Anal Bioanal Chem (2014) 406:3957–3975
DOI 10.1007/s00216-014-7804-x
REVIEW
Graphene-based sensors for detection of heavy metals
in water: a review
Jingbo Chang & Guihua Zhou & Erik R. Christensen &
Robert Heideman & Junhong Chen
Received: 25 January 2014 / Revised: 16 March 2014 / Accepted: 31 March 2014 / Published online: 17 April 2014
# Springer-Verlag Berlin Heidelberg 2014
Abstract Graphene (G) is attracting significant attention be-
cause of its unique physical and electronic properties. The
production of graphene through the reduction of graphene
oxide (GO) is a low-cost method. The reduction of GO can
further lead to electrically conductive reduced GO. These
graphene-based nanomaterials are attractive for high-
performance water sensors due to their unique properties, such
as high specific surface areas, high electron mobilities, and
exceptionally low electronic noise. Because of potential risks
to the environment and human health arising from heavy-
metal pollution in water, G-/GO-based water sensors are being
developed for rapid and sensitive detection of heavy-metal
ions. In this review, a general introduction to graphene and
GO properties, as well as their syntheses, is provided. Recent
advances in optical, electrochemical, and electrical detection
of heavy-metal ions using graphene or GO are then highlight-
ed. Finally, challenges facing G/GO-based water sensor de-
velopment and outlook for future research are discussed.
Keywords Graphene . Graphene oxide . Water sensors .
Metal ions . Detection limits
Published in the topical collection Chemosensors and Chemoreception
with guest editors Jong-Heun Lee and Hyung-Gi Byun.
J. Chang : G. Zhou : J. Chen (*)
Department of Mechanical Engineering, University of
Wisconsin-Milwaukee, 3200 North Cramer Street, Milwaukee,
WI 53211, USA
e-mail: jhchen@uwm.edu
E. R. Christensen
Department of Civil and Environmental Engineering, University of
Wisconsin-Milwaukee, 3200 North Cramer Street, Milwaukee,
WI 53211, USA
R. Heideman
AO Smith Corporation, 12100 West Park Place, Milwaukee,
WI 53224, USA
Introduction
The need for sensors that can measure metals in water is
triggered by concerns about the effect of metal ions on human
health and the environment [1]. For example, sensors that can
make real-time measurements of metals such as cadmium,
lead, and mercury in water at low concentrations are desirable
for maintaining safe water supplies [2]. The real-time sensing
capability can ensure adequate time to take safety measures if
maximum limits of contaminant metal ions are exceeded.
Graphene-based sensors [3–5] are relatively new and have
the potential to meet the goal of rapid in situ measurement
of metals in water. The number of publications on graphene-
based sensors for the detection of metal ions as a function of
time (Fig. 1) clearly suggests the rapid growth of this field
since 2009.
Graphene has drawn considerable scientific attention since
its initial production through mechanical exfoliation by
Novoselov and co-workers in 2004 [6], which led to the
2010 Nobel Prize in Physics [7]. Pristine graphene, graphene
oxide (GO), and reduced graphene oxide (rGO) are all mem-
bers of the ‘graphene family’. Graphene consists of 2D carbon
atoms arranged in a regular hexagonal pattern similar to
graphite, but it is a single layer of graphite, as shown in
Fig. 2a. Graphene is relatively light; a 1 m2 sheet weighs only
0.77 mg [10]. The International Union of Pure and Applied
Chemistry (IUPAC) defines graphene as ‘a single carbon layer
of the graphite structure, describing its nature by analogy to a
polycyclic aromatic hydrocarbon of quasi infinite size’ [11].
Graphite is a naturally occurring mineral that is already used
abundantly and poses no threat to the environment. It was
named by Abraham Gottlob Werner in 1789 from the Ancient
Greek, ‘to draw/write,’ for its use in pencils, where it is
commonly called lead (not to be confused with the metallic
element lead) [12]. GOs are layered, oxygenated graphene
sheets that contain oxygen functional groups, such as
3958
Number of publications 60
45
30
15
0
2009 2010 2011 2012 2013
Year of publications
Fig. 1 Time-dependent number of publications on graphene-based sen-
sors for the detection of metal ions. Source: SciFinder
epoxides, carboxyls, hydroxyls, and alcohols, on their basal
planes and edges (Fig. 2b). Chemical analysis shows that the
carbon to oxygen ratio is approximately 3:1 [13].
Traditionally, GO is seen as a precursor to large-scale
graphene synthesis [14]. GO can be reduced to almost
graphene by chemical reduction [15], electroreduction [16],
thermal annealing [17], flash reduction [18], and enzymatic
reduction [19]; however, some possible applications of GO
have recently been reported [10, 20].
After reduction, GO transforms into rGO with some resid-
ual oxygen and structural defects, yielding high thermal con-
ductivity comparable to that of doped conductive polymers,
about 36 times higher than that of Si and about 100 times
higher than that of GaAs [21]. Figure 3 illustrates the classi-
fication and possible transformation routes of graphene-
related materials. Route 1 is the transformation from the
oxidation of graphite to graphite oxide, route 2 is the process
from the stepwise exfoliation of graphite oxide to obtain GO,
route 3 is the reduction of GO, route 4 is mechanical exfoli-
ation of graphite to produce graphene, route 5 is the transfor-
mation process from the oxidation of graphene sheets to GO,
a b
Fig. 2 a The hexagonal structure model of graphene. Reproduced with permission from Ref. [8]. Copyright 2011 American Chemical Society. b
Chemical structure of graphene oxide (GO). Reproduced with permission from Ref. [9]. Copyright 2011 Elsevier
J. Chang et al.
route 6 is the thermal decomposition of a SiC wafer, and route
7 is the growth of graphene films by chemical vapor deposi-
tion (CVD). Group A includes graphene materials primarily
used for their electronic properties and group B for their
optical properties [22].
Graphene properties
Graphene exhibits many outstanding and unique properties.
The zero band gap within the structure enables its ultrahigh
electron mobility (200,000 cm2 V−1 s−1), which is much
higher than that of carbon nanotubes (CNTs) [23]. It has
ultrahigh capacitance [24], excellent thermal conductivity
(≈4,000 W m−1 K−1) [25], outstanding electrical conductivity
(3,189 S cm−1) [26, 27], mechanical strength [28, 29], an
extremely high surface-to-volume ratio (2,600 m2 g−1), and
the possibility of atomically clean graphene sheets on lattice
symmetry structure-free graphene [30]. Besides these excel-
lent properties, the exceptionally low electronic noise of
graphene enables the possibility of the sensitive detection of
various analytes using graphene [31].
The optical and electrical properties of graphene are shown
in Fig. 4. Figure 4a shows the transmittance of the graphene
films on a quartz plate. The discontinuities in the absorption
curves arise from the different sensitivities of the switching
detectors. The upper inset in Fig. 4a shows the UV-induced
thinning and consequent enhancement of transparency. The
lower inset in Fig. 4a shows the changes in transmittance (Tr)
and sheet resistance (Rs) through UV/ozone etching. The
minimum sheet resistance is about 280 Ω m2. Figure 4b shows
the electrical properties of monolayer graphene devices show-
ing the half-integer quantum Hall effect and high electron
mobility. The upper inset of Fig. 4b shows a four-probe
electrical resistance measurement on a monolayer graphene
Hall bar device (lower inset) at 1.6 K. A gate voltage, Vg, was
applied to the silicon substrate to control the charge density in
the graphene sample. The multi terminal electrical measure-
ments showed that the electron mobility of graphene was
3,750 cm2 V−1 S−1 at a carrier density of 5×1012 cm−2. The
Graphene-based sensors for detection of heavy metals in water 3959

Fig. 3 Classification of
graphene-related materials.
Reproduced with permission
from Ref. [9]. Copyright 2012
Elsevier

main panel shows longitudinal (Rxx) and transverse (Rxy)
magneto resistances measured in this device for a magnetic
field B=8.8 T. In Fig. 4b, the monolayer graphene quantum
Hall effect is clearly observed, showing the plateaux with
filling factor ν=2 at Rxy =(2e2/h)−1 and zeros in Rxx. (Here e
is the elementary charge and h is Planck’s constant.) Quantum
Hall plateaux (horizontal dashed lines) develop for higher
filling factors. Figure 4c shows variation in the resistance of
a graphene film transferred to a ≈0.3-mm-thick polydimeth-
ylsiloxane (PDMS)/polyethylene (PET) substrate for different
distances between holding stages (that is, for different bending
radii). The left inset in Fig. 4c shows the anisotropy in four-
probe resistance, measured as the ratio, Ry/Rx, of the resis-
tances parallel and perpendicular to the bending direction, y.

Fig. 4 Optical and electrical

properties of graphene films.
Reproduced with permission
from Ref. [32]. Copyright 2009
Nature
3960
The right inset of Fig. 4c shows the bending process, which
suggests the excellent mechanical stability of graphene.
Figure 4d displays the resistance of a graphene film trans-
ferred to a PDMS substrate isotropically stretched by about
12 %. The left inset in Fig. 4d shows the case in which the
graphene film is transferred to an upstretched PDMS sub-
strate; the right inset shows the movement of holding stages
and the consequent change in the shape of the graphene film
[32].
Synthesis of graphene
Extensive efforts have been made to manufacture graphene,
and until now graphene has mainly been produced using four
different methods [15]. In general, different synthetic methods
could potentially result in ‘graphene’ with different chemical
structures, shapes, sizes, and numbers of layers [22, 33]. The
most commonly used method is the direct synthesis of large-
scale graphene films on copper using a CVD method [32].
When monolayer graphene is transferred to silicon dioxide
substrates at low temperatures, it exhibits good electron mo-
bility and a half-integer quantum Hall effect. It implies that the
quality of graphene grown by CVD is as high as mechanically
cleaved graphene. Figure 5 shows the synthesis, etching, and
transfer processes for large-scale, patterned graphene films.
Fig. 5 Synthesis, etching, and transfer processes for large-scale,
patterned graphene films. a Synthesis of patterned graphene films
on thin nickel layers. b Etching using FeCl3 (or acids) and transfer
of graphene films using a polydimethylsiloxane (PDMS) stamp. c
J. Chang et al.
Another key method is epitaxial growth on electrically
insulating surfaces, such as SiC [34], which is also called
‘thermal decomposition.’ For example, at temperatures
around 1,500 °C, it is possible to produce large-area graphene
with controlled sublimation of silicon from the SiC crystal. As
outlined in Fig. 6, scientists have condensed monolayer car-
bon on the silicon-terminated (0001) face of the SiC crystal
and the carbon-terminated (0001) face [35]. It is graphene of
one to two atomic monolayers thick with an area of several
cm2.
Micromechanical exfoliation of graphite is the third meth-
od [6]. In 2004, Geim and co-workers first reported graphene
sheets prepared by mechanical exfoliation of highly ordered
pyrolytic graphite (HOPG), which was derived from earlier
work on micromechanical exfoliation from patterned graphite
[36]. This method, shown in Fig. 7, also called the ‘Scotch-
tape method’ or the ‘peel–off method,’ yields a high-quality
graphene monolayer and few-layer graphene. However, this
method is unsuitable for large-scale production.
The fourth method is the creation of colloidal suspensions
made from graphite, derivatives of graphite (such as graphite
oxide), and graphite intercalation compounds [38]. This meth-
od is scalable to exhibit the possibility of high-volume pro-
duction. For example, macroscopic-scale graphene films were
prepared by two-dimensional assembly of graphene sheets,
which are chemically derived from graphite crystals and GOs.
Etching using a buffered oxide etchant (BOE) or hydrogen fluoride
(HF) solution and transfer of graphene films. RT is room temperature
(≈25 °C). Reproduced with permission from Ref. [32]. Copyright
2009 Nature
Graphene-based sensors for detection of heavy metals in water
Fig. 6 Schematic view of the
two-step growth model for
preparing epitaxial graphene.
Reproduced with permission
from Ref. [35]. Copyright 2011
Elsevier
Park et al. reported a simple route for the preparation of a
homogeneous aqueous suspension of graphene sheets from
graphite stack [39]; the resulting graphene sheet is chemically
modified graphene with good electrical conductivity. The
precursor GO was first dispersed in water, followed by the
addition of an aqueous solution of KOH (Fig. 8). The addition
of hydrazine monohydrate to KOH-treated GO produces a
homogeneous suspension of hydrazine-reduced KOH-
modified graphene (hKMG), which can remain stable for at
least four months. In terms of being well suited for chemical
functionalization, this method is versatile to enable a wide
range of applications of high-yield graphene colloidal suspen-
sions [15, 40]. However, there are also some negative aspects
associated with this method. For example, the defective
Fig. 7 a Graphite flakes on the surface of a flat piece of wax paper;
b magnesium foil and paper are rubbed together; c graphite is
transferred from the paper to the magnesium foil; d and e the
magnesium foil holding the graphite is added to a heterogeneous
liquid–liquid mixture between toluene and an aqueous solution of
HCl; d in which magnesium is dissolved in an exothermic reaction;
e and the carbonaceous material remains dispersed in the liquid; f the
3961
graphene structure hinders its application in fields that require
excellent conductivity, such as applications in transparent
conductive film [41]. On the other hand, when such graphene
layers are used as a sensing material, the defective area plays a
positive role in exhibiting a good capability to interact with
target molecules and ions [42].
Water sensor applications
GO-based fluorescence sensors
Compared with conventional materials, carbon-based fluores-
cent materials are more interesting due to their greater
mixture is submitted to an ultrasonic bath to produce a water/toluene
emulsion; g ultrasonication is switched off, the mixture is kept still,
and few-layer graphene dispersed in the emulsion agglomerates into a
continuous and homogeneous film located at the toluene/water inter-
face; g and h the self-assembled film is transferred to an arbitrary
substrate. Reproduced with permission from Ref. [37]. Copyright
2013 Elsevier
3962 J. Chang et al.

Fig. 8 Reduction of graphite

oxide (GO in a stabilization
medium). A simple route for the
preparation of a homogeneous
aqueous suspension of graphene
sheets from a graphite stack: a a
graphite stack is oxidized to
separate the individual layers of
(GO), b GO is dispersed in water
and treated with an aqueous
solution of KOH to obtain KOH-
modified oxidized graphene
(KMG), and finally c KMG is
reduced by using hydrazine to
produce hydrazine-reduced
KOH-modified graphene
(hKMG) in the form of a stable
aqueous dispersion of individual
graphene sheets. Reproduced
with permission from Ref. [39].
Copyright 2008 American
Chemical Society

stability, biocompatibility, and lower cytotoxicity [43]. In
particular, the fluorescence property of graphene can be tun-
able by surface functionalization and size manipulation of
graphene sheets [44]. Due to the small sp2 carbon domains
embedded in the sp3 matrix, GO exhibits visible-near-infrared
fluorescence [45]. Strongly heterogeneous atomic and elec-
tronic structures of GO suggest that fluorescence in GO arises
from a recombination of electron hole pairs in localized elec-
tronic states originating from various possible configurations.
The size of GO can be controlled within a few nanometers,
enhancing its optical properties to be applied for chemical
sensors [46]. Interestingly, the presence of various oxygenated
functional groups of GO contributes to opening the band gap
of graphene and results in a unique photoluminescence emis-
sion pattern [47]. The dominant fluorescence is from electron-
ic transitions between the non-oxidized carbon regions and the
boundary of oxidized carbon regions. The oxygen-containing
functional groups (C–O, C=O and O=C–OH) and some
oxidized sp3 sites significantly contribute to fluorescence
[48]. The control of the sp2 domain in the sp3 matrix of GO
can tune the fluorescence intensity as well as the emission
wavelength. There have been a number of reports on visible
and UV fluorescence from amorphous [49] and disordered
carbons [50]. The intrinsic and tunable fluorescence from GO
in the visible and near-infrared range makes it attractive for
numerous applications [51, 52], such as water sensor and
biosensor applications. As it is well known, some metal ions
such as Hg2+, Pb2+, and Cd2+ pose severe risks to human
health. Accordingly, exploring sensitive, rapid, and simple
analytical methods for precise monitoring of metal ions in
drinking water is urgently needed. So far, a number of spec-
troscopic techniques have been used in metal ion determina-
tion [53–55]. We briefly introduce several studies to provide
insights into how the unique optical properties of GO can be
used for the detection of heavy-metal ions in drinking water.
Fu and co-workers demonstrated a platform for effective
sensing of Pb2+ using GO-Au nanoparticles (NPs) through the
quenching of the fluorescence of GO by Au NPs [56]. The
interaction between GO and Au NPs may quench the fluores-
cence intensity of GO due to fluorescence resonance energy
transfer (FRET) [57, 58]. Pb2+ can accelerate the leaching rate
of Au NPs on the surface of graphene, which affects the
fluorescence of GO, resulting in ‘turn-on’ fluorescence. The
sensing strategy for Pb2+ based on graphene–Au nanocom-
posites is illustrated in Fig. 9a. After adding Pb2+ and 2-
mercaptoethanol (2-ME), the Au NPs could be rapidly dis-
solved to form Au(2-ME)2− complexes in solution. As a
result, the fluorescence of the graphene–Au NPs increased
Graphene-based sensors for detection of heavy metals in water
Fig. 9 a Schematic of the sensing mechanism for the detection of Pb2+
ions. b Fluorescence spectra of graphene Au nanocomposites in a 5 mM
solution of glycine upon the addition of increasing concentrations of Pb2+
ions (0 M−1,000 nM) under optimal conditions. Reproduced with per-
mission from Ref. [56]. Copyright 2012 American Chemical Society
owing to the gradual dissolution of Au NPs. The fluorescence
properties were strongly dependent on the size of the precur-
sor GO. GO with a lateral size of <1 μm was used due to a
high “turn-on” efficiency of fluorescence. Figure 9b shows an
increase in the fluorescence intensity with increasing concen-
tration of Pb2+. The relative fluorescence intensity showed a
good linear response to the logarithm of the Pb2+ concentra-
tion in the range of 50–1,000 nM. The relative standard
deviation of the relative fluorescence intensity was less than
0.3 %, indicating that the method is repeatable. The sensor
platform demonstrated high selectivity over common
coexisting metal ions (Al3+, Ca2+, Cd2+, K+, Mg2+, Zn2+,
Li+, Co2+, and Ni2+) and a lower detection limit of 10 nM.
Kundu et al. [59] reported a fascinating tool for the selec-
tive sensing of Au3+ ions in aqueous media using enhanced
fluorescence of GO. They proposed that the enhanced fluo-
rescence properties of GO in acidic media were due to pas-
sivation by hydrogen bonding between the hydroxy group of
polyvinyl alcohol (PVA) and the hydroxy groups of GO, as
shown in Fig. 10a. They studied the effect of different metal
ions on the optical properties of the hybrid, such as Au3+,
Cu2+, Ag+, Mg2+, Ca2+, Zn2+, K+, Pb2+, Co2+, Ni2+, Pd2+,
Fe2+, Fe3+, and Cr3+, as shown in Fig. 10b. They clearly
demonstrated that Au 3+ chloride caused fluorescence
quenching (≈83 %) of the GO/PVA hybrid, whereas all of
the other metal salts had a significantly smaller effect on the
fluorescence of the hybrid. With the addition of Au3+
3963
solutions, the fluorescence will be quenched more, as shown
in Fig. 10c. The highly fluorescent GO/PVA hybrid showed
selective sensing of Au3+ ions in aqueous media with a lower
detection limit of 1,400 nM and a high selectivity to Au3+ due
to a higher reduction potential than that of other metal ions.
Interestingly, GO itself has a fluorescence property, but it
can also quench fluorescence as an energy acceptor. Graphene
is a zero-energy band-gap semiconductor that exhibits metal-
lic behavior due to sp2 domains [60–62]. Similar to the metal,
charge transfer or energy transfer may play a role in fluores-
cence quenching between the fluorescent species and GO
[63]. These interaction elements can be simplified such that
their separation distance (d) dependences are sole functions of
their geometric arrangement. FRET occurs through the di-
pole–dipole interaction between an energy donor and an ac-
ceptor, following a 1/d6 separation distance dependence. It is
well known that traditional sensors based on FRET have a
limited detectable distance of 6 nm between molecular donors
and acceptors, either organic or metallic [64]. GO was report-
ed to be a fluorescence superquencher with the long-range
nanoscale energy-transfer property as an energy acceptor. The
efficient quenching distance is estimated to reach up to 30 nm
[65], which provides great flexibility for the construction of
fluorescent sensors. GO is the best acceptor of quantum dot
(QD) FRET donors with a quenching efficiency of 97 %,
compared with graphite, CNTs, and carbon nanofibers [66].
The quenching efficiency of GO can be improved after reduc-
tion. The quenching effect may originate from FRET, or non-
radioactive dipole–dipole coupling, between the fluorescent
species and GO [67, 68]. Owing to these unique features, GO-
based water sensors have been developed for the detection of
heavy-metal ions. The water sensor concept is based on the
fluorescence quenching of fluorophore-labeled materials,
such as single-stranded DNA (ssDNA), upon binding with
GO. More specifically, the fluorophore-labeled probe material
undergoes a conformational change after the introduction of
target materials and releases the fluorophore from GO to
reverse the quenching effect.
Zhao et al. [69] designed a water sensor using Pb2+-depen-
dent GR-5 DNAzyme as the catalytic unit, as illustrated in
Fig. 11a. The introduction of GO with the DNAzyme–sub-
strate solution would result in strong binding between the
large ssDNA loop of DNAzyme–substrate and GO through
hydrophobic and π-stacking interactions, resulting in signifi-
cant quenching of the fluorescence of the fluorophore carbo-
xyfluorescein. Upon the addition of Pb2+, the DNAzyme
cleaves the substrate strand at the RNA site into two parts,
releasing a short fluorophore carboxyfluorescein-linked
oligonuleotide fragment, leading to recovery of the fluores-
cence. As shown in Fig. 11b (black bars), 100 nM of Pb2+
could induce a significant fluorescence enhancement of the
sensing system, while all other metal ions at concentrations of
10 μM did not give any clear fluorescence change. The sensor
3964 J. Chang et al.

Fig. 10 a Schematic illustration

of supramolecular interactions
between GO and PVA. b Bar
diagram of quenching efficiencies
for different additional metal ions
(600 μM) and an Au3+ ion
concentration of 300 μM. c
Fluorescence intensity decrease
of GO-PVA1 upon gradual
addition of Au3+ solution (μM).
Reproduced with permission
from Ref. [59]. Copyright 2012
American Chemical Society

showed a linear relationship between the fluorescence en-
hancement and the Pb2+ concentration from 1 to 100 nM.
By taking advantage of the super fluorescence quenching
efficiency of GO, the water sensor exhibits a high sensitivity
and selectivity toward the target with a lower detection limit of
300 pM for Pb2+.
Wen et al. [70] designed a graphene-based fluorescent
nanoprobe for the detection of silver(I) ions by using GO
and a silver-specific oligonucleotide (SSO; 5′-FAM-CTCT
CTTCTCTTCATTTTTCAACACAACACAC-3′). When
GO is added to selectively adsorb the unbound SSO, the
fluorescence is quenched, whereas the Ag+ ions complexed

Fig. 11 a Schematic illustration of the DNAzyme-GO-based fluorescence sensor for Pb2+ detection. b Selectivity detection of Pb2+ over other
competing metal ions using the DNAzyme-GO-based sensor. Reproduced with permission from Ref. [69]. Copyright 2011 American Chemical Society
Graphene-based sensors for detection of heavy metals in water
with SSO remain free and their fluorescence is retained, as
shown in Fig. 12a. The fluorescence intensity change of SSO
can be used to provide a quantitative readout for Ag+. Due to
the selective interaction of Ag+ ions with cytosine–cytosine
(C–C) mismatches, the graphene-based fluorescent
nanoprobes showed very high selectivity for the detection of
Ag+ ions over all other metal ions, as shown in Fig. 12b. The
resulting curve for Ag+ was calibrated, which showed a lower
limit of detection of 5 nM (signal-to-noise ratio larger than 3).
The limit of quantification was calculated to be 20 nM (10 s).
Based on the response of 20 nM of Ag+ (limit of quantifica-
tion) with the background signal (0 nM of Ag+), the limit of
quantification can be clearly distinguished.
Compared with fluorescent organic dyes, QDs possess
more advantages, such as a high quantum yield, low
photobleaching, size dependency, and tunable absorptions
and emissions. The combination of QDs with graphene should
provide more obvious advantages in the design of novel
FRET-based sensors. Li et al. [65] reported a highly sensitive
and selective ‘turn-on’ fluorescent sensor for detection of Pb
ions based on the CdSe/ZnS QDs/aptamer–GO ensemble.
When Pb2+ ions are present in a GO/aptamer–QD ensemble
assay, the interaction of Pb2+ with the aptamer induces a
conformational change in the aptamer, leading to the forma-
tion of a G quadruplex/Pb2+ complex. The QDs that are linked
to the G quadruplex/Pb2+ complex are detached from the GO
sheet, which ‘turns on’ the fluorescence of QDs, as shown in
Fig. 13a. As seen in Fig. 13b, no evident change in the
fluorescence of the GO/aptamer–QD ensemble assay was
observed when any other metal ion (Ag+, Ca2+, Cd2+, Co2+,
Cu2+, Fe2+, Hg2+, Ni2+, and K+) was present in the assay,
except for Pb2+. The linear response range of the sensor was
0.1–10 nM. The lower limit of detection was defined as three
times the standard deviation/slope by IUPAC standards,
which was 90 pM (0.019 ppb) (http://www.iupac.org/home/
about.html).
Fig. 12 a Schematic illustration of a fluorescence sensor for the
detection of Ag+ ions, based on the target-induced conformation-
al change of a cytosine-rich SSO and the interactions between
3965
A GO-based platform for the optical detection of heavy-
metal ions has several advantages over other related materials,
such as CNTs. GO has excellent water solubility without any
assistance from surfactants. The two-dimensional GO sheet
contains a range of functional groups (epoxide and hydroxyl)
that can interact with water in an ionic, covalent, or
noncovalent manner. Its effectiveness in quenching fluores-
cence affords advantages over alternative carbon materials,
such as nano diamonds [71]. Its low cost, multiple molecular
target detection, and high sensitivity suggest that it may
emerge as the next-generation optical sensing platform for
heavy-metal ions. Furthermore, the possibility of controlling
the ratio of sp2 to sp3 fractions by reduction chemistry offers a
powerful way to engineer the band gap of GO through chem-
ical reduction, resulting in tailored electrical and optical prop-
erties of GO. Therefore, the tunable fluorescence from GO
could be used to develop GO-based devices for practical
applications.
Graphene-based electrochemical sensors
Electrochemical sensor analysis, particularly stripping volt-
ammetry, is very attractive for on-site monitoring of heavy-
metal ions, as well as for addressing other environmental
needs [40, 72–75]. These sensors are inherently sensitive
and selective towards electroactive species, fast, accurate,
portable, and inexpensive [76–78]. Generally, carbon mate-
rials (graphite or glassy carbon) are widely used as electrode
materials in analytical and industrial electrochemistry due to
their low cost, chemical stability, wide potential window,
relatively inert electrochemistry, and electrocatalytic activity
for a variety of redox reactions. Furthermore, electrochemical
sensors can be easily packed into a compact system. Bulk
electrodes have been developed in anodic stripping voltamm-
etry (ASV) analysis of heavy metals [79, 80], but the sensi-
tivity is very low and the detection limit cannot meet the
the fluorogenic SSO probe and GO. b Selectivity of the analysis
of Ag+ ions. Reproduced from Ref. [70] with permission from
the RSC
3966
Fig. 13 a Illustration of the operating principle of the “turn-on” fluores-
cent sensor for Pb2+ detection. b Selectivity detection of the GO/aptamer–
QD ensemble assay toward Pb2+ over other metal ions. F0 and F are the
requirements specified by the US Environmental Protection
Agency (US EPA) [1]. An effective way to solve these prob-
lems is to use micro- or nanoelectrodes. Compared with bulk
electrodes, nanoelectrodes have several advantages, such as a
higher surface area, which can improve the electron transfer
rate, the increased mass-transport rate, the lower solution
resistance, and the higher signal-to-noise ratio. Particularly,
graphene has tremendous potential for electrochemical appli-
cations as a novel electrode material [81]. Considering the
excellent properties of graphene, such as large surface-to-
volume ratio, high conductivity and electron mobility at room
temperature, robust mechanical properties, and flexibility [19,
82, 83], graphene-based electrochemical sensors [84] have
been developed for environmental analysis and the detection
of heavy-metal ions [85, 86]. The electrochemical responses
of graphene electrodes have more favorable electron-transfer
kinetics than graphite and glassy carbon electrodes. The main
advantage of graphene is the availability of a large, active
surface area and the presence of oxygen-containing groups on
its edges or surface, resulting in easy discrimination of target
analytes based on their respective peaks, which commonly
overlap on conventional graphite electrodes [87]. In addition,
most of the graphene used in electrochemistry is produced
from the reduction of GO and usually has functional groups
such as hydroxyl and carboxyl, which may form complexes
with heavy metal ions [88, 89]. We highlight here important
applications of graphene and graphene nanocomposites in
electrochemical sensors for heavy-metal ions.
Li et al. [90] reported that Nafion–graphene (Nafion-G)
composite film-based electrochemical sensors not only exhib-
ited improved sensitivity for metal ion (Pb2+ and Cd2+) detec-
tion, but also alleviated interference due to the synergistic
effect of graphene nanosheets and Nafion. The stripping cur-
rent signal is thus greatly enhanced on graphene electrodes.
The high sensitivity is due to a combination of enhanced
electron conduction of rGO and the cation exchange capacity
of Nafion [91–93]. Linear calibration curves have been
J. Chang et al.
fluorescence intensity at 567 nm in the presence and absence of Pb2+ or
other metal ions, respectively. Reproduced with permission from Ref.
[65]. Copyright 2013 Elsevier
confirmed for 0.5 to 50 mg L −1 Pb 2+ and for 1.5 to
30 mg L−1 Cd2+. Willemse et al. [94] also reported a Nafion-
G nanocomposite solution in combination with an in situ
plated mercury film electrode as a highly sensitive electro-
chemical platform for the determination of Zn2+, Cd2+, Pb2+,
and Cu2+ by square-wave anodic stripping voltammetry
(SWASV). The electrode of a Nafion-G nanocomposite is
suitable for the accumulation of Zn2+, Cd2+, Pb2+, and Cu2+
on the electrode surface (−1.3 V was used as the optimum
deposition potential for Zn2+, Cd2+, and Pb2+; an optimum
deposition potential of −1.0 V was chosen for Cu2+), resulting
in high sensitivity. Zn2+, Cd2+, and Pb2+ can be easily identi-
fied using Nafion-G-Hg sensors, as shown in Fig. 14. Copper
was not determined simultaneously with Zn2+, Cd2+, and Pb2+
due to intermetallic interference that exists between Cu and
Zn. For individual metal ion detection, the lower detection
limits were 0.07 μg L−1 (0.338 nM) for Pb2+, 0.08 μg L−1
(1.23 nM) for Zn2+, 0.13 μg L−1 (2.03 nM) for Cu2+, and
0.08 μg L−1 (0.71 nM) for Cd2+. A linear response for indi-
vidual metal detection ranging from 1 to 7 μg L−1 for Zn2+,
Cd2+, and Pb2+ and 20–180 μg L−1 for Cu2+ has been obtain-
ed. For simultaneous detection, the detection limits/correlation
coefficients were 0.07 μg L−1 (0.338 nM)/0.990 for Pb2+,
0.13 μg L−1 (1.16 nM)/0.983 for Cd2+, and 0.14 μg L−1
(2.15 nM)/0.999 for Zn2+. The accuracy of the analysis in real
applications at the Nafion-G modified electrode was compa-
rable to that of inductively coupled plasma mass spectrometry
(ICP-MS). Nafion-G was sensitive enough to be able to detect
Zn2+, Cd2+, and Pb2+. ICP-MS only showed a higher sensi-
tivity for Cd2+. A highly enhanced sensing platform based on
the Nafion-G nanocomposite film was used for the detection
of individual ions as well as simultaneous determination of
Zn2+, Cd2+, Pb2+, and Cu2+ by SWASV. The excellent lower
detection limit and high sensitivity for measuring Zn2+, Cd2+,
Pb2+, and Cu2+ is due to the combination of the advantages of
the high conductivity of graphene and the high cation ex-
change capacity of Nafion.
Graphene-based sensors for detection of heavy metals in water
Fig. 14 Simultaneous detection of Zn2+, Cd2+, and Pb2+ with concentra-
tions of 0.5–5.0 μg L−1 based on Nafion-G-Hg electrodes. Reproduced
with permission from Ref. [94]
Although the Nafion-G composite electrochemical sensors
discussed above showed high sensitivity for the detection of
metal ions, this simple mixture method to make nanocompos-
ites could easily lead to irreversible agglomerates and even
restacking of graphene to form graphite after the drying of
dispersion solutions, due to van der Waals forces and π–π
stacking interactions among individual graphene sheets [95,
96]. One strategy to minimize aggregation problems of
graphene sheets is to incorporate NPs into graphene sheets.
Recently, graphene-based nanosensors were fabricated with
the aim of employing them in electrochemical heavy-metal
ion sensors, such as graphene decorated with metal or metal
oxide. Gong et al. [85] distributed monodispersed Au NPs
onto the graphene nanosheet matrix, which could greatly
facilitate electron-transfer processes between Hg2+ and the
electrode; this exhibited a good performance for the detection
of Hg2+ in practical water samples. The sensor had a high
sensitivity of 708.3 μA/ppb, and its lower detection limit
(6 ppt) was far below the guideline value of drinking water
specified by the World Health Organization (1 ppb) [97]. Wei
et al. reported an SnO2/reduced GO nanocomposite modified
glassy carbon electrode, which was used for the simultaneous
and selective electrochemical detection of ultratrace amounts
of Cd2+, Pb2+, Cu2+, and Hg2+ ions in drinking water [98].
Simultaneous analysis by SWASV of Cd2+, Pb2+, Cu2+, and
Hg2+ ions using an SnO2/reduced GO nanocomposite elec-
trode at increasing concentrations is shown in Fig. 15. It
shows individual peaks at approximately −0.8, −0.6, −0.1,
and 0.24 V for Cd2+, Pb2+, Cu2+, and Hg2+ ions, respectively.
The corresponding linear calibration curves for Cd2+, Pb2+,
Cu2+, and Hg2+ were valid from 0.3 to 1.2 μM, with the
corresponding correlation coefficients of 0.995, 0.984, 0.976
and 0.965, respectively. The lower detection limits of the
SnO2/reduced GO nanocomposite modified glassy carbon
electrode for Cd2+, Pb2+, Cu2+, and Hg2+ were 0.1015,
3967
0.1839, 0.2269, and 0.2789 nM, respectively, which were well
below the guideline value specified by the World Health
Organization [97].
Graphene-based electrochemical sensors also show good
performance in real water sensing, which is critical for prac-
tical applications. Recently, Liu et al. reported cysteic
acid/reduced GO composite films for the selective detection
of Ag+ in natural waters, which showed a high sensitivity and
a low detection limit (1 nM) [99]. Natural water samples (1
and 2) obtained from different sections of the Slender West
Lake and processed wastewater samples (3 and 4) prepared in
the laboratory were measured by the differential pulse anodic
stripping voltammetry (DPASV) method, as shown in Table 1.
The sensors showed good recoveries of 102 and 97.0 % for
natural water samples. The metal concentrations were very
close to those measured by the ICP-MS method with a relative
standard deviation (RSD) of less than 4.2 %. The proposed
electrochemical sensors demonstrated ultrahigh sensitivity
and good recovery for the detection of trace Ag+ without
any interference from other metal ions.
Reduced GO as a collection of nanoelectrodes for electro-
chemical applications has advantages over conventional
macroelectrodes [100–102], including (1) a high signal-to-
noise ratio because of the ultrahigh electron mobility of
graphene and its unique structural properties, such as one-
atom thickness; (2) a low power that enables stripping analysis
in a high resistive media, which makes the supporting elec-
trolyte unnecessary, and hence, reduces interference effects;
(3) graphene-based electrodes serve as an ideal platform for
accommodating metal ions and facilitating metal ion electron
transfer; (4) graphene-based electrochemical electrodes can
detect an individual ion as well as simultaneously monitor
multiple metal ions with a low detection limit; and (5) the
capability of on-site measuring of the metal ion concentration
change in groundwater samples.
Graphene-based FET sensors
Field-effect transistor (FET) sensors based on nanomaterials,
such as nanowires, nanotubes, and NPs, are emerging as a
powerful sensing platform for the detection of chemical/
biological species due to their various attractive features:
ultrasensitivity, label-free, and real-time response comparable
with or better than those of conventional techniques (e.g.,
ELISA) [103, 104]. FET sensors are capable of label-free
detection of heavy metals by using the interaction between
the analyte and the semiconductor [105–107]. One- and two-
dimensional semiconducting nanomaterials, such as a single-
walled CNT or graphene, are especially attractive for FET
sensors because they have very high surface-to-volume ratios
and charge mobility, leading to high sensitivity [108].
Nanomaterials as semiconducting channel materials usual-
ly require surface modification for the specific detection of
3968 J. Chang et al.

a probe to detect Ca2+ ions. At a gate voltage of −0.6 V (p-type

Fig. 15 SWASV response of the SnO2/reduced GO nanocomposite for
the detection of Cd 2+, Pb2+, Cu2+, and Hg2+ ions at concentrations of 0,
0.3, 0.4, 0.5, 0.6, 0.7, 0.9, and 1.2 μM for each metal ion. Reproduced
with permission from Ref. [98]. Copyright 2012 American Chemical
Society
chemicals [27, 109, 110], which will degrade their electronic
properties by generating defects through chemical or phys-
ical adsorption, resulting in the degradation of device per-
formance and instability. GO naturally has functional groups
(mainly carboxyl and hydroxyl groups) for the immobiliza-
tion of target materials. In particular, reduced GO materials
offer a relatively high charge mobility, a large detection area,
a relatively low 1/f noise [111], and tunable ambipolar
field-effect characteristics [108]. Recently, not only scientists
but also engineers have shown tremendous interest in
graphene FETs, and remarkable achievements have been
made due to graphene’s unique electronic properties
[15–18].
Sudibya et al. [108] constructed water sensors based on
rGO micropatterns with surface modification of calmodulin as
region), the lower detection limit was 1 μM for Ca2+, which
was consistent with the binding affinity of calmodulin (0.1–
1.0 μM). They also explored the possibility of detecting heavy
metals by using rGO-FET sensor platforms with different
probes of metallothione in type II proteins. These devices
provided similar results at the same gate voltage for the
detection of Hg2+ (detection limit: 1 nM; range: 1–28 nM)
and Cd2+ (detection limit: 1 nM; range: 1–55 nM). Both
detection limits strongly depended on the binding affinity
and device sensitivity [112, 113]. The rGO-FET device read-
ily fabricated on a bench top can be used to rapidly in a label-
free manner detect various metal ions in solution with high
sensitivity and a low detection limit. Wen et al. [114] fabricat-
ed a graphene-based electronic sensor for the label-free detec-
tion of lead (Pb2+) ions using Pb2+-dependent DNAzyme as a
probe (Fig. 16a and b), in which the device showed high
sensitivity (lower detection limit 0.02 nM) and high selectiv-
ity. Bare graphene, AuNP decorated graphene (AuNP-
graphene), nonspecific double-stranded DNA and AuNP
complex decorated graphene (NSDNA-AuNP-graphene),
and DNAzyme and AuNP complex decorated graphene
(DNAzyme-AuNP-graphene) devices were investigated for
detection sensitivity, as shown in Fig. 16c (note that the unit
of Vg, min is mV). Only DNAzyme-functionalized devices
showed a high response to Pb2 + ions in a dose-dependent
manner, indicating the high selectivity of DNAzyme-
mediated detection. Compared with other methods, this ap-
proach offers several advantages. First, such nanoelectronic
detection is simple, label-free, and low cost [115, 116].
Second, it is extremely sensitive (lower detection limit of
20 pM for Pb2+). Finally, using Pb2+-dependent DNAzyme
as a probe, the detection is highly specific. Some consider-
ation should also be given to the response time of
measurements.

Table 1 Determination of Ag+ in water samples

Water Original concentration (M) Added (M) Present method found (M) RSD (%) Recovery (%) ICP-MS found (M)

Sample 1 ND 8.00×10−8 8.17×10−8 4.0 102.0 8.08×10−8

Sample 2 ND 8.00×10−8 7.82×10−8 4.2 97.8 8.02×10−8
Sample 3a 4.56×10−7 0 4.49×10−7 3.4 – 4.56×10−7
5.00×10−7 9.48×10−7 3.2 98.4 9.63×10−7
1.00×10−6 1.43×10−6 3.0 97.4 1.46×10−6
Sample 4a 5.85×10−7 0 5.85×10−7 3.3 – 7.94×10−7
5.00×10−7 1.07×10−6 3.1 97.0 1.09×10−6
1.00×10−6 1.56×10−6 3.0 97.5 1.59×10−6

Reproduced from Ref. [99] with permission from the RSC

ND not detected
a
Samples were obtained from laboratory wastewater at different times. Samples had been treated by the wastewater treatment system containing
0.53 μM Zn(II), 0.37 μM Ni(II), 0.45 μM Cd(II), 0.39 μM Fe(III), 0.02 μM Hg(II), 0.16 μM Pb(II), 0.48 μM Cu(II) and 0.36 Cr(VI)
Graphene-based sensors for detection of heavy metals in water
Fig. 16 a Schematic illustration of the graphene transistor functionalized
with DNAzyme molecules. b Schematic of Pb2+-induced self-cleavage of
the DNAzyme. c The dose–response (shift of Vg, min) of different devices
Recently, Chen et al. [117] prepared FET sensors based on
thermally rGO with thioglycolic acid (TGA)-functionalized
Au NPs (or rGO/TGA-AuNP hybrid structures) to detect
mercury(II) ions in aqueous solutions. Figure 17 shows a
schematic illustration of the rGO/TGA-AuNP hybrid sensor,
including GO across the electrodes, TGA-functionalized Au
NP decorated GO, and monitoring electrical changes through
introducing target materials.
Figure 18a shows a SEM image of a single rGO sheet
spanning across a pair of gold interdigitated electrodes. After
Au NP assembly, Au NPs were seen to be uniformly distrib-
uted on the surface of the rGO sheet without agglomeration, as
shown in Fig. 18b. The drain current (Ids) of the rGO/TGA-
AuNP hybrid sensor as a function of the drain voltage (Vds) or
Fig. 17 Schematic diagram of the rGO/TGA-AuNP hybrid sensor. TGA-
modified Au NPs are anchored to the rGO sheet surface and function as a
specific recognition group for immobilizing mercury(II) ions.
Reproduced with permission from Ref. [117]. Copyright 2012 American
Chemical Society
3969
to various Pb2+ concentrations (the unit of Vg, min is mV). Reproduced
with permission from Ref. [114]. Copyright 2013 Wiley-VCH
the gate voltage (Vg) was measured as the sensor was exposed
to water and a 10−5 M solution of Hg2+ ions, as shown in
Fig. 18c. The drain current increases for the rGO/TGA-AuNP
hybrid sensor after exposure to the solution of Hg2+ ions is due
to the formation of R-COO–(Hg2+)–OOC-R chelates through
reactions between Hg2+ ions and the carboxylic acid groups of
the TGA molecules on the Au NPs. The coupling of Hg2+ ions
with carboxylic acid groups can cause changes in the charge-
carrier concentration in rGO sheets. To counteract the accu-
mulation of positive charges from Hg2+ ions, electrons may
transfer from the rGO to the Au NPs, increasing the hole
concentration in the rGO, and thereby, increasing the drain
current. Therefore, compared with water, exposure to the
solution of Hg2+ ions increased the conductance of the rGO/
TGA-AuNP hybrid sensor. As shown in Fig. 18d, the Dirac
point of the rGO/TGA-AuNP hybrid sensor shifted about +
10 V because of the immobilization of the Hg2+ ions. The
device showed a lower detection limit of 25 nM and
responded to Hg2+ within a few seconds with excellent selec-
tivity over other metal ions. The improved sensing perfor-
mance was attributed to the chelation interaction of heavy-
metal ions with the carboxyl group of TGA as well as the high
charge mobility of rGO. The encouraging results suggest the
promise of using the rGO/NPs hybrid sensing platform for the
detection of various chemicals and bacteria in an aqueous
environment.
However, due to the zero band gap of graphene [16], the
on–off ratios of these devices are small, which makes it
difficult to turn off a graphene FET and to incorporate it into
logic electronic devices. Thus, opening up a band gap for
graphene is crucial to obtain the necessary switching and
power gain effects. Many methods have been tried and report-
ed, such as reforming graphene into graphene nanoribbons
3970
Fig. 18 SEM images of a GO
sheet (a) and an rGO sheet
decorated with TGA-AuNPs (b)
spanning across interdigitated
electrodes [104]. Ids −Vds (c) and
Ids −Vgs (d) characteristics of an
rGO/TGA-AuNP hybrid sensor
exposed to water (black) and a
10−5 M solution of Hg2+ ions (red;
at 0.01 V drain voltage).
Reproduced with permission
from Ref. [117]. Copyright 2012
American Chemical Society
[118] or graphene nanomesh [119–122], and applying an
electric field to bilayer graphene [123]. In addition to the zero
band gap of graphene, some intrinsic drawbacks and limita-
tions cannot be neglected. Defects in graphene ribbons, disor-
ders at the edges, and impurities in the supporting substrate
remain as scattering sources that limit the mobility of these
devices. For this problem, Diez-Perez et al. [124] successfully
implemented a bottom-up fabrication method to manufacture
n-type nanoscale graphene FETs. In their study, they used a
scanning tunneling microscope (STM) break junction method
to measure the performance of the nanoscale graphene FETs,
which were composed of large graphene molecules acting as
electron-transfer channels and ionic liquids acting as gate
electrodes. An on–off ratio as high as 50 was achieved when
the graphene molecules were terminated by thiol groups; this
is much larger than those of most large-area graphene FETs
fabricated through top-down approaches. Besides opening up
a sizable band gap for graphene, this bottom-up approach has
several potential advantages over a top-down method. It can
not only provide accurate control of defects, disorder, size,
and shape, but can also control the chemical properties and
electrode contacts of the molecules.
Metal complexation and detection limits
One difficulty with sensing metal ions is that they can form
complexes with inorganic ligands, such as hydroxyl ions and
bicarbonate ions. Binding of ions to hydroxide and oxide
surfaces, as well as to organic matter, including
J. Chang et al.
ethylenediaminetetraacetic acid (EDTA) and nitrilotriacetate
(NTA), is also a common occurrence. Furthermore, mercury
can undergo biological methylation whereby its toxicity is
increased. Thus, although ionic concentrations of metals are
important and can be measured with the described sensors,
usually a significant portion of the metal is not in a free ionic
form, but rather it is bound to ligands, surfaces, or organic
matter. Fortunately, the amounts of each phase of several
metals can often be estimated by chemical metal speciation
computer programs, such as Visual MINTEQ (2009) (http://
vminteq.lwr.kth.se/).
Table 2 lists several metals of interest with an indication of
the common forms. The maximum metal contaminant level or
the action level is also shown, along with the detection limits
for several of the graphene-based sensors described above.
The maximum contaminant levels or action levels are from a
list promulgated by the National Sanitation Foundation [125].
From the results given in Table 2, it can be seen that detection
limits for many metals are very low compared with the max-
imum guideline levels. For example, the detection limit for
cadmium using a SnO2/rGO sensor is 0.102 nm L−1 compared
with the regulatory guideline of 44.5 nM. In cases where the
detection limits are given for more than one type of sensor, the
preferred sensors are as follows: the SnO2/rGO sensor has the
lowest detection limit for cadmium and copper, the GO/
aptamer QD sensor for lead, and the Au-NP-G sensor for
mercury. The low detection limits, the rapid response, and
the small dimensions of graphene-based sensors form the
basis for their potential use to measure low levels of metals
in water.
Graphene-based sensors for detection of heavy metals in water 3971

Table 2 Methods of measuring metal ions in water using graphene-based sensors with maximum levels and detection limits (nM)

Metal Oxidation Common form(s) Max. metal Fluorescence sensors Electrochemical sensors FET sensors
state at near-neutral contaminant
pH values or action levela

mg/L nM GO-PVA GO/SSO GO/aptamer Au-NP- Nafion-G- SnO2/rGO rGO-FET rGO/TGA-

hybrid [59] [70] QD [65] G [85] Hg [94] NCs [98] [114] AuNP [117]

Cd +2 Cd2+ 0.005 44.5 0.712 0.102

CdCl+, Cd(OH)+,
Cd(HCO3)+
Cu2+
Cu(OH)+, CuCl+,
Cu(HCO3)+ Cu+
Cu +2 Au3+ 1.3 20500 2.03 0.227
Pb2+
Pb(OH)+, PbCl+,
Pb(HCO3)+
Pb(C2H5)4,
Pb(CH3)4
+1 Cu+
Au +3 Au3+ 1400
Pb +2 Pb2+ 0.015 72.4 0.09 0.338 0.184 0.02
Pb(OH)+,PbCl+,
Pb(HCO3)+
Pb(C2H5)4,Pb(CH3)4
Hg +2 Hg2+ 0.002 9.97 0.0299 0.279 25
+1 Hg+
0
0 Hg,CH3Hg+
−2 (CH3)2Hg
Ag +1 Ag+ 0.1b 927 5
2+
Zn +2 Zn 5 76500 1.23
Zn(OH)+,ZnCl+,
Zn(HCO3)+

For listed non-complexed metal ions

a
Sum of all metal forms. From National Sanitation Foundation [125], except for silver
b
World Health Organization [97]. Where silver salts are used to maintain bacteriological quality of drinking water, levels up to 0.1 mg L−1 can be
tolerated without risk to health

Conclusion and FET sensors; (ii) use or develop different molecular

The unique chemical structure of graphene and GO, along
with heterogeneous electronic structure due to the presence of
sp2 and sp3 bonding, offers exciting optical and electrical
properties for water sensor applications. By taking advantage
of fluorescence emission and fluorescence quenching in re-
duced GO, interesting sensing applications based on charge
transfer and contrast enhancement have been demonstrated.
Future applications based on the exceptional quenching ability
of GO should push the detection limit resolution of water
sensors beyond the current state-of-the-art. To move forward,
chemists from various backgrounds will be needed to develop
strategies for further tuning the properties of graphene or GO.
Enormous efforts have been made to develop heavy-metal
sensors using graphene or GO to (i) explore different signal
transduction mechanisms resulting in optical, electrochemical,
recognition probes, including small organic molecules,
DNA, aptamer, and proteins; (iii) incorporate graphene or
GO into sensors, leading to significant improvement in the
sensing performance, especially detection limit and sensitivi-
ty. However, most of the current studies only demonstrated
proof-of-concept for water sensor applications that could de-
tect heavy metals in buffer solutions. It is a tremendous
challenge to apply the GO-based sensors to real-world sam-
ples (tap or river water) for real-time, on-site detection of
heavy metals. Due to severe interference of additional chem-
ical and biological species in the samples (such as blood, and
urine in river water), the sensing signals will be complicated.
Some sample preparation is required before final analysis
(e.g., separation or preconcentration). An effective solution
to these problems is to develop sensitive and specific detection
devices that integrate sensors with microfluidics on a single
3972
chip. Furthermore, graphene-based water sensor devices com-
bined with a wireless detection system will be attractive for
various environmental applications.
Acknowledgments Financial support for this work was provided by
the U.S. National Science Foundation (IIP-1128158) and University of
Wisconsin-Milwaukee Research Foundation Bradley Catalyst Grant.
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