UV light irradiation. After being exfoliated un-
der strong ultrasonication, GO dispersion was mixed with N-
hexadecyltrimethylammonium chloride and chloroauric acid,
and then the mixture was irradiated for 5 h with the aid of
mercury lamp under continuous stirring. TEM images showed
that high-density AuNPs with diameters of about 25 nm were
uniformly dispersed on the rGO. During the UV irradiation
process, photo electrons was excited which caused the reduc-
tion of Au(III) to Au(0), while the irradiation caused the de-
tachment of oxygen-containing functional groups, leading to
the reduction of GO. However, the UV irradiation synthesis is
somewhat time-consuming. Nayak [58] presented a rather
rapid decoration of metal NPs over GO-CNT by using focused
sun light as the energy source. Briefly, a fine mechanical mix-
ture of purified GO-CNT and palladium chloride was irradiat-
ed for 1 ~ 2 min by focused sun light using a convex lens. The
rapid heating by lens created sudden rise in temperature,
which decomposed the metal salt to metal NPs and simulta-
neously deposited on GO-CNT.
Electrodeposition is another efficient way to anchor metal
NPs to graphene surface. For example, He [59] described a
interest method for the electrodeposition of Co/GO by succes-
sive cyclic scans in GO-Co(Ac)2 mixed dispersion under irri-
tation of ultrasonic waves. SEM images showed that the
resulting nanocomposites had hierarchical cobalt (Co)-
nanoflowers on petalage-like graphene structure. Here,
ultrasonication is essential to the formation of special
flower-like feature, which can provide an increased mass
transport regime and may change the reaction kinetics as well
as on the deposits in terms of appearance, adherence and grain
morphology. Electrodeposition can also be employed to form
bimetallic NPs functionalized graphene. Zhan [27] treated
graphene modified electrode in mixed solution of HAuCl4
and PdCl2 under a constant potential, the Au-Pd NPs appeared
7
at the graphene surface with fairly even, ordered and close-
packed distribution. The bimetallic NPs played an important
role similar to the electron conducting tunnel, and showed
superior electrochemical performance in comparison with that
of NPs alone.
Mechanically mixing is a simple way to prepare metal NP-
graphene nanocomposites. Since metal NPs and graphene sus-
pensions are synthesized individually in advance, the ratio of
the two components can be precisely controlled. For instance,
AuNPs [64] and Pd nanocubes [65] were decorated onto the
graphene surface uniformly by ultrasonicating the mixed so-
lution or grinding the mixed slurry containing metal particles
and graphene. Signal [66] demonstrated the covalently linking
of PtNPs to GR-CNT surface. Prior to the attachment, GR-
CNT was functionalized with pyrenemethylamine through π-
stacking. Then, mercaptopropionic acid capped PtNPs were
modified onto GR-CNT via amidation with the help of EDC-
NHS system. The resulting Pt/GR-CNT nanocomposite com-
bined the advantages of large surface area of the GR-CNT and
ultra-high density of active graphene edge planes together
with high surface to volume ratio of electroactive PtNPs,
which was further employed for the construction of a sensitive
impedimetric cardiac troponin-I (cTnI) sensor.
Until now, most works about metal NP-graphene nano-
composite based electrochemical sensors are concerned with
noble metals, though a few reports on non-precious metal can
be traced. The synergistic electrochemical characteristics of
the metal NP-graphene are attributed to the large surface area,
high conductivity, low interfacial resistance, facilitated elec-
tron transfer, and special catalytical activity. Metal NP/
graphene nanocomposites can not only act as excellent elec-
trochemical sensing materials, but also provide ideal matrix
for the immobilization of enzyme and DNA, enabling the
design of highly selective and sensitive electrochemical
biosensors.
Metal oxide nanoparticle-graphene nanocomposite
Metal oxide NPs have received extensive attention in analysis
field due to their unique advantages of good biocompatibility,
easy preparation, high adsorption ability and catalytical activ-
ity [5, 44, 45]. Metal oxide-graphene nanocomposites are ex-
pected to exhibit excellent material properties of parent com-
ponents and become promising electrode materials. Metal ox-
ide NPs are usually deposited onto GO sheets via hydrother-
mal growth [67–72], chemical reduction [73–79], or electro-
deposition [80–84] in solutions containing metal ions precur-
sors. Mechanically mixing [85] is also effective approach to
prepare metal oxide-graphene nanocomposites. Table 2 lists
relevant information dealing with the preparation of metal
oxide NP-graphene nanocomposites and their electroanalyti-
cal application.
8 Microchim Acta (2017) 184:1–44

Table 2 Relevant information

dealing with the preparation and Materials Methods Analytes Ref.
the electroanalytical application
of metal oxide NP-graphene ZnO/GR hydrothermal growth H2O2 [67]
nanocomposites ZnO/rGO hydrothermal growth nitrite [68]
CeO2/GO hydrothermal growth thymol [69]
Ag/CeO2/rGO hydrothermal growth H2O2 [70]
Ag/Co3O4/rGO hydrothermal growth H2O2 [71]
Y2O3/N-rGO hydrothermal growth L-cysteine [72]
SnO2/rGO spontaneous redox reaction humidity [73]
Cu2O/rGO chemical reduction ascorbic acid [74]
Cu2O/rGO chemical reduction glucose [75]
Au-SnO2/rGO chemical reduction epinephrine [76]
Au-MnO2/CNT-GO chemical reduction dopamine [77]
Pd-CuO/rGO chemical reduction glucose [78]
Co(OH)2-Cu2O/rGO chemical reduction caffeine [79]
MnO2/rGO electrodeposition norepinephrine [80]
NiO-CuO/GR electrodeposition acetaminophen [81]
ZrO2/GO electrodeposition methyl parathion [82]
CoOx/rGO electrodeposition glucose [83]
CuOx-CoOx/rGO electrodeposition glucose [84]
SnO2/rGO mechanically mixing dopamine [85]

Low [67] prepared ZnO-graphene nanocomposite by hy-
drothermal method. Briefly, graphene oxide and zinc nitrate
were dispersed in ethanol and the solution pH value was ad-
justed to 12 by hydroxide solution. The mixture was then
heated in Teflon stainless steel autoclave at 90 °C. SEM im-
ages confirmed that ZnO NPs formed on the graphene surface
were spherical in shape with diameter around 200 nm. The
resulting hybrids exhibited excellent electrocatalytic activity
to the reduction of H2O2. Zhao [69] reported the synthesis of
CeO2-graphene via similar route. SEM images illustrated that
well-dispersed CeO2 NPs with a diameter of 10 nm were
deposited onto graphene surface. The graphene sheets stabi-
lized the CeO2 NPs while the CeO2 NPs prevented the GR
from aggregating and restacking.
Chen [73] developed a friendly green method to prepare
SnO2-rGO hybrid. GO suspension was mixed with desired
amount of tin power and the solution was then conditioned
at 85 °C under stirring. Different from the hydrogen spillover
mechanism, the GO was directly reduced by the Sn powder
and no acid was needed. During the redox reaction, Sn was
transformed to small SnO2 nanocrystals and anchored to rGO
surface. HRTEM images showed that these small SnO2 crys-
tals aggregated to form round SnO2 NPs with diameters of
about 45 nm. Dhara [78] demonstrated the synthesis of nano-
composite consisting of rGO decorated with palladium-
copper oxide NPs (Pd-CuO/rGO) via single-step chemical
reduction by using NaBH4 as the reductant. PdNPs with a
diameter of about 10 nm and elongated CuO NPs (about
80 nm in length) were uniformly dispersed on the rGO matrix.
Compared with the Au-NiO/rGO, Au-CuO/rGO and Pt-CuO/
rGO nanocomposites, the Pd-CuO/rGO showed better sensing
characteristics for the determination of glucose.
Electrodeposition is a powerful approach to form metal
oxides-graphene nanocomposite. For example, Vilian [80] de-
scribed the preparation of MnO2/GO via electrodeposition.
Typically, GO modified electrode was performed consecutive-
ly for two cycles in a potential range of 0.5 V to −0.3 V in
KMnO4 and H2SO4 aqueous solutions. The oxygen contain-
ing groups in GO were expected to direct the deposition of
MnO2 NPs due to the hydrogen bonding or dehydration reac-
tions. EDX spectra indicated that the deposition rate of MnO2
was very high, which was beneficial to improve the electro-
catalytic activities. Liu [81] presented the co-deposition of
NiO and CuO NPs onto graphene via successive cyclic
voltammetric (CV) scans in aqueous solution containing Cu
(NO3)2 and NiCl2. SEM images illustrated that the NiO-CuO
deposited on the surface of graphene had a quasi-nanosphere
feature. The resulting composites exhibited excellent electro-
catalytic performance and were applied for the simultaneous
determination of dopamine, acetaminophen and tryptophan.
Du [82] presented the synthesis of ZrO2-graphene nanocom-
posite by one-step electrodeposition. Typically, a mixture so-
lution of ZrOCl2, rGO and chitosan was applied to a pre-
anodized GCE and electrochemically deposited by consecu-
tive CV scans. SEM images demonstrated that the graphene
layers rolled up like flowers, in which wrapped ZrO2 NPs with
an average size of 50 ~ 80 nm. The resulting nanocomposite
combined the large surface area and the fast electron-transfer
Microchim Acta (2017) 184:1–44
of graphene with the strong affinity of ZrO2 to the phosphate
group, leading to synergistic enhancing effect for the electro-
chemical reduction of methyl parathion.
Magnetic nanoparticle-graphene nanocomposites
Magnetic NPs (MNPs) have been actively purchased to en-
hance the sensitivity and the stability of sensors and biosen-
sors due to their own advantages such as supermagnetism,
biocompatibility, high mass transference, and ease of prepara-
tion [86, 87]. The combination of MNPs and graphenes has
developed into an emerging interdisciplinary research area
and will enlarge the application span of each family of mate-
rials because of the existence of some synergistic effects [88].
Many works have managed to functionalize graphene with
MNPs for electroanalytical purposes.
Among all kinds of MNPs, Fe3O4 MNPs is the most stud-
ied one since its intrinsic peroxidase mimetic activity offers
potentials for cathodic electroanalysis with minimized inter-
ference. In situ chemical co-precipitation of Fe2+ and Fe3+ at
the presence of GO is the classic method for the preparation of
MNP-graphene nanocomposites, where NaOH [89] and am-
monia [90, 91] often acted as the precipitator. A modified
procedure involves the partial reduction precipitation of Fe3+
to Fe3O4, while GO is reduced to rGO at the same time.
Bagheri [92] prepared Fe3O4-graphene nanocomposite by
adding hydrazine hydrate to the mixture solution of GO,
Fe3+ and ascorbic acid under stirring. SEM images showed
that Fe3O4 NPs were well-distributed and strongly anchored
on the surface of graphene. The deposited Fe3O4 NPs facili-
tated the electron transport, which significantly improved the
electrochemical performance in the oxidation of melatonin
and dopamine. Wang [93] described the solvothermal synthe-
sis of Fe3O4/rGO by heating mixture solution of GO, Fe3+ and
ethylene glycol. Similarly, Liu [94] prepared MNP-graphene
by using diethylene glycol as the reductant. The resulting
nanocomposite was employed as carriers for the capture
Fig. 3 Schematic of the
preparation process for 3D rGO
Fe3O4-Pd nanohybrids. Reprinted
with permission from Ref [95].
Copyright (2015) American
Chemical Society
9
DNA, which not only promoted washing after synthesis, but
also facilitated the electronic transfer due to their excellent
biomagnetic separation capability and electrical properties.
Zheng [95] synthesized 3D graphene nanohybrids with in
situ-formed Fe3O4 NPs and PdNPs on it by the one-pot
solvothermal method, which had intrinsic oxidase-like and
oxidase activity. During the preparation process, 3D rGO
sheets and partial magnetite were used as supporters for the
in situ growth of PdNPs, and L-glutamic acid served as a
linker between PdNPs and Fe3O4 NPs (Fig. 3). Besides
Fe3O4, other MNPs were also studied for the functionalization
of graphene. Afkhami [96] demonstrated the hydrothermal
synthesis of NiFe2O4-GO nanocomposites. The combination
of graphene and NiFe2O4 NPs remarkably improved the elec-
tron transfer kinetics of tramadol and acetaminophen as well
as significantly lowered their over potentials, leading to a con-
siderable enhancement in sensitivity, repeatability and repro-
ducibility in their simultaneous determination.
Covalently cross-linking is also an efficient way to attach
MNPs onto graphene. Roy [97] conjugated rGO with silane
group modified MNPs, which was further reacted with a new
rGO sheet to form an rGO dendrite type of structure. The
nanocomposite showed good magnetic susceptibility
(180.2 emu·g−1) as well as excellent electrochemical behavior
towards ferrocyanide probe molecule, and was applied as a
substrate of molecularly imprinted polymer for the electro-
analysis of europium metal ion. Sun [98] combined meso-
2,3-dimercaptosuccinnic acid (DMSA)-modified Fe3O4 NPs
with polyethyleneimine (PEI)-functionalized rGO via forma-
tion of amide bonds between COOH groups of DMSA and
amine groups of PEI in the presence of 1-ethyl-3-(3-
dimethylaminopropyl) carbodiimide (EDAC) and NHS. The
profiles of the magnetization curves given by vibrating sample
magnetometer (VSM) indicted that the corresponding mag-
netic nanocomposite was superparamagnetic NPs. The
magnetic-graphene nanocomposite was employed for the de-
velopment of a competitive electrochemical immunosensor,
10
which displayed excellent analytical performance for the de-
tection of cortisol.
Metal sulfide-graphene nanocomposites
Metal sulfide NPs often have the virtues of semi-conductivity,
excellent electrocatalytic activity and the possibility of pro-
moting electron transfer reactions at a lower overpotential
[99]. The functionalization of graphene by metal sulfide NPs
is always realized via hydrothermal chemical synthesis by
using different sulfur sources. For instance, Bai [100] reported
a synthesis process of CuS-rGO nanocomposites. Briefly,
Na2S aqueous solutions was added to mixture solutions con-
taining CuCl2, GO and polyvinylpyrrolidone (PVP), then the
suspension was transferred to Teflon-lined stainless steel au-
toclave and conditioned at 180 °C for 24 h. The oxygen-
containing groups uniformly existing on graphene oxide can
provide multiple binding sites, where the anchoring of CuS
NPs occurs. TEM images indicated that a large number of
CuS NPs with uniform size of about 40 nm were well-
dispersed on the surface of the graphene. The CuS-rGO NPs
exhibited good catalytical ability toward the H2O2 reduction.
Organic sulfur chemicals are more favorable for the synthesis
of sulfide NPs because they can release sulfide ions in a con-
trolled way. Giribabu [101] described another method for the
preparation of CuS/N-rGO nanohybrid. When the mixture of
GO and copper bis-(hexadecyldithiocarbamate) was irradiated
in a microwave, simultaneous reduction of graphene oxide
and decomposition of copper bis-(hexadecyldithiocarbamate)
complex occurred, forming a cluster of CuS on the surface of
N-rGO (Fig. 4). Hu [102] presented the preparation of CdS-
rGO nanocomposites. GO and cadmium acetate were dis-
persed in dimethylsulfoxide and then heated in an autoclave
at 180 °C. Here, the sulfide came from dimethylsulfoxide.
SEM images confirmed that the graphene was decorated with
Fig. 4 Schematic representation
for the synthesis of N-rGO/CuS
nanohybrids. Reprinted with
permission from Ref [101].
Copyright (2015) Springer
Microchim Acta (2017) 184:1–44
CdS NPs while AFM images revealed that the CdS-rGO film
had a much rougher surface morphology than rGO film.
Huang [103] synthesized WS2-GO nanocomposite by using
L-cysteine as the sulfur source. The specific surface area of the
WS2-GO nanocomposites was nearly as twice as that of GO,
indicating that the decoration of WS2 effectively decreased the
stacking of graphene. MoS2 has a graphene-like 2D structure
and has similar electronic structures with platinum, indicating
a potential alternative to precious platinum in catalysis. Xing
[104] presented the synthesis of MoS2/rGO nanocomposite by
a one-pot hydrothermal process, where thiourea was
employed as the sulfur source. The MoS2/rGO nanocomposite
displayed a loose porous and flower-like nanostructure
consisting of 2D petal-like nanoflakes and can improve elec-
trocatalytic performance toward oxidation of ascorbic acid,
dopamine, and uric acid by enlarging peak separation and
increasing peak current. By similar strategy, MoS2/rGO
[105], MoS2/rGO-CNT [106] and NiS-rGO [107] nanocom-
posites were prepared, all of which possessed large electro-
chemically active surface, wide potential window, high con-
ductivity and large porosity.
Graphene has been integrated with various nanomaterials
to form nanocomposites, attracting increasing interest in elec-
troanalysis field owing to the large surface area and combined
physical and chemical properties. According to whether the
formation of nanocrystallites is in the present of graphene or
not, the aforementioned synthesis approaches for
nanomaterial-graphene nanocomposites can be generally
summarized as two categories: in situ approaches and ex situ
approaches. The in situ approaches have the advantage that
extra protecting regents become less necessary and almost
every synthesis techniques for individual nanomaterials can
also be used. GO provides favorable conditions for the nucle-
ation, growth, and attachment of nanomaterials due to the
presence of defects and oxygen functional groups on the
Microchim Acta (2017) 184:1–44
surface. In addition, the synthesis can be induced or facilitated
by heating, ultrasonication, microwave and light. However, it
is sometime difficult to control the size, morphology and dis-
tribution of the nanomaterials. Ex situ approaches are espe-
cially promising in the case that incompatibility occurs be-
tween graphene and the precursors of nanomaterials.
Moreover, since the nanomaterials are prepared individually
in advance, better control of the amount, size and density of
the nanomaterial components can be achieved by ex situ ap-
proaches. Electrodeposition is a simple, fast, low cost, auto-
mate and green technique for the preparation of graphene
based nanocomposites, where the size and shape of the
nanomaterials can be precisely tuned by simply altering the
conditions of electrochemical deposition. It is worth noting
that simultaneous deposition of multi-nanomaterials as well
as the reduction of GO can also be achieved by electrochem-
ical method. In fact, a optimal approach for the preparation of
nanomaterial-graphene nanocomposite should be as conve-
nient as possible providing the potential of the individual com-
ponents is fully exerted, enabling the design of highly selec-
tive and sensitive electrochemical (bio)sensors.
Inorganic functionalization of graphene
GO can form various multifunctional nanocomposites through
chemical modification with inorganic. This type of the nano-
composite has some advantages in certain application of
chemical sensing and biosensing. In this respect, several inor-
ganic materials, such as polyoxometalates, metal
hexacyanoferrates and minerals can be used to synthesize
well-defined graphene nanocomposites.
Polyoxometalate functionalized graphene
Polyoxometalate (POM) cluster anions constitute a large class
of discrete molecular structures, and there properties can be
readily altered by the elemental composition of the POM clus-
ter itself [108]. Zhang [109] prepared phosphomolybdate-
functionalized nanocomposite by simply dispersing graphene
in phosphomolybdate solutions containing chitosan (CHIT)
with the aid of ultrasonic. The nanocomposite suspension
was very stable since phosphomolybdate intercalation
prevented the aggregation of graphene sheets. The nanocom-
posite exhibited high electrocatalytic activity towards the
Fig. 5 Electrodeposition of
heteropolymolybdate-rGO
composite films. Reprinted with
permission from Ref [111].
Copyright (2015) Elsevier
11
oxidation of ascorbic acid and can be applied for its sensitive
determination. Our group [110] demonstrated the self-
assembling of phosphotungstic acid-graphene oxide (PTA-
GO) nanocomposite by alternately immersing the pre-
anodized electrode into positively charged amine-GO and
negatively charged PTA aqueous solution. SEM images indi-
cated that PTA formed a uniform layer on the amine-GO sur-
face instead of disc-like crystals on the bare electrode surface.
The resulting nanocomposite greatly enhanced the oxidation
peak current of methyl jasmonate. They also lowered the ox-
idation peak potential from 1.38 V to 1.245 V. Guo [111]
developed an electrochemical growth method for the prepara-
tion of heteropolymolybdate-rGO composite films (Fig. 5).
Typically, the ITO electrode was alternatively immersed in
H4SiMo12O40-H2SO4 solution and GO-CHIT suspensions
for consecutive CV scans. SEM images revealed that the com-
posite film displayed translucent, wrinkled texture and well-
defined porous structure. The rough and porous surface pro-
vided the largely exposed catalytically active sites, which was
beneficial for the electrochemical reduction of persulfate.
Metal hexacyanoferrate functionalized graphene
Metal hexacyanoferrates (MHCF) are good candidates for con-
struction of electrochemical sensors due to the fast charge trans-
fer rate and the insolubility of both the oxidized and reduced
states. Among all MHCFs, Prussian blue (PB) has attracted the
most attention. Cao [112] described a in situ growth of PB-
functionalized graphene by refluxing the mixed solution con-
taining suitable amount of FeCl3, K3[Fe(CN)]6, PEI and GO. In
this case, PEI acted as reductant for the reduction of both Fe(III)
to Fe(II) and GO to rGO, leading to the direct deposition of PB
onto rGO surface. TEM images showed that well-separated PB
nanocubes with an average size of about 40 nm spread out on or
below the surface of rGO nanosheets. Chen [113] depicted the
decoration of PB by using K3[Fe(CN)]6 as the only precursor.
In this case, Fe3+ was slowly released due to the partial disso-
ciation of [Fe(CN)6]3−, while mushroom extract reduced
[Fe(CN)6]3− to [Fe(CN)6]4−. Therefore, Fe4[Fe(CN)6]3 was de-
posited onto the surface of graphene. Functionalization of
graphene with PB or PB analogues can also be realized via
electrochemical method. For example, Luo [114] immersed
rGO modified electrode in mixture solutions containing equal
concentration of CoCl2 and K3[Fe(CN)6] for constant cyclic
12
potential scans. The CoHCF/GO nanocomposite significantly
enhanced the oxidation peak current of nitrite and hydrazine.
According to similar procedure, NiHCF/GO [115] and LuHCF/
GO [116] were prepared for the construction of electrochemical
sensors. Mixed metal hexacyanoferrates can show special elec-
trochemical characteristics different than their respective single-
metal hexacyanoferrates. Wang [117] reported the preparation
of NiCoHCF/rGO nanocomposite by an electrochemical redox
reaction. The NiCoHCF microparticles supported on graphene
surface had smaller particle size and higher dispersion com-
pared with NiCoHCF alone, leading to superior electrocatalytic
activity for the oxidation of dopamine and ascorbic acid.
Mineral functionalized graphene
Clay-graphene nanocomposites are often obtained by mechan-
ically mixing with each other. Ding [118] manually ground GO
and laponite and the resulting mixture was easily dispersed in
water. The laponite-GO suspension was very stable, which
maybe due to the hydrophilic character of the laponite and the
electrostatic repulsion between the negatively charged laponite
coating on the graphene surface. In another report [119], ultra-
sonic agitation was employed to synthesis bentonite-GO hy-
brid. Zhang [120] described the hydrothermal synthesis of cu-
prous oxide-attapulgite-graphene. Briefly, attapulgite was first
immersed in CuSO4 solution under stirring, then dispersed in
GO suspensions, and finally reduced by hydrazine. SEM im-
ages indicated that Cu2O-decorated attapulgite nanorods were
well dispersed on the crumpled graphene. Hydroxyapatite is a
bioceramic analogous to the mineral component of bone with
good biocompatibility and adsorption capacity. Bharath [121]
gradually added (NH4)2HPO4 solution to the aqueous suspen-
sion containing CaCl2 and GO, the mixture was then sealed and
heated for hydrothermal treatment. The functional groups on
GO offered favored nucleation sites for the growth of hydroxy-
apatite, enabled the growth of homogeneously well dispersed
hydroxyapatite nanorods on graphene surface.
Organic functionalization of graphene
The organic functionalization of graphene can be realized by
two distinct approaches, namely covalent and non-covalent
approaches. Based on this principle, many research works
have been concentrated on the development of new synthetic
methods enabling an effective preparation of graphene nano-
composites with various functions. Some functional mole-
cules and the methods of molecular functionalization are sum-
marized as follows.
Amino acids as functional molecules
Tryptophan has an indole-conjugate structure and can non-
covalently anchor onto graphene via π-interaction. Lian
Microchim Acta (2017) 184:1–44
[122] synthesized tryptophan-functionalized GO nanocom-
posite by mechanically mixing with the aid of ultrasonication.
The charged groups of amino acid can effectively alleviate the
aggregation of graphene sheets and stabilize the aqueous dis-
persion. Qiao [123] described the covalent modification of GO
under heating. Methionine may react with GO by condensation
and nucleophilic addition between the amino groups of the
former and the carboxyl or epoxy groups on the latter. The
grafting of terminal carboxyl groups supplied enough negative
charge and the resulting electrostatic repulsion made the
graphene dispersions more stable. Vilian [124] reported the
electrochemical decoration of graphene with glutathione. In
the potential cycling process, the glutathione monomer was
oxidized to form an amino free radical, which can easily com-
bine with the GO surface. Compared with the unmodified GO,
the glutathione-GO exhibited much stronger catalytic activity
toward the oxidation of 4-aminophenol. Li [125] presented a
single-step thermolysis strategy to prepare amino acid-
functionalized nitrogen-doped graphene quantum dots by using
glycine as both carbon and nitrogen source. The uniform gly-
cine functionalized quantum dots exhibited an average size of
about 3 nm, and the height varied from 1 to 2 nm, which
revealed that the quantum dot contain 3 ~ 6 layers of graphene.
Surfactants as functional molecules
Surfactants have been proved to be helpful additives for the
dispersion of carbon nanomaterials. For example, our group
have [126] demonstrated stable and homogeneous aqueous
surfactant-CNT suspension based on the hydrophobic interac-
tions between the hydrophobic tails of dihexadecyl hydrogen
phosphate and the sidewall of the CNTs. The similar strategy
can also be applied for the functionalization of graphene.
Meng [127] reported the analytical application of sodium do-
decyl sulfate (SDS) functionalized graphene. The SDS-GR
was synthesized by electrifying high purity graphite rods in
SDS solution. The resulting SDS-GR nanocomposite can pro-
mote the electron transfer rate and discriminate 5-
methylcytosine from other nucleic acid bases. Mao [128] pre-
pared hexadecyl trimethyl ammonium bromide (CTAB) func-
tionalized graphene by mixing PVP stabilized graphene sus-
pension with CTAB solution under ultrasonication. This pos-
itively charged detergent with a long hydrophobic chain may
facilitate the accumulation of azo dyes and increase the sensi-
tivity for Sudan I determination. Compared with CTAB-GR,
bis (cetyldimethylammonium) butane dibromide, a gemini
surfactant (Gem), functionalized graphene has better
dispersibility in aqueous solution and displays lower surface
roughness [129]. Unlike the unavoidable strong aggregation
of CTAB on GO, Gem was on GO in the form of a molecular
layer with uniform surface coverage. Gem was more
homogenously adsorbed on the GO surface due to the im-
proved amphiphilic property and interface behavior.
Microchim Acta (2017) 184:1–44
Organic dyes as functional molecules
Some aromatic-containing organic dyes, such as Congo Red,
can combine with the surface of carbon nanomaterials via
strong π-interactions, which is helpful for the formation of sta-
ble, homogeneous, high-concentration aqueous dispersions
[130]. Yasri [131] utilized a triazo dye, Direct Blue (DB) to
obtain an aqueous dispersion of graphene. The strong hydro-
phobic aromatic backbone of DB was stacked on graphene
surface, while the sulfonic acid groups of DB aided in solubi-
lizing them in water due to electrostatic repulsion, leading to the
effectively exfoliation and stabilization of graphene sheets.
Thionine was also employed to non-covalently functionalize
GO with the aid of ultrasonication [132] [133], sometimes dur-
ing the reduction of GO in the presence of thionine [134]. Song
[12] described the covalent decoration of rGO by organic dye
via a two-step method. Prior to the chemical reduction process,
GO was firstly grafted by acyl chlorides, which were then
substituted by neutral red. The neutral red residue groups were
located at the edges of graphene nanosheets, where the acyl-
chlorination reactions mainly occurred. Different from the seri-
ous aggregation of rGO suspensions, the dye grafted rGO ex-
hibited excellent stability in aqueous solution even after being
stored for more than three weeks. Wang [135] reported the
electropolymerization of Alizarin Violet 3B (AV3B) over the
3D nano-network of CNT-GO hybrid. The resulting homoge-
neous nano-structured composite possessed the advantages of
both poly(AV3B) and CNT-GO nanohybrid with a synergistic
effect, which displayed excellent electrocatalytic activity for
oxidation reactions of acetaminophen (AP), theophylline (TP)
and caffeine (CF). Toluidine blue (TB) was also electrodepos-
ited on rGO surface, which not only acted as electron transfer
mediators but also provided a friendly polymer matrix for en-
zyme immobilization [136]. Our group [137] demonstrated the
electrochemical functionalization of graphene by safranine T.
GO was absorbed onto the surface of graphite pencil electrode
and the electropolymerization of safranine T was carried out
subsequently. The resulting composite exhibited high sensitive
response for the oxidation of indole-3-acetic acid.
Ionic liquids as functional molecules
Ionic liquids (ILs) have some fascinating properties, including
wide electrochemical potential range, high polarity and the
ability of solvating various species. The simplest procedure
for the preparation of IL-GO nanocomposite is mechanically
mixing, whether by hand [138] or with the aid of
ultrasonication [139]. Wang [140] described the synthesis of
1-butyl-3-methylimidazolium 2-amino-3-mercaptopropionic
acid salt ([Bmim][Cys]) IL functionalized graphene compos-
ites. The IL was non-covalently attached onto graphene
through π-interactions, while the thiol groups of the IL acted
as a mild reducing reagent for the reduction of GO, leading to
13
the formation of stable dispersion of IL-rGO. The composites
showed superior electrical conductivity due to the high ionic
conductivity of the IL and the synergistic effect of graphene
and the IL. Valentini [141] reported the synthesis of IL-GO
nanocomposites by anodic etching of graphite electrode in 1-
butyl-3-methylimidazolium bromide bath. Due to a complex
reaction mechanism based on the anodic oxidation of water
and anionic intercalation from IL, graphene multilayers can be
electrochemically exfoliated from the graphite surface and
combine with the IL via π-interactions between the
imidazolium rings and the conjugation of graphene sheets.
Li [142] prepared poly(ionic liquid)-rGO composite by radical
polymerization of 1-vinyl-3-ethylimidazolium tetrafluorobo-
rate monomer on graphene matrix. Compared with rGO, the
composite had larger electrochemical effective surface area,
showed higher peak current as well as lower overpotential for
the reduction of phenylethanolamine A.
Macrocycles as functional molecules
Macrocycles, including cyclodextrins (CDs), crown ethers
(CEs), calixarenes (CXs) and cucurbiturils (CBs), play impor-
tant roles in electroanalytical field owing to their potential of
molecular selectivity and enantioselectivity.
CDs have hydrophobic inner cavities and hydrophilic ex-
teriors, which makes them very attractive in the construction
of electrochemical sensors. β-CD has proven to be a stabilizer
for graphene and stable dispersion of β-CD/rGO can be ob-
tained by simple ultrasonication [143, 144]. Liu [145] synthe-
sized CD functionalized rGO by reducing GO in the presence
of 2,6-dimethyl-β-CD. It was supposed that the oxygen-
containing groups of rGO formed strong hydrogen bonding
with hydroxyl groups on both conical faces of CDs, leading to
the CDs cover on the surface of rGO which prevented their
coalescence and aggregation. Zhu [146] prepared CD-rGO
nanohybrids by using 3,4,9,10-perylene tetracarboxylic acid
(PTCA) as a bridge. The pyrenyl group of PTCA may strong-
ly anchor onto the surface of rGO and the carboxyl groups of
PTCA can easily react with amine groups of mono-(6-
ethanediamine-6-deoxy)-β-CD. Muñoz [147] synthesized
AuNP@rGO on which thiolated β-cyclodextrin was sequen-
tially assembled via Au-S covalent bonding. Zhang [148] re-
ported the electrodeposition of β-CD on GO by cyclic poten-
tial scans. TEM images showed that β-CD was well implanted
in GO film with nanosize, implying a favorable distribution
with compact multilayer composite-films.
Compared with CDs, other macrocycles are less popular
for the functionalization of graphene. Olsen [149] reported the
covalent functionalization of rGO with 1-aza-18-
crown[6]ether by using N-boc protected glycine as a linker.
The surface coverage of CE functional groups was approxi-
mately one CE unit per 50 rGO carbon atoms in the graphene
plane. The new material can selectively bind potassium ions
14
even in the presence of other alkali and alkaline earth metal
ions at high concentrations. Yang [150] prepared calix[6]arene
functionalized graphene via a one-pot wet-chemical strategy
based on glucose reduction of graphene oxide in the presence
of 4-sulfocalix[6]arene (CX6) hydrate. The synthesized CX6-
rGO was employed for the competitive host-guest recognition
of cholesterol by selecting methylene blue as a mediator. It’s
suggested by the molecular docking studies that hydrogen
bonding, electrostatic interactions, and hydrophobic interac-
tions should be the predominant driving forces for the forma-
tion of the inclusion complex. Buaki-Sogo [151] described the
reduction of GO in the presence of cucurbit[8]uril (CB8). The
resulting CB8-rGO hybrid combined the high electrocatalytic
activity of graphene with the specific molecular recognition
ability of CBs and exhibited excellent performance for the
detection of tryptophan.
Organometallics as functional molecules
Metalporphyrins and metalphthalocyanines (MPcs) can non-
covalently bind to graphene via strong π-interactions and offer
very stable functional matrixes. Metalporphyrins have been
extensively used in electrochemical sensor applications due to
the strong complexing ability and intrinsic electrocatalytic ac-
tivity. For example, Wang [152] demonstrated the non-covalent
assembling of iron (III) meso-tetrakis (N-methylpyridinum-4-
yl) porphyrin (FeTMPyP) on carboxylic GO. The π-π stacking
between tetrapyrrole aromatic ring and graphene led to stable
FeTMPyP monolayers on both sides of the GO, and the hybrid
showed greatly enhanced peroxidase activity and may be used
as a trace label for DNA sensing. Silva [153] presented the
microwave assisted synthesis of Fe(III) tetra-(N-methyl-4-pyr-
idyl) porphyrin modified rGO. The resulting nanocomposite
acted as an electron transfer mediator to shuttle electrons be-
tween oxygen and substrate electrodes, which was promising
for oxygen detections at extreme low overpotential.
MPcs are attractive sensing materials owing to their interest-
ing electrochemical properties. Wang [154] developed a one-
step microwave radiation-assisted method for the
functionalization of graphene with MPc. Briefly, a mixture con-
taining suitable amount of graphene, phthalonitrile, CoCl2 and
dimethylethanolamine was ultrasonically dispersed and heated
in a microwave reactor for certain time. In this case, graphene
induced the accumulation of CoPc on its surface via intermo-
lecular π-interactions and hydrophobic interactions. TEM im-
ages showed that the MPcs presented a nanorod structure and
were uniformly distributed onto the surface of graphene.
Ferrocenes (Fcs) are well-known as electron mediators due
to their good electrochemical reversibility and stable redox
forms. Fan [155] described the preparation of Fc-rGO by using
ethylenediamine as a bridge. GO was firstly aminated with
ethylenediamine in the presence of dicyclohexyl-carbodiimide,
then covalently bonded with Fc carboxaldehyde, and finally
Microchim Acta (2017) 184:1–44
reduced by NaBH4. The resulting Fc-rGO not only retained
the reversible redox activity of Fc, but also showed fast electron
transfer and good stability.
Other organics as functional molecules
Compounds containing aromatic ring can be easily adsorbed
onto the surface of graphene via π-π stacking. For example,
Hua [156] and Yu [157] reported 1-formylpyrene and N-[(1-
pyrenyl-sulfonamido)-heptyl]-gluconamide functionalized
rGO respectively. Nanocomposites based on these pyrene de-
rivatives were applied for the sensitive electrochemical deter-
mination of phenol [156] and Hg2+ [157]. It’s well-known that
phenylboronic acid derivatives can preferentially bind with
vicinal diols via cyclic ester bond formation. Wang [158] pre-
pared 4-aminophenylboronic acid modified graphene and
discussed its application for non-enzymatic sensing of sugar
by using Fe(CN)64− as redox species. The peak current of
significantly decreased with the addition of sugar and the cur-
rent changes were proportional to the sugar concentration.
As for nonaromatic compounds, covalent bonding is an
effective way for the functionalization of graphene.
Veerapandian [159] demonstrated the modification of GO
with a chemically anchored biomolecule glucosamine under
ultraviolet irradiation. The chemically anchored glucosamine
formed the C-N bond on the lattice, provided new sp2 and sp3
domains, lattice orientation and its derived electroactive
charge carriers, which may help charge transfer from the
graphene matrix to the adsorbing molecules and lead to im-
proved electrochemical properties.
Carboxyl groups are often the predominant anchoring sites
for the covalent biofunctionalization of graphene oxide, but
they are only available in very small amounts. In order to
enhance the amount of carboxyl groups on graphene sheets,
Bonanni [29] developed a robust chemical modification pro-
cedure to introduce perpendicularly grafted carboxyl groups.
RGO was functionalized by free-radical addition of
isobutyronitrile produced by the thermal decomposition of
azobisisobutyronitrile, then the nitrile group was hydrolyzed
under alkaline condition to give carboxylate salt, which gave
free carboxylic acid upon acidification. The high amount of
carboxyl groups grafted to graphene can be used as anchoring
points for biomolecule attachment by carbodiimide chemistry.
By comparison, modification with surfactant mainly leads
to enhanced dispersibility, while amino acid can improve the
processability at the same time. ILs and macrocycles can en-
dow the nanocomposite affinity to certain analytes, and spe-
cial catalytical activity may result from functionalization with
organic dyes and organometallics. In one word, organic
functionalization will lead to a variety of terminated groups,
which can not only remarkably improve the dispersibility,
processability and sensing performance, but also offer oppor-
tunities for further functionalization and modification.
Microchim Acta (2017) 184:1–44
Graphene-based polymer nanocomposites
Graphene-based polymer nanocomposites have prompted the
development of novel modified electrodes for electrochemical
application. These nanocomposites exhibited outstanding
sensing performance and multifunctional properties with the
aid of advanced synthetic route and assembly technology if
suitable molecular structural and interfacial organization is
achieved. Here, we briefly summarize the designs and synthe-
sis of graphene-based polymer nanocomposites.
Conventional polymer-graphene nanocomposites
PVP is a neutral macromolecule that displays food film-
forming ability and strong adsorption character. Shan [25]
reported the preparation of PVP protected graphene by simply
mixing them with each other under stirring. During the pro-
cess, PVP was adsorbed onto graphene via strong hydropho-
bic interactions, endowed the PVP-GO with good solubility
and stability. The as prepared composite was redispersed read-
ily in water by ultrasonication and had good electrochemical
reduction toward O2 and H2O2. Araque [160] described the
covalent synthesis of a polyamidoamine dendrimer-rGO hy-
b r i d . Ty p i c a l l y, G O w a s f i r s t g r a f t e d w i t h ( 3 -
glycidyloxypropyl) trimethoxysilane by using hydroxyl
groups as anchoring points. Then the silanized GO was further
functionalized and reduced by treatment with the fourth-
generation ethylenediamine-core polyamidoamine dendrimer
(PAMAM). This amino-enriched hydrophilic hybrid provided
stability to the aqueous graphene dispersions as well as the
possibility of functionalizing with biomolecules, and was
employed for the construction of enzyme based biosensors.
Polyelectrolyte-graphene nanocomposite
CHIT is a polycationic polymer that possesses high water
permeability and good susceptibility to chemical modifications
due to the reactive amino and hydroxyl functional groups. Han
[161] synthesized CHIT functionalized graphene by a together-
blending and in situ chemical reduction method. CHIT mole-
cules were intercalated between graphene layers and act both as
dispersant and stabilizer. The obtained CHIT-graphene nano-
composite exhibited both increased sensitivity and selectivity
towards oxidations of ascorbic acid (AA), dopamine (DA) and
uric acid (UA). In addition, the amino groups of CHIT endowed
the nanocomposite plenty of active sites for further
functionalization [162, 163]. PEI with abundant amino groups
can serve as a reductant to reduce graphene oxide and amount
of amino groups can be embedded in graphene platform during
the reaction process. Luo [13] covalently linked PEI to GO
under reflux and obtained PEI-rGO composite. The synthetic
PEI-rGO was positively charged and exhibited superior perfor-
mance in the detection of gallic acid owing to its excellent
15
adsorption ability. Poly(allylamine hydrochloride) (PAH) is a
weak cationic polyelectrolyte with many ionizable amine
groups which is fully protonated in neutral and acid solutions.
Istrate [164] dispersed GO into PAH aqueous solution under
ultrasonication to acquire a stable suspension, which was ap-
plied for the construction of modified electrode. The presence
of PAH stabilized the graphene based electrode material and
favored the electrostatic interaction with nicotinamide adenine
dinucleotide (NADH). Poly(diallyldimethylammonium chlo-
ride) (PDDA) is a positively charged linear polyelectrolyte that
can effectively non-covalently functionalize graphene. Xu
[165] reported the facile preparation of PDDA-rGO. Since the
interaction between PDDA and rGO was relatively mind, the
unique properties of graphene were preserved when the
dispersity and stability were greatly improved. The resulting
hybrids were able to greatly enhance the current response to
negatively charged substances.
Contrary to PDDA, poly(sodium 4-styrenesulfonate)
(PSS) is a negatively charged polyelectrolyte. Navaee [166]
added hydrazine to the mixture of GO and PSS solution and
hydrothermally synthesized PSS-rGO. The composite showed
excellent electrocatalytic activity toward the oxidation of mor-
phine, noscapine and heroin and was used for their simulta-
neous detection without any separation or pretreatment proce-
dures. Nafion is a typical cationic ion exchange resin and has
been widely used for the construction of highly selective elec-
trochemical sensors. Wang [167] prepared Nafion-GO com-
posite by dispersing GO in Nafion solution under
ultrasonication. The hydrophobic backbone of Nafion can
combine with graphene by hydrophobic interactions, while
the hydrophilic groups can endows them good water
Bsolubility^. Nafion can increase the immobilization stability
of GO on the electrode surface and exclusively facilitate the
accumulation of positive charged species. Moreover, due to its
negatively charged feature, Nafion can act as a barrier to dis-
criminate against anions as well as prevent the fouling caused
by nonspecific adsorptions of negatively charged species [168].
Conducting polymer-graphene nanocomposites
Conducting polymers contain a large resonation structure with
many sp2-carbon atoms that permits delocalized transport of
charge carriers, and may act as conducting conduits that inter-
face with graphene and analytes or play the role of sensitizing
agents to give rise to high performance sensors [20].
Electropolymerization is the favorite method for the control-
lable synthesis of stable, adhesive, uniform conducting
polymer-graphene nanocomposite. Among all conducting
polymers, polyaniline (PANI) is the most extensively studied
one. Feng [28] and Sharma [169] demonstrated the electro-
chemical synthesis of PANI-GO composite. Typically, the an-
iline monomer and GO suspension was dropped onto elec-
trode surface by spinning coating and then conducted by
16
scanning the potential. During the scanning process, aniline
monomer was oxidized and polymerized along the surface of
GO and GO was reduced at the same time. The obtained com-
posite film showed large specific area, high conductivity, good
biocompatibility, fast redox properties, perfect layered and en-
capsulated structures, which was very promising for the devel-
opment of biosensors. Polypyrrole is also a widely studied
conducting polymer. Gao [170] electrochemically synthesized
over-oxidized polypyrrole-GO composite by CV scanning the
electrode in mixture solution of pyrrole monomer, GO and
LiClO4. The resulting polypyrrole-GO nanocomposite showed
a rather porous nanostructure, which extremely increased the
active surface area. The nanocomposite can prompt the adsorp-
tion of the adenine and guanine via strong π-interactions and
shows high electrocatalytic ability for their simultaneous detec-
tion. Poly(3,4-ethylenedioxythiophene) (PEDOT) is a very sta-
ble conducting polymer with highly conductive cationic-doped
state. Wang [171] investigated the electropolymerization of
EDOT on the surface of rGO, followed by the electrodeposition
of CoNPs. It was observed that the fibrillar network structure of
PEDOT-rGO played an important role in the formation of inten-
sively distributed small CoNPs. Weaver [172] described the
electrochemical synthesis of PEDOT/GO nanocomposite by
using GO as dopants. During the electrodeposition, oxidation
of the EDOT monomer via electrical stimulation elicited free
radical polymerization, incorporating negatively charged GO
to electrostatically balance positive charges formed on the poly-
mer backbone. Covalent modification of the PEDOT/GO nano-
composite with an aptamer led to highly sensitive and selective
detection of dopamine [173]. Many other polymer-GO compos-
ites were also electrochemically synthesized for the construction
of sensors according to similar strategy by using different mono-
mers as starting materials, including aminobenzene sulfonic acid
[174], xanthurenic acid [175], indole-5-carboxylic acid [176],
sulfosalicylic acid [177], 2,6-pyridinedicarboxylic acid [178],
carbazole [179], imidazole [180], melamine [181], quercetin
[182], and methylthiophene [183].
Molecularly imprinted polymer-graphene nanocomposites
Molecular imprinted polymers (MIPs) are artificial recognition
units with good selectivity and have become ideal candidates
for the fabrication of various chemical sensors. However, ap-
plication of insulating MIP films in electrochemical sensors
seems hindered due to the lack of a direct path for electron
conduction between the MIP recognition sites and the electrode
transducer [184]. Functionalization with graphene can provide
a promising solution to overcome these shortcomings. Deng
[185] prepared MIP-GO via a simple casting-drying method.
Generally, aqueous suspension containing bisphenol A, CHIT
and GO was cast onto the electrode surface and air-dried. It was
then immersed in sulfuric acid solution for cross-linking,
followed by the removal of the template molecules.
Microchim Acta (2017) 184:1–44
Combining the excellent electrical conductivity of GO and
the recognition ability of MIP, the resulting MIP sensor showed
high sensitivity and good selectivity for the determination of
bisphenol A. Chen [186] synthesized MIP grafted GO by
heating the mixed solution of graphene, template molecule,
functional monomer, porogen solvent, cross-linking agent and
initiator. The MIP/GO based sensor was applied for the simul-
taneous determination of 4, 4-methylene diphenylamine and
aniline. Dadkhah [187] presented an effective approach for
the preparation of MIP/GO based sensor. Prior to polymeriza-
tion, 3-aminopropyltriethoxysilane (APTES) was employed to
introduce amino groups onto the surface of GO, which provid-
ed sufficient active sites for the anchoring of both the template
molecules and the cross-linker molecules, terminal vinyl
groups of ethylene glycol dimethacrylate (EGDMA). Based
on the inherent selective recognition affinity of MIP and elec-
trochemical conductivity of GO, a bisphenol A sensor with
high selectivity and sensitivity was developed. Luo [188] de-
veloped a facile strategy for producing MIP-GO composite by
oxide self-polymerization of dopamine in the presence of
graphene and template molecules (Fig. 6). The reactions were
conducted in nearly neutral aqueous solution at ambient tem-
perature without any initiators, which was close to the natural
environment of proteins. The MIP-GO composite displayed
specific recognition to target protein and was employed for its
competitive determination by using hexacyanoferrate as elec-
trochemical probes. Besides free-radical polymerization,
electropolymerization is another frequently used method for
MIP’s preparation. The main advantage of this process is that
the polymer thickness can be regulated by electrochemical con-
ditions. In addition, electropolymerized MIPs are mostly con-
ductive. Silva [189] described the electropolymerization of
MIP on GO film modified electrode. The formation and growth
of the MIP film was performed in supporting electrolyte solu-
tions containing template molecules and pyrrole by CV. The
MIP-GO film exhibited a high selectivity and sensitivity toward
the oxidation of trimethoprim.
Biomolecules-functionalized graphene
A number of studies have confirmed that biomolecules-
functionalized graphene is a kind of excellent nanocomposite
for constructing electrochemical biosensors by non-covalent
combining interaction and/or covalent modification method.
Synthesis of such nanomaterial has been intensively investi-
gated not only in the biological engineering but also in elec-
trochemical sensing. The following describes the progress of
research in this area.
Proteins-functionalized graphene
Graphene has been proved to be capable of enhancing the
enzyme loading amount while facilitating direct electron
Microchim Acta (2017) 184:1–44 17

Fig. 6 The preparation route for

the MIP-GO composite by oxide
self-polymerization of dopamine
and the sensing mechanism.
Reprinted with permission from
Ref [188]. Copyright (2014)
Elsevier

transfer between enzymes and electrode, leading to sensitive
and selective biosensors. Li [190] reported the non-covalent
combining of graphene oxide with microperoxidase-11 (MP).
The MP-GO had a sandwich structure with the MP molecules
on both sides of graphene sheets. UV-Vis spectra showed that
MP retained its natural character. When a single MP-GO sheet
collided with the surface of the Au microelectrode with
Brownian motion, it became a nanoelectrode for millisecond
contact period and the resulting amplified redox currents pro-
vided information about the electron transfer kinetics at the
single molecule level. Apart from the non-covalent attach-
ment, also of importance is the covalent immobilization of
enzyme. Araque [191] developed a procedure for the covalent
modification of GO with enzyme (Fig. 7). GO was grafted
with carboxymethyl cellulose through a (3-aminopropyl)
triethoxysilane linkage, then tyrosinase was covalently at-
tached via amide bond. SEM analysis and EIS experiments
suggested a high protein loading on the biocomposite.
Srivastava [30] prepared bienzyme-GO biocomposite by
covalently immobilizing urease (Urs) and glutamate dehydro-
genase (GLDH) to mixed acid treated GO with the aid of NHS
and EDC. In the presence of NADH, the bienzyme function-
alized graphene modified electrode showed good current re-
sponse to urea. This procedure may also be applied for other
enzyme-graphene based biosensor.
Nucleic acid-functionalized graphene
The base pairs stacked within double helical nucleic acid can
provide an effective platform for development of electrochem-
ical biosensors. Nucleic acid can be bound to graphene via
ether non-covalent π-π stacking or covalent-conjunction
[192, 193]. In the case of nucleobase π-π stacking, the
physisorption can induce an additional interfacial dipole be-
tween the nucleobases and graphene due to the close associa-
tion of electron-rich aromatic rings of the bases and the polar-
izable graphene surface, which is important for binding ener-
gy contribution [194]. Wang [195] described the formation of

Fig. 7 Schematic display of the

steps involved in the preparation
of the rGO–CMC hybrid
nanomaterial and the Tyr/rGO–
CMC/GCE enzyme electrode.
Reprinted with permission from
Ref [191]. Copyright (2014)
Wiley
18
DNA-GO composite by simple adsorption. Briefly, a single-
stranded DNA (ssDNA) modified Au electrode was immersed
in GO solutions. During this process, DNA-GO composite
was formed through π-π stacking interactions between
graphene and DNA bases. Ferreira [196] refluxed the mixture
of GO, hydrazine and single-stranded DNA (ssDNA) to pre-
pared DNA-rGO nanocomposite. This DNA-rGO nanocom-
posite provided a favorable support for the efficient immobi-
lization of methylene blue (MB), a well-known redox indica-
tor. Based on MB’s electron mediating characteristic and the
electrocatalytic properties, a sensitive NADH biosensor was
developed. Wang [197] prepared amino groups modified rGO
(NH2-rGO) via nitrogen plasma treatment, which resulted in a
wide range of functional nitrogen groups evenly incorporated
into the carbon lattice, providing plenty of anchoring sites for
the covalent conjunction of ion specific DNA and DNAzyme.
The DNA-NH2-rGO nanocomposite exhibited high specifici-
ty and sensitivity for the impedimetric determination of Pb2+
and Hg2+. Aptamers can bind target proteins with high affinity
and specificity. Wang [15] prepared thrombin binding
aptamer (TBA)-rGO by covalent interaction between
amino groups of TBA and electrogenerated carboxyl
groups of rGO (Fig. 8). In the presence of target throm-
bin, complex of quadruplex-thrombin is formed and will
greatly restrain the access of electrons for the redox probe,
which provide a universal approach for constructing label-
free electrochemical biosensors. According to similar proto-
col, Gao [198] and Erdem [199] synthesized aptamer-GO for
the selective and specific detection of hemin and lysozyme,
respectively.
Flexible graphene nanocomposites
Flexible and stretchable electrochemical sensors have shown
great promise for a wide range of portable, wearable and im-
plantable applications. Graphene fibers and papers would be
idea candidates for the construction of flexible sensors
Fig. 8 A schematic diagram of
the construction of the GO-TBA-
based aptasensor and its sensing
mechanism. Reprinted with
permission from Ref [15].
Copyright (2012) Royal Society
of Chemistry
Microchim Acta (2017) 184:1–44
because of their extraordinary electrical conductivity, stability
and mechanical robustness [200, 201].
Li [202] prepared graphene fiber by injecting GO and AA
mixture suspension into propylene pipeline, which was then
sealed and heated for reduction of GO and finally dried in air,
leading to a graphene fiber with a neat surface and a uniform
diameter of about 200 mm. The graphene fiber displayed good
ultimate elongation and tensile strength, excellent laundering-
conductivity durability as well as bend-conductivity. Xiao
[203] demonstrated the fabrication of flexible rGO paper
using a simple and scalable mold-casting method. Briefly,
aqueous suspension of GO was placed in a casting mold made
of polytetrafluoroethylene (PTFE) and dried under room tem-
perature to form an integral layer of GO paper, which was then
immersed into an HI solution in a sealed cuvette to reduce GO
to rGO (Fig. 9). The electrochemical behaviors of the rGO
paper based flexible electrode were nearly immune to its
bending states, suggesting potential applications in miniatur-
ized electrochemical sensors and portable diagnostic electron-
ics. Zhang [204] reported the preparation of flexible graphene
sensor via vacuum filtration. In order to improve the mechan-
ical property of the graphene paper, an anodic aluminum ox-
ide (AAO) membrane was selected as the filter since Al3+ ions
released can act as perfect cross-linkers for connecting GO
sheets. The resulting free-standing graphene paper had high
conductivity, robust mechanical strength and can be rolled or/
and bent, which can be used as flexible, disposable, non-
enzymatic hydrogen peroxide sensors.
Ghosh [205] cast rGO dispersion on a Whatman filter pa-
per for vacuum filtration, the rGO-coated filter paper was then
dried in air and finally aluminum were deposited on the sam-
ple. The flexible sensor showed selective resistance response
to ammonia, and the response obtained in bending statue (40°)
was similar to that in flat position. Fan [16] fabricated a flex-
ible transparent electrode by assembling graphene onto poly-
ethylene terephthalate (PET). Typically, GO film coated cel-
lulose acetate microfiltration membrane was pressed onto the
Microchim Acta (2017) 184:1–44 19

Fig. 9 Illustrative fabrication

process of the flexible graphene
electrode and its optical
photographs. Reprinted with
permission from Ref [203].
Copyright (2012) Wiley

PET sheet, then the composite film was treated by acetone and
mixture steam of hydroiodic acid and acetic acid sequentially.
The flexible graphene electrode exhibited good transparency
and conductivity, suggesting a competitive alternate for indi-
um tin oxide (ITO).
Three dimensional graphene composites
Three-dimensional (3D) graphene networks have the advan-
tage of high surface area, plenty of active sites, and excellent
conductive channel to facilitate the fast electron transfer, lead-
ing to rapid and sensitive determination of target analytes
[206, 207]. 3D graphene networks can be realized by chemical
vapor deposition (CVD) from carbon-containing precursors
on nickel foams or deposition of GO on 3D templates.
Cao [208] reported the growth of 3D graphene network via
CVD by using nickel foams as the growth substrate and eth-
anol as the precursor. The porous 3D graphene network not
only provided an extraordinary matrix for the loading of
electroactive materials (as shown in Fig. 10) but also enabled
the efficient contact between the electrolyte and electrode sur-
face, resulting in rapid and sensitive response to H2O2. Kung
[209] prepared porous 3D graphene foam by similar protocol
except for the use of CH4 as carbon source. The 3D graphene
foam exhibited a macroporous structure and slightly wrinkled
morphology, which was very important to prevent the aggre-
gation of graphene and maintain high active surface.
Penmatsa [210] prepared 3D carbon micropillars by pyro-
lyzing finely patterned photoresist and then coated graphene
onto such 3D carbon by electrostatic spray deposition (ESD).

Fig. 10 SEM images of a 3D

graphenes and after deposition of
b PtNPs, c CNTs, and d MnO2
nanowalls. Inset in (A): HRTEM
image of a graphene sheet of 3D
graphenes. Reprinted with
permission from Ref [208].
Copyright (2013) Wiley
20
The ESD of graphene had a conformal feature and thus a
porous graphene-carbon micropillar electrode array was con-
structed. This micropillar electrode array exhibited fast charge
transfer and high electrochemical activity towards H2O2, dem-
onstrating a promising approach to fabrication 3D electrodes
with controllable morphology for further analytical
applications.
Yu [211] presented the preparation of 3D–rGO by reduc-
tion of GO in the presence of polystyrene spheres (PSs). GO
can self-assemble onto surface of PS via π-interaction. After
the removal of PS by toluene, the graphene exhibited a porous
structure and the pore size was similar to the diameter of PSs.
Zhao [212] synthesized 3D–rGO similarly by using amino-
modified SiO2 spheres as sacrificial templates. In that case,
HF was employed for the removal of SiO2 and the porous 3D–
rGO based electrode was applied for the non-enzymatic deter-
mination of glucose.
Yong [213] introduced an interest 3D–rGO-hybridized bio-
film. The 3D biofilm was constructed by the onestep self-
assembly of Shewanella oneidensis MR-1 and graphene oxide
(GO) coupled with in situ bioreduction of GO to rGO by the
bacteria. The 3D macroporous network enabled the incorpo-
ration of large amount bacteria and exhibited extraordinarily
enhanced bidirectional electron transfer over that of naturally
occurring biofilms.
As different strategies, covalent and non-covalent ap-
proaches both have their own advantages and limitations.
Covalent interactions are very strong and specific, leading to
extremely effective and stable functionalization of graphene.
However, the disruption of native electronic structure of
graphene will unavoidably cause the degradation of its charge
transfer properties. In addition, the covalent procedures are
often time-consuming and sensitive to the synthesis condi-
tions. Compared with covalent functionalization, the interac-
tions resulting from non-covalent functionalization are rela-
tively weak, but multiple non-covalent interactions working
in concert can also lead to highly stable functionalization.
Moreover, the non-covalent approaches are more versatile
and the original structures and properties of graphene can be
better retained. Whichever approach is employed for the
functionalization of graphene, the properties of the resulting
nanocomposites are not just a simple combination but a syn-
ergistic effect of both graphene and the functional materials.
Application of graphene nanocomposite
in electrochemical sensors and biosensors
Graphene nanocomposites have been extensively exploited to
design the next-generation chemical and biological sensors
due to its outstanding physicochemical properties, excellent
catalytical activity and low fabrication cost [3–5, 7–10,
17–23]. In the following subsections, we will discuss several
strategies employed for the electroanalysis according to the
Microchim Acta (2017) 184:1–44
specific transducing technique adopted, including voltamme-
t r y, a m p e r o m e t r y, p o t e n t i o m e t r y, i m p e d i m e t r y,
electrochemiluminescence, photoelectrochemistry, field effect
transistor, and immunoreaction. Moreover, considering their
unique importance in analysis field, the recent advances of
electrochemical gas sensors, enzyme and nucleic acid based
biosensors will be described in the subsequent three
subsections.
Voltammetric sensors
Voltammetric methods are the most adopted transducing tech-
niques in the development of electrochemical sensors, which
are based on measuring the resulting current of redox active
analyte at the modified electrode when scanning potential in
supporting electrolyte. Voltammetric approaches can not only
provide sensitive and fast quantitative analysis, but also reveal
the characteristic of the electrochemical process occurred on
the surface of the sensing electrode. In addition, voltammetric
approaches can offer simultaneous determination of different
potentially interfering substances. Among all voltammetric
methods, linear sweep voltammetry (LSV), differential pulse
voltammetry (DPV), square-wave voltammetry (SWV) and
stripping voltammetry (SV) are the most preferred techniques
applied for the detection of ions [143, 214–225], small organic
molecules [39, 56, 135, 226–240] and even proteins [241].
The performance of various graphene nanocomposite-based
voltammetric sensors is presented in Table 3.
It’s well known that heavy metal ions can cause significant
health risk and there sensitive detection is very important. Zhu
[214] reported the simultaneous determination of Cd2+ and
Pb2+ using square wave anodic stripping voltammetry at a
gold nanoparticle-graphene-cysteine composite modified bis-
muth film electrode. The synergistic effect of cysteine as well
as the enlarged, activated surface and good electrical conduc-
tivity of AuNPs and graphene contributed to the deposition of
Cd (II) and Pb (II) on the electrode surface. Under the opti-
mum conditions, a linear relationship existed between the cur-
rents and the concentrations of Cd2+ and Pb2+ in the range
between 0.50 to 40 μg·L−1 with the detection limits (DL) of
0.10 μg·L−1 for Cd2+and 0.05 μg·L−1 for Pb2+. Zhang [216]
developed a stable sensing interface based on covalent anchor-
ing GO on gold substrates for the simultaneous determination
of Pb2+, Cu2+ and Hg2+. By using Osteryoung square wave
voltammetry, the potential of the three ions were separated
enough with about 0.3 V and the DLs were observed to be
as low as 0.3, 1.7 and 1.7 ppb, respectively. The high sensi-
tivity was due to the binding of GO to phenyl group terminat-
ed gold electrodes resulting in faster electronic communica-
tion between metal ions and substrates. Silwana [217] con-
structed an rGO impregnated antimony nanoparticle sensor
for the electroanalysis of platinum group metals. The electro-
chemical behavior of platinum group metals at the modified
Microchim Acta (2017) 184:1–44 21

Table 3 Various voltammetric sensors based on functionalized graphene

Analytes Modified electrode Technique Linear range/μM Detection limit/μM Ref.

Cd2+, Pb2+ Au-GR-Cys/GCE SWV 0.50 ~ 40 μg·L−1 0.10, 0.05 μg·L−1 [214]
Cd2+, Pb2+ N-GR/nano-CPE SWV 1.0 × 10−5 ~ 1.0 × 10−3 8.0 × 10−6 [215]
Pb2+, Cu2+, Hg2+ GO-CO-NH-Ph/AuE SWV 3.3 ~ 100, 17 ~ 100, 34 ~ 200 ppb 3.3, 17, 17 ppb [216]
Pd2+, Pt2+, Rh3+ rGO-Sb/GCE DPV 40 ~ 400, 0 ~ 260, 40 ~ 400 pg·L−1 0.45, 0.49, 0.49 pg·L−1 [217]
Pb2+ Nafion/Hg(II)/GO/GCE SWV 5 ~ 70 ng·L−1 0.13 ng/L [218]
Pb2+ β-CD-rGO/GCE SV 0.001 ~ 0.100 0.0005 [219]
Cu2+ NH2-rGO/β-CD/GCE SWV 0.030 ~ 100 0.0028 [143]
Cu2+ GO-C7Me/AuE SWV 0 ~ 100.0 2.7 [220]
Hg2+ rGO-Au/GCE SV 0.001 ~ 0.200 0.0006 [221]
Fe(III) rGO/MB/Au/GCE DPV 0.3 ~ 100 0.015 [222]
As(III) Nafion/Leucine/GO/AuE CV 5 ~ 50 ppm 0.05 ppm [223]
As(III) TTCN-Au-GR-PE SV 2.5 × 10−5 ~ 0.034 8 × 10−6 [224]
S2− rGO/GCE CV 5.0 ~ 7400 4.2 [225]
glucose Nafion/Pt3Pd/rGO/GCE SV 0.002 ~ 300 0.002 [56]
DA Fe3O4-GR/Nafion/GCE DPV 0.020 ~ 130.0 0.007 [226]
AA NiO/GR/GCE DPV 0.05 ~ 1100 0.0167 [227]
norepinephrine rGO/GCE SWV 1 ~ 200 0.050 [228]
tizanidine GR-ZnO/GCE SWV 8.0 × 10−4 ~ 10.0 μg·mL−1 0.10 ng·mL−1 [229]
sophoridine PP-rGO/GCE SWV 0.80 ~ 100 0.20 [230]
cis-jasmone PTA-C60-GO/GE DPV 0.3 ~ 50.0 0.1 [232]
nebivolol Nafion/GR/GCE DPV 0.5 ~ 24.0 0.046 [233]
p-aminothiophenol Au-ATPGO/GCE SWV 1.0 × 10−6 ~ 1.0 × 10−5 3 × 10−7 [234]
acetaminophen poly(AV3B)/CNT-GO/GCE DPV 0.2 ~ 100 0.5 ~ 120 1.0 ~ 120 0.01 0.02 0.10 [135]
theophylline caffeine
DA, UA, AA rGO/imidazolium alkoxysilane /GCE DPV 0.1 ~ 200, 20 ~ 490, 30 ~ 2000 0.03, 5, 10 [235]
butylated hydroxyanisole Au-PVP-GR/GCE LSV 0.2 ~ 100.0 0.04 [236]
nicotine PDDA-rGO/Au/GCE DPV 0.5 ~ 300 0.12 [237]
imidacloprid GO/GCE CV 0.8 ~ 10 0.36 [238]
clenbuterol isopropanol-Nafion/PSS-GR/GCE LSV 0.075 ~ 25 0.022 [239]
trinitrotoluene rGO-PAMAM/GCE DPV 0.05 ~ 1.2 ppm 0.0015 ppm [240]
p-dihydroxybenzene GNR/CNT/GCE DPV 0.08 ~ 3.00 0.02 [39]
glycated Hb PBA-PQQ/rGO/GCE DPV 9.4 ~ 65.8 μg·mL−1 1.25 μg·mL−1 [241]

electrode was studied by adsorptive differential pulse cathodic
stripping voltammetry in the presence of dimethylglyoxime as
chelating agent. Kumar [223] reported the fabrication of high-
ly sensitive and selective electrochemical sensor for the detec-
tion of arsenic using L-leucine as bio-recognition element
based on graphene oxide. The sensor exhibited a high and
reproducible sensitivity of 30 μA ppm−1 cm−2 with a DL of
0.5 ppm and was applied to detect arsenic in real environmen-
tal samples.
Numerous works have been dedicated to the development
of graphene nanocomposite-based sensors for the
voltammetric analysis of small organic molecules that plays
important role in biomedical system or may influence our
health. Dopamine (DA) is an important catecholamine neuro-
transmitter found in serum samples at very low physiological
concentration. It is often present along with high
concentrations of ascorbic acid (AA) and uric acid (UA).
Zhao [231] developed a promising electrochemical sensor
for the simultaneous detection of AA, DA and UA by electro-
deposition of MgO nanobelts on a graphene-modified tanta-
lum wire electrode. The sensor not only exhibited good elec-
trocatalytic activities towards the oxidation of the three sub-
stances, but also resolved the overlapping CVoxidation peaks
of these three species into three well-defined peaks. Cis-
jasmone (CJ) is a metabolite derived from the biosynthesis
of jasmonic acid that can change the benzoxazinoid levels in
crops and reduce the aphid population. Based on electrode-
posited PTA-C60-GO nanocomposite [232], a novel CJ sensor
was prepared, which exhibited high electrocatalytic activity
and accumulation ability for the direct electrochemical oxida-
tion of CJ with an apparently reduced oxidation over potential
and considerably higher sensitivity. Nebivolol is a competitive
22 Microchim Acta (2017) 184:1–44

and highly selective 1-receptor that is usually used clinically
for the treatment of hypertension and chronic heart failure. Er
[233] reported the electrochemical analysis of nebivolol on
graphene-Nafion nanocomposite modified electrode using
voltammetric techniques. The sensor showed a good linear
relationship of the oxidation peak current with respect to con-
centrations of nebivolol cross the range of 0.5 ~ 24.0 μM with
a low DL of 46 nM. Imidacloprid is a highly efficient insec-
ticide that is present in the environment that exerts serious
impacts on the natural environment and the health of human-
ity. Lei [238] fabricated a GO modified glassy carbon elec-
trode for the fast and sensitive electrochemical detection of the
imidacloprid insecticide with high selectivity and stability.
The reduction peak current varies linearly with the concentra-
tion of imidacloprid over the ranges of 0.8 to 10 μM, and the
DL is 0.36 μM. Clenbuterol is often illegally abused as food
additive for livestock to enhance the muscle growth and de-
crease fat deposition. Wang [239] reported a novel clenbuterol
electrochemical sensor based on isopropanol-Nafion-PSS-
rGO composite film modified glassy carbon electrode.
Applying LSV, a high electrocatalytic performance towards
the oxidation of clenbuterol in the linear range of
7.5 × 10−8 ~ 2.5 × 10−5 M and a DL of 2.2 × 10−8 M were
achieved.
Determination of glycated hemoglobin is very useful for
the long-term glycemic control of diabetes without the influ-
ence of short-term fluctuations of blood glucose. Zhou [241]
developed a voltammetric sensor for the determination of
glycated hemoglobin based on the composites of
phenylboronic acid-modified pyrroloquinolinequinine and
rGO. Herein, pyrroloquinolinequinine acted as an electro-
chemical probe and its oxidation peak current decreased upon
the addition of glycated hemoglobin.
Amperometric sensors
In amperometry, the cell current is monitored over time after
the application of a fixed potential. Amperometric method can
response to successive injection of analytes and can be applied
to electroactive substances that can exhibit redox current as a
function of time. The various amperometric sensors adopted
for the sensitive determination of H2O2 [33, 55, 242–244],
glucose [245–247] and other species [168, 248–256] are listed
in Table 4.
Hydrogen peroxide (H2O2) is one of side products of bio-
chemical reactions and plays important physiological roles in
biosystems. Noor [55] described a GO-silver NPs modified
electrode for the amperometric determination of H2O2. The
sensor showed an excellent electrocatalytic performance on
H2O2 reduction and the amperometric i-t curve displayed a
linear range of 100 μM ~ 11 mM with the DL of 28.3 μM.
In another work, Zhang [242] reported a more sensitive H2O2
sensor for the reductive determination of H2O2 based on rGO-
Pt nanocomposites. The sensor exhibited lower working po-
tential (0.08 V vs. Ag/AgCl), wider linear range
(0.5 μM ~ 3.475 mM), higher sensitivity (~460
mAM−1 cm−2) and lower DL (0.2 μM), which preceded both
PtNPs and graphene modified electrode. The sensor can be

Table 4 Various amperometric sensors based on functionalized graphene

Analytes Modified electrode Working potential Linear range/μM Detection limit/μM Ref.

H2O2 N-GNR/SPCEa −0.4 V(vs. Ag/AgCl) 5 ~ 85, 135 ~ 1285 1.72 [33]
H2O2 GO-Ag/GCE −0.3 V(vs. Ag/AgCl) 100 ~ 11,000 28.3 [55]
H2O2 rGO-Pt/GCE −0.08 V(vs. Ag/AgCl) 0.5 ~ 3475 0.2 [242]
H2O2 Nafion/GO-Co3O4/GCE 0.76 V(vs. Ag/AgCl) 1.0 ~ 5000 0.3 [243]
H2O2 PB@GR/GCE −0.05 V(vs. SCE) 5 ~ 4000 0.005 [244]
glucose GO-Ag/GCE 0.6 V(vs. SCE) 1000 ~ 14,000 4 [245]
glucose NiO-GR/GCE 0.35 V(vs. Ag/AgCl) 20 ~ 4500 5 [246]
glucose rGO-Cu2O/GCE 0.6 V(vs. SCE) 10 ~ 6000 0.05 [247]
S2− hemin-rGO/GCE 0.05 V(vs. Ag/AgCl) 2 ~ 212 1.3 [248]
NO GR/Au/GCE 0.8 V(vs. SCE) 0.036 ~ 70 0.018 [168]
NO2− Pt-PANI-GR/GCE 0.75 V(vs. SCE) 400 ~ 7010 0.13 [249]
N2H4 GR-Bi/GCE 0.3 V(vs. Ag/AgCl) 0.020 ~ 280 0.005 [250]
acetaminophen rGO/GCE 0.5 V(vs. Ag/AgCl) 0.005 ~ 4 0.00213 [251]
tert-butyl hydroperoxide GR-CoPc/GCE –0.5 V(vs. SCE) 26.0 ~ 4810 5 [252]
promethazine rGO/GCE 0.78 V(vs. Ag/AgCl) 1.99 ~ 1030 0.199 [253]
dopamine GO-Au/pDAN-EDTA/GCE 0.3 V(vs. Ag/AgCl) 0.010 ~ 1 0.005 [254]
NADH rGO/GCE 0.35(vs. Ag/AgCl) 0 ~ 500 0.6 [255]
tyrosine Co3O4-GR/GCE 0.95 V(vs. SCE) 0.010 ~ 40 0.001 [256]
a
SPCE: screen printed carbon electrode
Microchim Acta (2017) 184:1–44
used to measure the release of H2O2 from living cells. Ensafi
[243] investigated the oxidative determination of H2O2 at
Nafion/GO-Co3O4 nanocomposite coated glassy carbon elec-
trode. The response of the modified electrode to H2O2 was
examined using amperometry (at 0.76 V vs. Ag/AgCl) and it
was found that the detection limit was 0.3 μM with a linearity
of up to four orders of magnitude.
Glucose detection is of great clinical importance, especially
for type 1 diabetes. Joshi [245] prepared GO-Ag nanocom-
posite with rudimentary simple electrochemical approach.
The composite was a superior catalyst material for electro-
chemical glucose oxidation due to synergistic interaction be-
tween the AgNPs and GO. The corresponding amperometric
sensor showed excellent selectivity and rapid detection for
glucose with good sensitivity. Zhu [246] developed a stable
and sensitive non-enzymatic glucose sensor based on electro-
chemically generated nickel (II) oxides-rGO nanocomposite.
This sensor has an about 1.5 times larger current response
toward the oxidation of glucose in alkaline media than that
of conventional nickel (II) oxides-modified electrode. The re-
sponse to glucose is linear in the 20 μM to 4.5 mM concen-
tration range with a DL of 5 μM. Zhou [247] presented an
rGO-Cu2O modified electrode for the amperometric detection
of glucose. The sensor exhibited excellent electrocatalytic ac-
tivity toward glucose oxidation with fast response (within 3 s),
wide linear range (0.01 ~ 6.0 mM), low DL (0.05 μM), high
sensitivity (185 μA mM−1) and selectivity.
Amperometric sensors are also employed for the detection
of other ions and small molecules. Nitric oxide (NO) is a
messenger molecule that plays important role in many physi-
ological and pathological processes. Wang [168] fabricated
GO-Au modified electrode for the amperometric analysis of
nitric oxide. The sensor exhibited high sensitivity and good
stability toward the oxidation of NO. Zhang [249] fabricated a
nitrite sensor based on a sandwich structure nanocomposite of
PtNPs supported on PANI modified graphene. Mir [254] con-
structed a highly sensitive amperometric sensor for selective
monitoring of K+-induced dopamine released from dopami-
nergic cells based on an ethylenediaminetertraacetic acid
(EDTA) immobilized-poly(1,5-diaminonaphthalne) (pDAN)
layer comprising GO and AuNPs. The sensor can discriminate
dopamine molecules from foreign species by catalytic effect,
surface charge, and hydrogen bonding-based interactions with
a probe molecule. Tabrizi [255] reported an rGO-based sensor
that exhibited fast response time, high stability, good
anti-fouling properties, low DL and high sensitivity for
the oxidation of NADH. Jiang [256] described an am-
perometric sensor based on Co3O4 NPs-GR nanocom-
posite film modified electrode for the determination of
tyrosine. The sensor performed excellently during the electro-
catalysis of L-tyrosine oxidation and satisfactory results were
achieved in the detection of drug samples as well as the repro-
ducibility and interference tests.
23
Potentiometric sensors
Potentiometric sensors operate by measuring the potential dif-
ference between the reference electrode and the indicator elec-
trode that changes its potential in response to the concentration
of analyte based on the Nernst equation. Potentiometric
methods are mainly applied to charged ions and sometimes
neutral molecules.
For example, Ping [257] reported a flexible potentiometric
sensor by using free-standing graphene paper as electrode
substrate (Fig. 11). The graphene paper acted as both electric
conductor and ion-to-electron transducer of the potentiometric
signals. Three integrated potentiometric sensing devices were
built by combining graphene paper-based ion-selective elec-
trodes and graphene paper-based reference electrodes, which
exhibited comparable performance with common types of po-
tentiometric detection system as well as excellent flexibility.
Abraham [258] developed a potentiometric sensor for Pb2+
based on 1,2-bis (N′-benzoylthioureido) benzene (BBTB)-
rGO modified electrode. The sensor can be used in a wide
range of pH from 4 to 8 and gives a good Nernstian slope of
30.37 ± 0.62 mV/decade for concentrations of Pb2+ between
6.31 × 10−8 to 3.98 × 10−2 M. Poursaberi [259] introduced a
novel fluoride-selective electrode based on metalloporphyrin
grafted-GO. The introduction of GO improved the dynamic
working range, detection limit, response time, life time, and
stability of the sensor. The electrode exhibited linear response
over a wide concentration range of 5.0 × 10−7 ~ 5.0 × 10−1 M
with a Nernstian slope of −58.3 mV per decade, and a short
response time of 20s.
Nooredeen [260] developed a potentiometric citrate selec-
tive electrode based on zinc monoamino-phthalocyanine-
graphene nanocomposite. The zinc-phthalocyanine mono-
amino covalently attached to graphene can act as a neutral
carrier for dihydrogen citrate anion. The sensor possessed
the optimum performance in glycine buffer 0.01 M of
pH 3.9 with a near Nernstian slope of −57.3 ± 0.5 mV per
decade, a linear range of 8 × 10−7 ~ 1 × 10−2 M and a DL of
5 × 10−7 M. Zhou [261] constructed a potentiometric sialic
acid sensor by electrodeposition of rGO at a GCE which was
then coated with a electropolymerized poly(anilineboronic ac-
id) (PABA) film. The electrochemical potential of the sensor
was sensitive to the reversible and covalent boronic acid-diol
binding between the composited film and sialic acid. Under
optimum conditions, the sensor exhibited low detection limit
of 0.8 μM with a wide linear range of 2 μM ~ 1.38 mM, high
stability, good regeneration, and remarkable selectivity.
Nikoleli [262] fabricated a potentiometric cholesterol bio-
sensor through the immobilization of cholesterol oxidase en-
zyme and polymerization mixture onto graphene electrode.
The strong biocompatibility among stabilized polymeric lipid
membranes and human biofluids endowed the presented bio-
sensor with appreciable reproducibility, good selectivity and
24
Fig. 11 Illustration of the
fabrication process of a graphene-
based potentiometric sensing
device. a Oxidation and
exfoliation, b reduction, c
filtration, d cutting, e coating, f
assembling, g dip-coating, and h
detecting. Reprinted with
permission from Ref [257].
Copyright (2013) Royal Society
of Chemistry
high sensing capability with a linear slope curve of ~64 mV
per decade. Rebelo [263] synthesized protein imprinted mate-
rials with charged binding sites by surface imprinting over
graphene layers to which the protein was first covalently at-
tached and the materials were used to develop simple and
inexpensive potentiometric sensor for prostate specific
antigen.
Impedimetric sensors
Electrochemical impedance spectroscopy (EIS) is particularly
suitable for monitoring changes in the interfacial properties of
an electrode surface since it does not require any additional
signal-generating labels and can be carried out with minimal
or no sample pretreatments. In addition, EIS is not destructive
and does not cause any alteration to the analytes [7]. This
technique has been adopted in combination with graphene
nanomaterials for chemical sensing and biosensing applica-
tions. Azadbakht [264] fabricated a ultrasensitive
impedimetric electrochemical iodate sensor based on GR-
PEI-AuNPs-polyacriflavine composite. Under optimized con-
ditions, the charge transfer resistance (Rt) values decreased
linearly with the concentrations of iodate in the range from
0.5 nM to 14.0 nM and the DL was calculated to be about
0.1 nM. Xiong [265] introduced a glassy carbon electrode
modified with β-CD-GR-1,10-diaminodecane nanocompos-
ite for the detection of di(2-ethylhexyl) phthalate (DEHP).
DEHP can enter into cyclodextrin cavity to form the guest-
host complex, leading to the increase of Rt. It was found that
the Rt value increased linearly with concentration of DEHP in
the range of 0.2 ~ 1.2 μM and the DL was about 0.01 μM.
Microchim Acta (2017) 184:1–44
Gutes [266] reported an impedimetric sensor for the detection
of polybrominated diphenyl ethers (PBDEs). The sensor was
fabricated by using AuNPs decorated single-layer graphene
and a specially designed binding peptide. With the increased
concentration of PBDEs, the Rt value increased due to the
high blocking capacity of the peptide-PBDEs structure. The
sensor showed a good linear response to decabromodiphenyl
ether in the range from 5 to 100 ppt and can discriminate non-
brominated diphenyl ethers. Kim [267] presented a novel
strategy for the construction of impedance sensing platform.
Probe protein molecules were denatured to render their hydro-
phobic residues exposed in order to facilitate their direct π-
stacking interactions with the surface of rGO nanosheets, ob-
viating the need for introducing external chemical groups of-
ten required for covalent immobilization. Bovine serum albu-
min (BSA) was selected as a model probe to assess the validity
of this approach and tens of femtomolar (25 fM) sensitivity for
anti-BSA antibody has been confirmed with EIS. Qi [268]
described an impedimetric biosensor for the detection of ma-
rine pathogen sulfate-reducing bacteria (SRB) based on cell-
mediated bioimprinted films where electrodeposited CHIT-
rGO hybrids served as the platform for bacterial attachment.
EIS experiments revealed that Rt increased with increased
SRB concentration and the linear relationship between ΔRt
and the logarithm of SRB concentration was obtained within
the concentration range of 1.0 × 104 to 1.0 × 108 cfu·mL−1.
Electrochemiluminescence sensors
Electrochemiluminescence (ECL) is an electrochemically
triggered optical radiation process produced by the energy
Microchim Acta (2017) 184:1–44
relaxation of excited species. Since no extra light source is
required, the background signals from scattered light and lu-
minescent impurities can be invalidated, leading to high sen-
sitivity. Moreover, ECL has high specificity due to the emitter-
coreactant relationship and good selectivity as the excited
states can be regulated by alternating the applied potential
[269, 270]. Graphenes are attractive carriers for luminophores
due to their high specific binding sites and excellent electro-
chemical performance [271].
Ru (bpy)32+ is a typical ECL reagent with high lumines-
cence and good electroactivity. Via π-interaction, Ru (bpy)32+
can be effectively immobilized on the surface of graphene. For
example, Gu [272] developed a one-step process for fabricat-
ing paper-based solid-state ECL sensor by screen-printing the
mixture of Ru (bpy)32+/PSS-GN/carbon paste on paper-based
chips. The sensor was very sensitive for the determination of
tripropylamine (TPA) with a low DL of 5.0 nM. Li [273]
constructed an ECL biosensor by immobilizing Ru (bpy)32+
nanowires (RuNWs) onto a GCE modified with rGO-Nafion
composite films. The introduction of rGO significantly en-
hanced the electrochemical signal of the RuNWs and hence
affected its ECL intensity. By taking TPA as co-reactant, the
ECL biosensor showed a wide linear response range
(1.0 × 10−12 ~ 1.0 × 10−5 M) and an extremely low DL
(3.1 × 10−13 M) for the detection of dopamine.
Hosseini [274] described a sensitive analytical method for
the determination of carbidopa, which is often administered as
a source of dopamine for the treatment of Parkinson’s disease.
The electrochemical oxidation of carbidopa at GR modified
gold electrode can lead to enhancement of the weak emission
of oxidized luminol. The ECL signal increases linearly with
increasing carbidopa concentrations over a range of
1.0 × 10−9 ~ 1.7 × 10−7 M, with a DL of 7.4 × 10−10 M.
Wang [275] prepared an ECL napropamide sensor by using
the luminol ECL system on Nafion-sulfonated GR modified
electrode. The sulfonated GR may act as solid-phase
Fig. 12 Schematic Diagram for
the Fabrication of the GO based
ECL immunosensor. Reprinted
with permission from Ref [277].
Copyright (2015) American
Chemical Society
25
microextraction material for napropamide. The aromatic π
stacking and electrostatic attraction between positively
charged napropamide and negatively charged Nafion-
sulfonated GR can enhance the ECL signal, resulting the high
selectivity and sensitivity.
Wang [276] designed an ECL sensor based on the CdSe
quantum dots (QDs) enhanced by GO-CHIT composite. The
porous structure of the GO-CHIT composite can not only load
much more CdSe QDs and provide large interface of electrode
reaction, but also facilitate the diffusion of coreactant K2S2O8
into the membrane, resulting in excellent ECL performance.
The sensor exhibited high ECL intensity, good biocompatibility
and long-term stability, and was used to detect of cytochrome C
(Cyt C). Lv [277] described an ECL sensor based on polypyr-
role intercalated amination graphene oxide (NH2GO) and
Ag2Se@CdSe nanoneedles (Fig. 12). The increased specific
surface area of NH 2 GO resulted in larger loading of
Ag2Se@CdSe, leading to the enhancement of ECL intensity
and the improvement the sensitivity. The sensor was employed
for the detection of a tumer marker CA72–4 in the presence of
K2S2O8, exhibiting good linear relationship in the range from
10−4 to 20 U·mL−1 and low DL of 2.1 × 10−5 U·mL−1. Xin
[278] designed an ECL cytosensor by using a ternary compos-
ite of hemin-rGO-AuNPs as a mimetic peroxidase which can
initiate sensitive ECL quenching of QDs due to the electrocat-
alytic reduction of the coreactant H2O2. Based on the consump-
tion of the H2O2 and the recognition between concanavalin A
and mannose or Nglycans on the cell surface, the cytosensor
was used to sensitively detect K562 cells with a linear calibra-
tion ranging from 4.8 × 102 to 5.0 × 105 cells per mL.
Photoelectrochemical sensors
Photoelectrochemical (PEC) method is a relatively new tech-
nique that works based on electron transfer between analyte,
photoactive species and electrode with photoirradiation, and
26
has attracted extensive attention in the field of bioanalysis and
environmental monitoring [279]. The introduction of GR can
enhance the charge separation and facilitate the charge transport,
and thus improve the analytical performances of PEC sensor.
Wang [280] fabricated a PEC H2O2 sensor based on the
composition of horseradish peroxidase (HRP), flower-like
CuInS2 and graphene. Herein, graphene acted as highly con-
ductive scaffolds for electron transport and accept
photogenerated electrons from CuInS2, thus inhibited the re-
combination of photogenerated electron-hole pairs and en-
hance the photocurrent. The photocurrent proportionally in-
creased with the concentration of H2O2 in the range of
5.0 × 10−7 ~ 5.3 × 10−4 M with a DL of 4.7 × 10−7 M.
Cheng [281] presented another PEC H2O2 sensor based on
ternary cooperative Au-CdS-rGO hetero-nanostructures. The
hetero-nanostructure facilitated more efficient utilization of
incident light, and the photogenerated electrons were more
efficiently transferred from CdS, leading to higher photocur-
rent density than that at Au-CdS modified electrode.
Zhang [282] presented a glucose biosensor using GR-CdS
QDs based photoelectrode. Graphene can serve as an excellent
electron-transport matrix to capture and transport electrons
from excited CdS, avoiding electron-hole recombination and
resulted in high light sensitivity. Under optimized conditions,
the sensor showed low applied potential of 0.2 V, wide linear
range of 0.1 ~ 4 mmol·dm−3 and low DL of 7 μmol·dm−3. Shen
[283] constructed a PEC cysteine sensor based on rGO/
CdS:Mn nanocomposites. The nanocomposites inherited the
excellent electron transport property of graphene and facilitated
the spatial separation of charge carrier, therefore exhibited en-
hanced photocurrent intensity. The sensor displayed excellent
analytical performance for the detection of cysteine with a wide
linear range from 0.1 μM to 20 mM and a low DL of 0.02 μM.
Wang [284] synthesized Gr-TiO2 nanohybrids for the PEC
determination of NADH. Since the sensor worked under vis-
ible light excitation, the destructive effect of UV light to bio-
molecules was reduced. The PEC sensor displayed good
photoelectrochemical activity towards NADH with wide lin-
ear range from 1.0 × 10−8 to 2.0 × 10−3 M and low DL of
3.0 × 10 −9 M. Qian [285] selected BiPO 4 -rGO as the
photoelectrochemically active materials and developed a
PEC chlorpyrifos sensor based on a different analytical strat-
egy. Upon the addition of chlorpyrifos, the formation of a Bi-
chlorpyrifos complex gave rise to an increase in steric hin-
drance, which consequently resulted in an obvious decrease
in photocurrent. The current change was linear to the concen-
tration of chlorpyrifos in the range from 0.05 to 80 ng·mL−1
with a low DL of 0.02 ng·mL−1.
Field effect transistor sensors
Field effect transistor (FET) sensors have the structure of a
common three-electrode transistor, where the source and drain
Microchim Acta (2017) 184:1–44
electrodes are bridged by a semiconductor channel and used
as the sensing component, while gate electrodes modulate the
channel [286, 287]. The unique electronic properties of
graphene make it an enticing electronic material in the design
of FET [288]. Maehashi [289] reported a solution-gated
graphene FET for the detection of K + by choosing
valinomycin as a selective ionophore (Fig. 13). K+ can bind
to the valinomycin in the graphene channel and affected the
electrical potential of the channel, resulting in a negative shift
of the transfer curves. The valinomycin-modified graphene
FETs demonstrated highly sensitive, selective electrical detec-
tion of K+ over a wide concentration range, from 10 nM to
1.0 mM. In another report [290], Sohn presented a pH sensor
based on solution-gated rGO FETs. A self-assembled
networked rGO film was incorporated as the sensing layer.
The oxygen-containing functional groups on the surface and
edges of rGO may enhance the pH responsiveness, leading to
reliable pH sensing capability. The FET was very sensitive to
H+ and was applied to the enzyme-based sensing of acetyl-
choline through the detection of H+ produced during the en-
zymatic reaction.
Zhang [291] reported a whole-graphene FET dopamine
sensor by using graphene as both channel and gate electrodes.
The sensing mechanism was attributed to the change of effec-
tive gate voltage applied on the transistors induced by the
electro-oxidation of dopamine at the graphene gate electrodes.
The FET sensor showed stable performance, high sensitivity
and the low DL down to 1 nM.
Huang [292] demonstrated the post-treatment of GO in
order to yield a practical liquid-gated FET sensor suitable for
real-time and sensitive detection of IL-6 proteins. A facile
atmospheric-pressure ethanol CVD treatment on top of pre-
coated GO can increase the size, graphitization and reduction
of GO and thus overcome the limitations of high electrical
resistance and variable coverage between fabricated chips in
Fig. 13 Schematic image of the measurement setup incorporating a
valinomycin-modified graphene FET device. Reprinted with permission
from Ref [289]. Copyright (2013) Elsevier
Microchim Acta (2017) 184:1–44 27

the case of non-treated GO. The FET sensor was very specific
for the detection of Interleukin-6 and the sensing window was
within the physiologically relevant range, from 4.7 to 300 pg·
mL−1. Chen [293] described a novel approach for enzymatic
assay at graphene FET. The approach involves real time mon-
itoring of drain current of rGO in the presence of phospholi-
pase A2 (PLA2). The rupture of reporter-encapsulated lipo-
somes triggered by PLA2 led to the release of reporter mole-
cules, which subsequently adsorb on rGO, thereby modulating
the conductance of rGO. In virtue of the signal enhancement
effect by the excess concentration of reporter molecules en-
capsulated in liposomes, the detection of PLA2 in terms of
both activity and concentration was achieved and the DL
was as low as 80 pM.
Electrochemical immunosensors
Electrochemical immunosensors are attractive analytical tools
based on the detection of biospecific recognition interactions
between antigen (Ag) and antibody (Ab), and have received
considerable attention in clinical diagnoses, biochemical stud-
ies and environmental monitoring [294, 295]. Graphene is
very attractive for the construction of electrochemical
immunosensors since their large surface area can offer high
loading amount of biomolecules, while their high conductivity
and good electrocatalytical activity can facilitate the electron
transfer rate of electroactive species [296]. Table 5 shows
various graphene based electrochemical immunosensors for
the detection of organic molecules [297–299], proteins
[300–308], and even virus [309] and bacteria [310, 311].
Eissa [297] constructed an immunosensor for the detection
of okadaic acid (OA), a kind of biotoxin, by covalently
immobilizing Ab on poly 4-carboxyphenyl (P4CP) modified
graphene electrodes. The assay relied on the competition be-
tween the free and the conjugated OA for OA-Ab
immobilized on the electrode surface. The less the free OA
in solution, the more the OA-ovalbumin conjugate will bind to
the Ab on the electrode surface, which will subsequently de-
crease the [Fe(CN)6]3−/4− reduction peak current in the square
wave voltammetry. Srivastava [298] prepared a label-free
immunosensor for the determination of another biotoxin, af-
latoxin B1, based on Abs bioconjugated with AuNPs on rGO.
The monodispersion of the Au nanoparticles on the rGO
sheets prompted the heterogeneous electron transfer, resulting
in improved biosensor efficacy.
Also based on AuNPs-rGO, Elshafey [300] reported a
label-free immunosensor for the detection of p53 antibodies.
The AuNPs-rGO hybrid interface not only provided a large
surface area for the effective immobilization of p53 antigens,
but also ascertained their bioactivity and stability. The
immunosensor showed excellent analytical performance for
the detection of p53 antibody with high selectivity and repro-
ducibility. Human chorionic gonadotropin (hCG) is a well-
known glycoprotein hormone acting as an important diagnos-
tic marker of pregnancy as well as a tumor marker for certain
cancers. Roushani [302] covalently attached Ab to AgNPs/
GR-IL-CHIT nanocomposite and developed an
immunosensor by using riboflavin as the redox probe. HCG
was detected by monitoring the DPV peak current changes
caused by the formation of Ab-Ag complexes. Due to large
amounts of anti-hCGs immobilized, the electrochemical
immunosensor showed a wide linear range and a low detec-
tion limit. Chen [304] described a novel sandwich-type
immunosensor for the ultrasensitive detection of Vangl1, a

Table 5 Various electrochemical immunosensors based on functionalized graphene

Analytes Product/probe analyzed Immobilizing support Technique Linear range (ng·mL−1) Detection limit Ref.
(for Ab/Ag) (ng·mL−1)

okadaic acid [Fe(CN)6]3−/4− P4CP /GR SWV ~5 0.019 [297]

aflatoxin B1 [Fe(CN)6]3−/4− Au/rGO CV 0.1 ~ 12 0.1 [298]
clenbuterol [Fe(CN)6]3−/4− octadecanoic acid -GO impedimetry 0.0 ~ 10 0.00657 [299]
p53 Ab [Fe(CN)6]3−/4− Au/rGO SWV 1 × 10−4 ~ 10 8.8 × 10−5 [300]
Prostate specific Ag [Fe(CN)6]3−/4− silk peptide-GO DPV 0.1 ~ 5.0, 5.0 ~ 80.0 0.053 [301]
hCG riboflavin Ag/GO-IL-CHIT DPV 0.0212 ~ 530 mIU·mL−1 0.0066 mIU·mL−1 [302]
prolactin α-naphthol Au/GO-CNT DPV 0.050 ~ 3.2 0.047 [303]
Vangl1 H2O2 rGO-TEPA-PTC-NH2 amperometry 1 × 10−4 ~ 0.450 3 × 10−5 [304]
α-fetoprotein [Fe(CN)6]3−/4− Au/GO-CNT DPV 0.01 ~ 100 0.003 [305]
myoglobin myoglobin Au/rGO DPV 1 ~ 1400 0.67 [306]
LMP-1 H2O2 CHIT-GO-CNT DPV 0.01 ~ 40 6.2 × 10−4 [307]
bovine interleukin-4 [Fe(CN)6]3−/4− rGO-CHIT impedimetry 0.1 ~ 50 0.080 [308]
Virus H7N9 methylene blue Sol-gel/Au/GR-CHIT DPV 0.008 ~ 0.060 8.1 × 10−4 [309]
E. coli Ag Ag/GO SSV 50 ~ 106 CFU·mL−1 10 CFU·mL−1 [310]
Salmonella pullorum Au Au/rGO DPV 100 ~ 1 × 106 CFU·mL−1 89 CFU·mL−1 [311]
28
highly conserved planar cell polarity protein which played
pivotal roles in embryogenesis. Herein, a nanocomposite
consisting of rGO, 3,4,9,10-perylenetetracarboxylic
dianhydride (PTC-NH 2 ) and tetraethylene pentamine
(TEPA) was used to immobilize the captured Abs, while
C60-templated AuPt bimetallic nanoclusters were utilized to
immobilize the secondary Ab for additional signal amplifica-
tion. Latent membrane protein 1 (LMP-1) is a cancer marker
that affects the differentiation, morphology, and growth of
human epithelial cells. Zhang [307] developed an electro-
chemical sandwich immunosensor for the determination of
LMP-1 based on capture antibody (Ab1) immobilized on
CHIT-GO-CNT nanocomposite. The detection antibody
(Ab2) marked with thionine was fixed on a composite of
HRP/Pd@Pt-CNT. Following exposure to LMP-1, an ampli-
fied signal was observed because of the synergistic effect be-
tween the Pd@Pt NPs and HRP in the presence of added
H2O2. The immunosensor exhibited high sensitivity and low
detection limit.
Influenza viruses are causative pathogens highly pathogenic
to human. Yang [309] reported a new electrochemical
immunosensor for of voltammetric detection of H7N9 virus.
AuNPs electrodeposited on GR surface acted as a support for
alcohol dehydrogenase (ADH) in a sol-gel containing thiol
groups, while protein A was used to properly orientate
immobilized antibody against H7N9 on the sol-gel. By using
a sandwich strategy with methylene blue as the indicator, the
immunosensor provided a powerful and versatile tool in point-
of-care test for H7N9 with a wide linear range of 8 ~ 60 pg·
mL−1 and a low detection limit of 0.81 pg·mL−1. Escherichia
coli (E. coli) is a common type of microorganism which has
been extensively used as an indicator organism for water qual-
ity in many countries. Jiang [310] fabricated an E. coli electro-
chemical immunosensor based on solid-state voltammetry
(SSV) by using GO-Ag-Ab nanocomposites as probes
(Fig. 14). The AuNPs were self-assembled on the electrode
surface and served as an effective matrix for Ab attachment,
and the analyte and the probes were simultaneously captured
onto the sensor under a sandwich type immunoassay format.
Combining the advantages of the high-loading capability of
graphene oxide with promoted electron-transfer rate of
AuNPs, this immunosensor exhibited a wide linear dependence
Fig. 14 Schematic image of the E. coli sensing strategy. Reprinted with permission from Ref [310]. Copyright (2013) Royal Society of Chemistry
Microchim Acta (2017) 184:1–44
on the logarithm of the concentration of E. coli ranging from 50
to 1.0 × 106 cfu·mL−1 with a DL of 10 cfu·mL−1.
Gas sensors
Gas sensors are devices that can be used to detect combustible,
explosive and toxic gases, and have played a significant role in
the fields of environmental analysis, safety monitoring and
process control [312]. Chemiresistors and FETs are the most
widely used configurations of electrochemical gas sensors, in
which the gaseous analytes were detected by measuring the
resistance changes or drain current changes of sensing layers
changes induced by adsorbing the gas molecules [313, 314].
Graphene has attracted much attention as a gas-sensing
nanomaterial because its promising potential for the selective
and rapid detection of various gas molecules due to the excep-
tional properties, especially the high carrier mobility and den-
sity, and low intrinsic noise [315, 316].
Choi [317] fabricated a flexible and transparent all
graphene sensor that exhibited high-performance with a
ΔR/R0 ratio of 10 % with 0.5 ppm NO2 gas. With the aid of
an integrated graphene heater layer, a rapid response and re-
covery time smaller than 20 s was achieved. In addition, the
combined devices are guaranteed with a gas sensing sensitiv-
ity ratio ΔR/R0 of 12 % for 1 ppm NO2 gas under a bending
strain rate of 1.4 %. The authors expected that their work may
present the possibility for an unconstrained size and design of
smart window and wearable nose-sensors. Since different gas
molecules can be adsorbed on the surface of graphene, the
selectivity of graphene based gas sensors may still need to
be improved. Lipatov [318] described a solution for this prob-
lem by employing an array of rGO-based integrated sensors
instead of focusing on the performance of a single sensing
element. The resulting gas sensor can reliably recognize
analytes of nearly the same chemical nature and was even
sufficient to discriminate between different alcohols, such as
methanol, ethanol and isopropanol. Chemical modification is
an effective approach for improving the performance of
graphene based gas-sensing applications. Yuan [319] reported
chemoresistor-type NO2 sensors based on chemically modi-
fied graphene nanomaterials. The chemical modification of
sulfonic acid or amine groups led graphene sheets to be further
Microchim Acta (2017) 184:1–44
hole-doped, which prompted the adsorption of electron-
withdrawing NO2 molecules, greatly improved the perfor-
mances of NO2 sensors. In addition, the sensors can sponta-
neously recover to their initial states by flowing N2 gas with-
out UV/IR light illumination or thermal assistance.
Functionalization with metals and metal oxides
nanomaterials can open up a sizable energy gap in graphene
through the quantum confinement effect, resulting in en-
hanced gas sensing performance [320]. Peng [321] fabricated
a H2 sensor by dielectrophoresis of Pd-Pt/rGO ternary nano-
composite. The sensor has a stable and repeatable response
due to carrier donation and crystal lattice expansion over hy-
drogenation and dehydrogenation. In the presence of H2, the
adsorption of atomic hydrogen led to the formation of hy-
drides, which lowered the work function of Pt and Pd nano-
particles, resulting in electron donation from the metal hydride
to the rGO. Uddin [322] constructed a chemiresistive type of
C2H2 gas sensor by synthesizing a Ag-ZnO-rGO hybrid. At
optimum conditions, the sensor showed a high response of
21.2 (100 ppm C2H2) at 150 °C, an acceptable detection range
of 1 ~ 1000 ppm, excellent repeatability, fast response/
recovery times of 25/80 s, good selectivity and performance
stability up to 31 % relative humidity concentration. In anoth-
er case, Su [323] described a novel room-temperature NH3 gas
sensors based on Pd-SnO 2 -rGO nanocomposite film.
Experimental results indicated that the gas sensor had high
sensitivity even at a low testing concentration of NH3 and
good linearity from 5 to 150 ppm at room-temperature.
Combination of conducting polymers and graphene also pro-
vides an effective and practical approach to advanced gas
sensor. Hasani [324] developed a gas sensor for volatile or-
ganic compounds (VOC) based on the incorporation of GO in
PEDOT-PSS, a non-stoichiometric polyelectrolyte complex.
Due to the enhanced direct charge transfers, increased specific
surface area and intrinsic sensing properties of the PEDOT-
PSS/GO nanocomposite, the VOC sensor exhibited high sens-
ing performance to methanol with concentrations ranging
from 35 to 1000 ppm at room temperature.
Enzymatic sensors
Electrochemical enzymatic sensors combine the special
catalytical activity of enzymes with the analytical power of
electrochemical device, and have been shown to be extremely
useful for the detection of a wide variety of substrates in clin-
ical, environmental, and food samples [325]. Graphene based
functional nanomaterials have proven to be helpful for the
effective immobilization of enzymes, increasing sensing area
and enhancement of the electron transfer rate, leading to high
biosensing performance [17, 326].
Liu [327] reported a phospholipid-graphene
bionanocomposite and demonstrated its application in enzyme
immobilization. Due to the excellent electrical conductivity of
29
graphene and the favorable biocompatibility of the phospho-
lipids, the immobilized microperoxidase-11 (MP-11) main-
tained its activity and can realize direct electrochemistry. The
biosensor was successfully employed for the electrocatalytic
detection of H2O2 and exhibited good performance. Zhou
[328] presented an amperometric H2O2 biosensor based on a
biosensing film consisting of poly(N-isopropylacrylamide)-b-
poly(2-acrylamidoethyl benzoate) (PNIPAM-b-PAAE), GO
and hemoglobin (Hb). The film provided a favorable micro-
environment for Hb to facilitate the electron transfer to the
electrode. Due to the temperature-responsive property of
PNIPAM-b-PAAE, the biosensor exhibited two different elec-
trocatalytic activities toward H2O2 upon temperature stimuli
from 26 to 36 °C.
Li [329] studied the direct electron transfer of glucose ox-
idase (GOx) adsorbed on the surface of CHIT-rGO-ZnO-Ag
nanocomposite modified electrode. The nanocomposite was
very effective in facilitating the electron transfer between ac-
tive sites of GOx and the electrode. Due to the synergistic
effects, the biosensor showed a broad linear measuring range,
low detection limit and high sensitivity for the determination
of glucose. Zhou [330] developed a biosensor based on the
direct electrochemistry of laccase (Lac) on 1-aminopyrene (1-
AP)-functionalized rGO-modified electrode (GCE) by encap-
sulation with chitosan. Results indicated that the AP-rGO was
a friendly platform for the immobilization of enzyme, which
facilitated the electron exchange. Without the aid of any elec-
tron mediator, the biosensor showed good reproducibility and
high sensitivity to 2,29-azinobis(3-ethylbenzothiazoline-6-
sulfonate)diammonium with a detection limit of 0.1 mM and
a linear concentration range of 2 ~ 1000 mM.
Zheng [331] fabricated a highly sensitive and organophos-
phorous pesticides (OPs) biosensor based on acetylcholines-
terase (AChE) immobilized by IL-GO-polyvinyl alcohol
(PVA) nanocomposites. The nanocomposite with excellent
conductivity and biocompatibility offered an extremely hy-
drophilic surface for AChE adhesion, effectively promoted
the electron transfer rate and facilitated the access of substrates
to the active centers. As a result, the prepared biosensor
showed high sensitivity, low detection limit, good fabrication
reproducibility and acceptable stability towards OP detection.
Ju [332] introduced a triazophos biosensor based on its inhi-
bition of AChE, which was immobilized onto the surface of
cysteamine functionalized coral-like gold nanostructures on
rGO. The biosensor showed linear response to
acetylthiocholine in the 0.3 ~ 300 μM concentration range
and the inhibition by triazophos can be determined in concen-
trations of up to 210 ppb, with a detection limit of 0.35 ppb.
Dey [333] developed a sensitive cholesterol biosensor
based on graphene-bienzyme hybrid materials. Cholesterol
oxidase and cholesterol esterase were immobilized on the Pt
nanoparticle decorated graphene, where the Pt nanoparticle
based hybrid material modified electrode efficiently catalyzes
30
the electrochemical oxidation of H2O2 (Fig. 15). The combi-
nation of electronically highly conductive graphene and cata-
lytically active Pt nanoparticle favors the facilitated electron
transfer for the oxidation of H2O2, resulting in fast, sensitive
and selective analysis of cholesterol. In another report, Parlak
[334] demonstrated a template-directed self-assembly ap-
proach for the construction of cholesterol biosensor. An an-
ionic surfactant was used to direct the assembly of cholesterol
oxidase and cholesterol esterase on the surface of the rGO;
while gold nanoparticles are incorporated into the hetero-
assembly to enhance the electro-biocatalytic activity. The bio-
sensor exhibited a linear response to H2O2 from 0.01 to
14 mM, with a DL of 25 nM; while the amperometric re-
sponse with cholesterol showed a linear range from 0.05 to
0.35 mM and a DL of 0.05 mM.
In some cases, an adequate electron-transfer mediator is
crucial to provide improved selectivity of biosensors. Kim
[335] synthesized a new electron-transfer mediator, an iron
complex with a phenanthroline attached to a bisthiophene-
pyrrole backbone. This complex can stably adsorb onto the
graphene surface through π-interaction, resulting in an en-
hanced electron-transfer process to the NADH-glucose dehy-
drogenase (GDH) system. Based on the mediator-rGO/
NADH-GDH nanocomposite, a disposable screen printed glu-
cose sensor was constructed. The sensor demonstrated excel-
lent performance for the detection of glucose.
Nucleic acid-based biosensor
Identification of specific DNA sequences can provide prom-
ising application in the field of genetic diseases diagnosis.
Electrochemical DNA sensors have attracted tremendous at-
tention because they can offer high sensitivity, high selectivity
and low cost for DNA detection [192, 336].
In the cases of voltammetric or amperometric biosensors,
electroactive species are often employed as indicators to report
Fig. 15 Scheme illustrating the
biosensing of cholesterol ester
with the GR-PtNPs based
biosensor. Reprinted with
permission from Ref [333].
Copyright (2010) American
Chemical Society
Microchim Acta (2017) 184:1–44
the electrochemical signals or changes occurring in the hy-
bridization of probe DNA with target DNA. Functionalized
graphene can not only benefit the immobilization of probe
DNA but also facilitate the electron transfer between
electroactive indicators and the electrode, leading to improved
analysis performance. For example, Chu [337] developed a
circulating tumor DNA sensing platform based on MoS2-
graphene nanocomposites. K3[Fe(CN)6] was used as the indi-
cator to monitor the DPV response decreases caused by DNA
hybridization. The biosensor can detect trace amounts of
DNA in the range from 1.0 × 10−16 M to 1.0 × 10−13 M with
a DL of 1 × 10−17 M. Similar strategy has be employed for the
construction of DNA sensor by using AuNPs/GO-VS2 [338],
AuNPs@PAMAM/GO [339] as probe DNA immobilization
materials. In some biosensing systems, the current response of
electroactive indicators are initiated by other reactions accom-
panied the hybridization process. Highly up-regulated in liver
cancer (HULC), a kind of long non-coding RNAs, is a novel
promising noninvasive biomarker for hepatocellular carcino-
ma. Liu [340] described a sandwich-type strategy for the de-
tection of HULC based on a PtPd-GO/Au/HRP/Au/thionine
composite. The application of GO may prompt the amount of
loading of PtPd, which can achieve triple-catalysis with HRP
and enhance the catalytic efficiency toward H2O2. As the
HULC concentration increased, the cathodic peak current of
H2O2 increased linearly with the HULC concentrations in the
range of 1.00 × 10−3 to 1.00 × 103 pM·mL−1.
Besides DNA detection, nucleic acid-based biosensors also
exhibit good performance in the analysis of other substances.
Aptamers are synthetic single-stranded oligonucleotides
which can bind to specific target biomolecules. Concerted
efforts have been put into developing aptasensors due to their
advantages such as high specificity, low molecular weight,
simple structure and easy synthesis. For example, Sanghavi
[341] reported a competitive electrochemical detection system
for the real-time monitoring of adenosine triphosphate (ATP)
Microchim Acta (2017) 184:1–44
based on AuNPs decorated-graphene (AuNP-GR) modified
electrode (Fig. 16). The modification with AuNP-GR caused
a net enhancement in signal sensitivity due to the enhanced
adsorption and electron-transfer kinetics of flavin adenine di-
nucleotide (FAD). Binding of FAD-prebound ATP to ATP
aptamer caused the release of an equivalent concentration of
FAD, which was quantitatively detected by electrochemical
adsorption stripping square wave voltammetry. As a result,
the ATP detection system exhibited a wide linear working
range of 1.14 × 10−10 to 3.0 × 10−5 M with a low DL of
2.01 × 10−11 M. Zhan [342] constructed a label-free electro-
chemical aptasensor for tetracycline (TET) by introducing the
aptamer on the surface of electrode modified with a nanocom-
posite consisting of rGO, Fe3O4 NPs and sodium alginate.
After the aptasensor was incubated with TET, the formation
of a complex of the aptamer and target made the aptamer
configuration rigid and resulted in the orientation of redox
probe towards the electrode, leading to distinctly increased
peak currents. Benvidi [343] also presented a TET biosensor
based on covalently immobilized aptamer on rGO modified
electrode. Under optimum conditions, a wide dynamic range
(1 × 10 −13 ~ 1 × 10 −5 M) and a low detection limit
(2.9 × 10−14 M) were obtained by EIS technique. Shamsipur
[344] described a biosensor for the determination of the serine
protease lysozyme, a fairly small protein responsible for
breaking down the polysaccharide walls of certain bacteria.
Thiolated aptamer was self-assembled on AuNP/rGO nano-
composite through Au-S bonds. The interaction of
immobilized aptamers with lysozyme led to the increased
charge transfer resistance (Rct) when using methylene blue
as a redox probe. Another lysozyme aptasensor was fabricated
by using aptamer-wrapped nanocomposite consisting of 3D
rGO, Cu2O, and plasma-polymerized propargylamine (PpPG)
as the sensing layer [345]. Taking advantages of both the high
affinity adsorption of aptamer towards PpPG and the relative
good electrochemical activity of the nanocomposite, the
aptasensor exhibited low detection limit and good stability.
Wang [346] developed a cancer cell sensor by the layer-by-
Fig. 16 Design of an ATP detection system with FAD displaced signaling. Reprinted with permission from Ref [341]. Copyright (2010) American
Chemical Society
31
layer (LBL) assembly of ferrocene-poly(allylamine hydro-
chloride) (Fc-PAH) functionalized graphene, PSS and aptamer
AS1411. LBL method can provide more effective probes to
improve the sensitivity. Once the bionanocomposite structure
binding target cancer cells, the current response decreased due
to the insulating properties of cellular membrane. The sensor
exhibited a widely detection range from 10 to 106 cells·mL−1
as well as good selectivity and stability. Jia [347] prepared a
Salmonella biosensor by covalently binding amino-modified
aptamer to rGO-CNT nanocomposite via amide bonds.
Combination of the bacteria and aptamer blocked the electron
transfer, resulting in a large increase in impedance. Therefore,
Salmonella can be easily determined in the range from 75 to
7.5 × 105 cfu·mL−1 and detection limit of 25 cfu·mL−1.
Moreover, the aptasensor can directly detect the whole bacte-
ria without pretreatment steps and an extraction procedure.
Conclusions and outlook
In this review, we try to provide insight into the synthesis of
graphene nanocomposite and its molecular functionalization
according to the functional materials and operational proce-
dures employed. Compared with other kinds of carbon
nanomaterials, such as carbon nanotubes, fullerene, carbon
dots and nanodiamond, graphene has the advantages of facile
synthesis, rich anchor sites, high surface area, excellent bio-
c o m p a t i b i l i t y, a n d i n e x p en s i v e p r o d u c t i o n c o s t .
Nanomaterials, inorganic/organic materials, polymers or
biomacromolecules functionalized graphene can be achieved
by various ways, including mechanically mixing, hybridiza-
tion, co-deposition, in situ growth, covalent or non-covalent
interaction, and so on. Graphene can cooperate with other
functional species to take advantage of the synergistic effect
and enhance the electroanalytical performances, and have
been utilized in a wide variety of electrochemical sensors
and biosensors, including voltammetric, amperometric, poten-
tiometric, impedimetric, immune, ECL, PEC, and FET, which
have promising electroanalytical applications in the fields of
32
environmental monitoring, food safe control, biomedical anal-
ysis, health care and clinical diagnose.
Despite the considerable advances during last several
years, much effort remains to be devoted to facilitating the
practical applications of functional graphene nanocomposite
and broadening the scope of their electrochemical sensing and
biosensing. Firstly, it is still challenging to synthesize mono-
disperse graphene sheets with controlled sizes, shapes and
electrochemical properties. Graphene often contains metallic
or carbonaceous impurities originated either from the starting
material (graphite) or from the production processes, which
directly influence the electrochemical behavior of the
graphene materials. Moreover, all current methods for
graphene synthesis are inefficient and time-consuming, while
even very small variations in the preparation process can lead
to varying electrochemical properties. Therefore, it’s impera-
tive to find effective procedures for the scalable production of
high-quality graphene. Secondly, although researchers have
confirmed the catalytical effect of graphene nanocomposite
in electrochemical sensors, there still remains much to be un-
derstood regarding the detailed sensing mechanism, such as
the mechanism of the oxidation/reduction of graphene them-
selves, the role of graphene in the catalytical mechanism of
electrode reactions, the interaction mechanism between
graphene and the analyte molecules, and the influence mech-
anism of the specific oxygen-containing groups at the edges of
graphene sheets on the catalytical activity. A more mature
theory may help functionalizing graphene with expected prop-
erties and bring new directions for the construction of
graphene nanocomposite based sensors. Thirdly, since the per-
formance of graphene nanocomposite is highly dependent on
their nanoscale architecture, it is desirable to explore efficient
methods for the precise design of the morphology and struc-
ture. On the one hand, it is still extremely difficult to fully
prevent the aggregation of graphene, especially for single- or
few-layered graphene. On the other hand, the same direct
nucleation-growth or other in situ functionalization ap-
proaches may accidently lead to much different micro-
structured nanocomposite. In the both cases, the properties
and the performance of the graphene nanocomposite are im-
pacted. So, novel strategies for synthesizing graphene nano-
composite with finely controlled architectures are very
important.
Mean while, many new trends on the functionalization and
electroanalytical application of graphene nanocomposite are
emerging. To begin with, since graphene possesses chemical
and physical properties that are highly desirable for flexible
electrochemical sensors, it has shown strong potential as a
component in wearable electronics, especially for daily health
monitoring. Next, due to its outstanding optical transmittance,
graphene has been regarded as an excellent replacement ma-
terial for ITO and has attracted great attention in the fabrica-
tion of transparent electrochemical sensors. Finally, graphene
Microchim Acta (2017) 184:1–44
is a promising material for screen-printed electrodes, which
are suitable to be drawn in different shapes with the virtue of
good reproducibility, mass production, easy miniaturization,
and low cost. The combination of ink chemistry about func-
tional graphene nanocomposite and the 3D printing tech-
niques will generate exciting opportunities for screen-printed
electrochemical sensors.
In conclusion, although challenges and problems still exist,
it is clear that functional graphene nanocomposite shows very
bright and exciting prospect in the electroanalysis field.
Researchers and engineers will find more efficient ways to
combine new functional materials and fabricating procedures
with advanced electronic technology, endow graphene nano-
composite based electrochemical sensors perfect analytical
performance and extend their scope for practical sensing
applications.
Acknowledgments This research is supported by the National Nature
Science Foundation of China (Nos. 31070885) and Wuhan Education
Foundation (2010005).
Compliance with ethical standards The author(s) declare that they
have no competing interests.
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