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Review-Electrochemical Synthesis of 2D Layered Materials and Their

Potential Application in Pesticide Detection

Article  in  Journal of The Electrochemical Society · December 2018

DOI: 10.1149/2.0641816jes

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 B848 Journal of The Electrochemical Society, 165 (16) B848-B861 (2018)
0013-4651/2018/165(16)/B848/14/$37.00 © The Electrochemical Society

Review—Electrochemical Synthesis of 2D Layered Materials and

Their Potential Application in Pesticide Detection
T. H. Vignesh Kumar,1 Santosh K. Yadav,2 and Ashok K. Sundramoorthy 1,z

1 Department of Chemistry, SRM Institute of Science and Technology, Tamil Nadu, India
2 Department of Chemical & Biological Engineering, Drexel University, Philadelphia, Pennsylvania 19104, USA

Two dimensional (2D) layered materials are receiving great attention due to various chemical functionality and anisotropic properties
which are related to the crystalline arrangement of atoms. Their biocompatibility along with their structural, electrical and mechanical
properties created interest in various fields of science and technology. The materials are flexible, transparent, light weight and have high
stability. 2D layered materials are highly electrically and thermally conductive in nature. Additionally, phase boundaries and dynamic
behavior can be observed in the same materials. It was expected that these layered 2D materials can be used as electrocatalyst to
study their interactions with various molecules by electrochemical methods. The 2D materials based electrode have shown promising
electro-catalytic activity, higher sensitivity, with selectivity, more stability and biocompatibility when used in chemical and biosensor
applications. Interestingly, various kind of layered 2D materials can be easily synthesized without any sophisticated instruments. In
this review, we have discussed about unique features of layered materials and various electrochemical exfoliation methods reported to
prepare 2D layered materials (For example; hexagonal boron nitride (hBN), molybdenum disulfide (MoS2 ), molybdenum diselenide
(MoSe2 ), tungsten dsulfide (WS2 ) and tungsten diselenide (WSe2 )) with fewer defects at a relatively low cost. In addition, the use
of 2D layered materials for electrochemical sensor fabrication and detection of pesticides were highlighted with their applications in
real-world samples. Since, pesticides are highly toxic even at very low concentrations, it is very important to identify and detect their
concentration level in fruits, vegetables and food to ensure human health and safety. For this purpose, 2D layered materials based
electrochemical sensors have been demonstrated as a promising alternative method. The keep increasing demand for wearable/flexible
sensor may utilize the simple electrochemical synthetic methods and electrode modification strategies to prepare electrochemical
transducers for on-site pesticides detection in food samples with relatively low-cost.
© 2018 The Electrochemical Society. [DOI: 10.1149/2.0641816jes]

Manuscript submitted September 4, 2018; revised manuscript received December 3, 2018. Published December 15, 2018.

Pesticides are commonly used to protect crops from insects in or-
der to increase the food production.1 It was reported that only 0.1%
of pesticide reach the target pest, and the remaining pesticides have
the potential to contaminate natural resources such as water, air, land,
etc. Some pesticides are harmful to humans and other animals based
on exposure (quantity and location) if they are exposed through our
food system such as in harvested, food storage, ground water, and
air pollution. Among these, contaminated food is the main source for
causing serious illness in our body.2,3 Long-term pesticide exposure
has been linked to the development of a neurological disorders, due to
their inhibitory effect on Acetylcholinesterase (AChE).4,5 The neuro-
logical disorders result from damage to different nerves in the human
and animal body, which may impair sensation, movement, gland se-
cretion or organ function. Other health issues may result from affected
nerves. Many environmental protection agencies list pesticides as pri-
ority hazardous. Some of the hazardous pesticides structures were
shown in Fig. 1. These harmful Organophosphate and carbamate pes-
ticides have to be accurately detected and quantified (monitored) in
food samples to assure the food safety. Pesticides are commonly de-
tected by routine methods such as mass spectrometry,6 liquid/gas
chromatography,6,7 Raman,8 fluorescence spectroscopy9 etc. How-
ever, there are still many challenges and requirements to overcome
such as speed and access of analysis methods, high selectivity with
sensitivity, interfering molecules, trained personnel, and current high-
cost levels.10,11
One promising area of research into chemical detection is electro-
chemical sensors which can be used as an alternative sensor platform
for detecting chemical contaminants, pesticides, etc. When the work-
ing electrode was modified with functional nanomaterials, it can detect
the target pesticide with high selectivity and sensitivity with a signif-
icantly shorter response time. An unmodified electrode does not have
high selectivity with regard to the target chemicals. In order to increase
the selectivity and sensitivity of the electrode, exfoliated 2D layered
materials were examined. Over the years, layered graphene-based
electrochemical sensors have been reported for various applications
due to graphene’s extraordinary electronic mobility in room temper-
ature [>50,000 cm2 /V.s)], good electrical and thermal conductivity,
and mechanical stability.12–14 However, graphene with zero bandgap
z
E-mail: ashokkumar.sun@ktr.srmuniv.ac.in
creates significant effects in most of the electrochemical based sen-
sor applications. The effects due to high adsorption toward target
molecules and high quality crystal lattice, leads to screen charge fluc-
tuations greater than other dimensional materials.15 Furthermore, to
synthesis high quality graphene films by bottom-up approach, very so-
phisticated methods such as chemical vapor deposition system (CVD),
molecular beam epitaxy (MBE), pulsed laser deposition (PLD) and
clean room facilities are required.16–19 On the other hand, graphene ox-
ide (GO), can be synthesized by exfoliation of graphite by Hummers
Method and other greener electrochemical methods, but the quality of
the graphene will be poor due to potential defects on the 2D crystal
lattice which thus reduces device performance.20–24
Hexagonal boron nitride (hBN) and transition metal dichalco-
genides (TMDs).—To alter the properties of graphene, opening the
bandgap of graphene by breaking the symmetry of the K and K
points from first Brillouin zone was investigated, which has led to ex-
plorations of hexagonal boron nitride (hBN).25 In this context, carbon
K and K position has been replaced by boron (B) and nitrogen (N)
elements which can then form defect free atomically flat hBN dielec-
tric interface structure resulting in a wide bandgap (∼6 eV) insulating
behavior.26 This defect free hBN could be effectively incorporated
with other materials for electrochemical sensing.27
Transitional metal dichalcogenides (TMDs) such as MoS2 , MoSe2 ,
WS2 and WSe2 with semiconducting and semi-metallic natures have
created huge interest for electrochemical sensor applications due
to their high electronic mobility and tunable bandgaps.19,28,29 The
weak Van der Waals energy factors directly allow to arrange het-
erojunctions consisting of distinct 2D layered materials (transition
metal atoms sandwiched between two chalcogen layers) when exfoli-
ated by facile electrochemical method.26 2D heterostructures such as
graphene, hBN, MoS2 , WSe2 and fluorographene are presented in the
Fig. 2.30
A single unit in a sheet of 2D TMD material consists of one tran-
sition metal atom coordinated with two chalcogen atoms (Fig. 3).
This unique structure of TMD materials provides high surface energy
of edge plane which consequently contrasts with surface inertness
of the basal plane. These anisotropic basal and edge planes create
potent electrochemical activity.31 Each TMD material has different
electrochemical properties. The properties depend on how transition

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 Journal of The Electrochemical Society, 165 (16) B848-B861 (2018)
Figure 1. Some of the hazardous pesticides and their chemical structures.
metal atoms coordinate the chalcogen atoms and the stacking arrange-
ment of multiple layers.32 A single sheet of TMD material commonly
has octahedral or trigonal prismatic coordination phase as shown in
Fig. 3.33 Additionally, 1T and 2H based TMD materials are also com-
mon. Here, 1T means one layer of tetragonal (D3d group) present in the
crystallographic unit cell and 2H means two layers of hexagonal (D3h
group) present in the crystallographic unit cell. 2D materials obtained
from group 6 elements have attracted more attention (i.e. molybde-
num and tungsten) because they were more stable and semiconducting
(2H) in nature.33
Intercalation of 2D materials.—The aforementioned 2H phase is
easily transferable to 1T phase by alkali intercalation methods due to
rearrangement of d orbitals and initiation of loan pair electrons within
the TMDs sheet.34–36 This transition could then alter the electronic
property of 2D materials and enhance the inherent electrochemical
activities. Therefore, 2D materials properties are dependent on transi-
tion metal coordination. For instance, single layer of 2H based MoS2
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B849
or WS2 offers an intriguing electrical and optical property, mean-
while 1T based MoS2 or WS2 has increased electrochemical redox
reactions due to reinforced catalytic activity.37,38 For instance, the
electrochemical properties based on phase transition ability of WS2
can be converted to 1T phase from 2H phase by tert-butyllithium
(t-BuLi) intercalator after exfoliation. Consequently, WS2 has more
catalytic activity than other TMD materials i.e. MoS2 , MoSe2 and
WSe2 .39,40 TMDs has the commonly known formula of MX2 , where
M (+4 oxidation state) means metal and X2 means two chalcogens
(–2 oxidation state). The above MX2 is electrochemically active due
to its electrochemical inherent nature.33
Unique feature of 2D materials.—Another unique feature of TMD
materials was that they exhibit permanence antisite defects in mono-
layer MoS2 structures where chalcogen atoms can fill up metal atom
sites or metal atoms can fill up chalcogen atom sites.41 For instance,
when a Mo atom replaces the sulfur pair within the lattice it will
break the hexagonal network of MoS2 symmetry, whereas sulfur pairs
 B850 Journal of The Electrochemical Society, 165 (16) B848-B861 (2018)

Figure 2. Various 2D layered heterostructures (adapted with permission from

Ref. 30, Copyright 2013, Springer Nature).

Figure 4. (A and B) Atomic resolution aberration-corrected scanning trans-

will be replaced immediately by molybdenum atom sites to maintain mission electron microscopy (AC-STEM) images of antisite defects in MoS2
the hexagonal crystal structure (Figs. 4A–4D).42 Recently, hBN has monolayer. (C and D) Atomic models of (A&B) with Molybdenum (Mo) atoms
received attention due to the structural triangular hole defect in mono- shown in magenta color and sulfur (S) atoms shown in yellow color, adapted
layer of hBN sheet as shown in Fig. 5.43 Nitrogen has a higher thresh- with permission from Ref. 42 Copyright 2013, American Chemical Society.
old value than boron so, 80 kV of electron beam is enough to knock off
the boron from hBN sheet to create boron vacancies with nitrogen ter-
minated edge plane along with hole defect edges as shown in Figs. 5c–
5f.43 This triangular hole defect, having a single zigzag configuration,
is another aspect of novelty when compared to other graphene hole
defects that have combination of armchair and zigzag symmetry.44 Ad-
ditionally, this can offer tunable bandgap, and large and thin surface
area for electrochemical sensor applications.28,29,33,45,46
For example Sarkar et al. successfully demonstrated MoS2 based
field effect transistor (FET) biosensor which had 74 times higher sen-
sitivity than graphene-based FET biosensor (Fig. 6a).47 The achieved
higher sensitivity of MoS2 based FET biosensor was attributed to
high ultra-thin nature and excellent electrostatic properties of MoS2

Figure 5. A summary of density functional theory calculations and molecular

Figure 3. TMDs coordination and stacking sequences in structural unit cells,
adapted with permission from Ref. 33 Copyright 2015, American Chemical
Society.
dynamics simulations of hole growth processes in monolayers of hBN. The
red and blue dots represent boron (B) and nitrogen (N) atoms. (a) Calculated
bond lengths between boron and nitrogen atoms in a triangular hole. (b) The
B–N bonds perpendicular to the hole edge are broken first and often bundles of
atoms are then knocked off. (c-f) A series of TEM images show the formation
of a single chain followed by its fluctuation in position and ultimate removal.
The scale bar is 1 nm, adapted with permission from Ref. 43 Copyright 2015,
Royal Society of Chemistry.

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 Journal of The Electrochemical Society, 165 (16) B848-B861 (2018) B851

Figure 6. (a) 2D Transition metal atoms sandwiched between two layers of chalcogen used for label free field-effect transistor (FET) based electrochemical
biosensor, adapted with permission from Ref. 47. Copyright 2014, American Chemical Society. (b) Au deposited 2H phase MoS2 and (c) Au deposited 1T Phase
MoS2 used to measure the contact resistance with gate bias. Insert was optical microscopic images of devices and 5 μm scale bars, adapted with permission from
Ref. 48 Copyright 2014, Springer Nature.

with tunable bandgap (the band gaps of bulk MoS2 and monolayer
MoS2 were 1.8 eV and and 1.2 eV, respectively) and also suppressed
leakage currents. This has led to excellent sub-threshold swing for
MoS2 based FET biosensor.47 Additionally, Au doped MoS2 have
no defects between Au and S atoms, because of the weak Van der
Waals interaction between Mo and S atoms. Recently, semiconduct-
ing 2H phase of MoS2 , WS2 , MoSe2 , and WSe2 to the metallic 1T
phase via lithium ion intercalation was achieved to reduce contact
resistance.26 It was successfully demonstrated that Au deposited 1T
phase MoS2 had shown a lower contact resistances of 200–300 .μm
when compared to direct Au deposited with 2H phase MoS2, due to
induced semiconducting 2H phase nanosheets (Figs. 6b and 6c).48
Additionally, phase boundaries and dynamic behavior can be ob-
served in the same materials, for instance semiconducting 2H and
metallic 1T phases existed in a monolayer of TMDs.40,43 This con-
figuration can promote the electron from electrode to active edge
surface.
Additional reading on graphene-based pesticide electrochemical
sensors where not discussed in details. The focus of here was on
the properties, electrochemical exfoliation methods and respective
strategies to synthesis of 2D layered materials (hBN, MoS2 , WS2 )
and their promising applications in detecting pesticides. Suggested
additional reading include the following referenced papers.13,14,49–52
Electrochemical Exfoliation of 2D Materials
Electrochemical exfoliation is a simple and environmentally
friendly (it does not generate any acid waste) way to synthesize high
yield mono-layer of 2D materials with less defects at relatively low
cost. Therefore, many interesting electrochemical methods have been
developed to exfoliate 2D layered materials.53
Electrochemical exfoliation of TMDs.—The electrochemical ex-
foliation of TMDs by an experimental set up is illustrated in Fig. 7a.54
You et al. successfully exfoliated MoS2 nanosheets by electrochem-
ical method (Fig. 7b).55 In this method, the bulk MoS2 crystal used
as a working electrode and connected to an anode and Pt electrode
connected (counter electrode) to cathode (Fig. 7b). The 0.5 M H2 SO4
aqueous solution was used as an electrolyte. The applied voltage was
varied from 1 to 10 V in 10 min time interval. After that, a constant

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 B852 Journal of The Electrochemical Society, 165 (16) B848-B861 (2018)

Figure 7. (a) Schematic diagram of experimental setup for electrochemical exfoliation of TMD based materials, adapted with permission from Ref. 54. Copyright
2014, American Chemical Society. (b) Experimental setup for electrochemical exfoliation of MoS2 nanosheets, adapted with permission from Ref. 55. Copyright
2014, Elsevier. (c) A schematic diagram for electrochemical lithiation process for the preparation of 2D nanosheets from bulk materials, adapted with permission
from Ref. 56 Copyright 2011, John Wiley and Sons.

10 V was applied for 30 min to complete the exfoliation process. Dur-
ing this electrochemical exfoliation process, anionic OH− and SO4 2−
ions were intercalated into the bulk MoS2 crystals, formation of gas
bubbles (SO2 , O2 ), which helped to separate the monolayers of MoS2
from bulk MoS2 crystals. The intercalated gas bubbles acted as a sepa-
rating force between bulk MoS2 layers to overcome the Van der Waals
force of attraction. These exfoliated MoS2 layers are then collected by
vacuum filtration method followed by washing with water to remove
the residual H2 SO4 . Later it was dried and dispersed in dimethylfor-
mamide (DMF). The monolayers of MoS2 sheets were collected after
centrifugation at 2500 rpm for 30 min. The sheets exhibited lateral
size up to 20 μm as measured by transmission electron microscopy
(TEM) that can be used for various applications.55
Similarly, 2D nanosheets of MoS2 were obtained by electrochem-
ical lithiation process (Fig. 7c).56 Initially, the bulk materials (e.g.
MoS2 ) were used to connect the cathode side and lithium foil was
used to connect the anode side (Step 1 in Fig. 7c). During this step,
lithium ions were intercalated into the bulk materials, following to
expand the interlayer distance due to weak van der Waals interaction
between the layers. Similarly, metallic Li reacts with water to form
Li(OH) and H2 gas, which H2 gas bubbles were pushes the layers
further apart. After lithium intercalation step (step 2 in Fig. 7c), the
intercalated layered materials were washed with acetone and then ul-
trasonicated in water or ethanol to exfoliate the 2D nanosheets (step
3 in Fig. 7c).56
Additionally, Nasir et al. successfully synthesized or separated 1T
phase of 2D TMDs such as MoS2 , MoSe2 , WS2 and WSe2 materials
from each TMD bulk powder in tert-butyllithium (t-BuLi) solution.57
These materials were subsequently stirred for 72 h under inert at-
mosphere to do Li+ ion intercalation into the bulk TMDs. Then, Li
intercalated bulk TMDs was separated by vacuum filtration method
and washed with hexane solvent. The separated materials were dis-
solved in water for repeated centrifugation to get the exfoliated 1T
phase 2D materials.57
Electrochemical exfoliation of hBN.—Synthesis of hBN
nanosheets were demonstrated by bipolar electrochemical method.
A potentiostat used to supply a constant 10 V for 30 min through plat-
inum (Pt) electrodes immersed into the bulk hBN particles dispersed
in 0.5 M NaSO4 solution (Figs. 8A and 8B).58 While the polarization
reaction was taking place, hBN particles acted as a bipolar electrode
in electric field between two Pt electrodes. In this condition, elec-
trochemical exfoliation was promoted even in the absence of direct
ohmic contact from Pt electrodes. The exfoliations of hBN nanosheets
were identified by observing color change from white to milky white
(Figs. 8C and 8D). The sheet sizes were up to 1.27 μm as measured
by scanning transmission electron microscopy (STEM).58
Electrochemical Detection of Pesticide Using 2D Layered
Materials
MoS2 based detection.—2D MoS2 possesses many predominant
properties like large surface area, high sensitive and selective sur-
face state, biocompatibility and simple functionalization.59–65 How-
ever, pristine 2D MoS2 has poor electro-activity due to aggregation or
restacking properties. In order to overcome these issues, various strate-
gies have been used to improve the performance of 2D layered ma-
terials based electrochemical sensors. Immobilization of biomolecule

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 Journal of The Electrochemical Society, 165 (16) B848-B861 (2018)
Figure 8. (A) Schematic diagram of experimental setup for bipolar electro-
chemical exfoliation of hBN nanosheet. (B) Photograph image of experimental
setup for bipolar electrochemical exfoliation of bulk hBN. (C) 5 mg/mL con-
centration contains pristine bulk hBN solution (before exfoliation). (D) Bipolar
electrochemical exfoliated hBN nanosheet suspension, adapted with permis-
sion from Ref. 58 Copyright 2018, Royal Society of Chemistry.
such as enzyme, DNA, RNA or Ag, Au and Pt nanoparticles or
non-metal atom (boron, nitrogen, sulfur, fluorine and phosphorous)
or conductive polymers were interfaced with 2D layered materials.
These materials have improved the selectivity, sensitivity, response
time, as well as operational and storage stability and reproducibility
of the sensors.66–68 Common immobilization strategies were adopted
include entrapment, adsorption, covalent linkage, cross linkage, or
affinity linkage.69–71 Porous silicone polymeric membranes, cellulose
acetate and polyurethane have been also used to immobilize 2D lay-
ered materials and avoid electroactive interferents while still allowing
analytes to reach the electrode surface.72 However, each immobiliza-
tion methods have associated with some merits and demerits, so the
selection of the optimum analytical condition is important.73
In this context, Song et al. demonstrated Ag nanoparticles (NPs)
decorated nitrogen (N)-fluorine (F) co-doped MoS2 (Ag-N-F-MoS2 )
Figure 9. Schematic illustration of the fabrication process of the electrochemical biosensor for pesticides detection, adapted with permission from Ref. 74
Copyright 2018, Elsevier.
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B853
with NH2 functionalized CNT-AchE enzyme coated GCE as an elec-
trochemical sensor for monocrotophos and chlorpyrifos pesticides
(Fig. 9).74 The proposed composite material exhibited large elec-
troactive surface area and high electron mobility compared to Ag-
MoS2 and pristine MoS2 . The pesticides were detected by differential
pulse voltammetry (DPV). The proposed biosensor showed oxida-
tion peak for ATCl, the peak current decreased after inhibited with
monocrotophos or chlorpyrifos pesticides as shown in Figs. 10A and
10C.74 The obtained calibration curves of the biosensor based on
inhibition value determined by monocrotophos or chlorpyrifos pes-
ticides as shown in Figs. 10B and 10D.74 This biosensor showed
0.4 pM–4 nM linear range and low limit of detection (LOD) was
0.2 pM and 3 pM for monocrotophos and chlorpyrifos, respectively
(Table I). The biosensor also showed relatively high stability with
6.7% electrode response decrease after storage of 30 days. They also
suggested that proposed electrochemical biosensor can be used for
real-time analysis.74
Currently food sensors for pesticides detection are often enzyme-
based biosensors. However, use of enzymes presents a number of prob-
lems in real-time analysis. The most of common and serious among
them is their poor stability due to denature of the enzymes, prone
to thermal and chemical degradation during fabrication, storage and
use. Moreover, protein deposition and fouling effects leads to drifts
the sensor performance with time and frequent calibration needed be-
fore onsite pesticide detection. Additionally, enzyme preparation and
purification methods are highly difficult and expensive processes.75,76
In order to avoid enzymes, we need to identify highly selec-
tive compounds which can preferentially bind or detect the target
chemicals. Recently, MoS2 and graphene nanosheets based GCE de-
signed for selective methyl parathion (MP) detection. The MoS2 -
graphene/GCE showed high sensing ability which was consistent with
charge transfer resistance as measured by electrochemical impedance
spectroscopy (EIS). The aforementioned MoS2 -graphene based elec-
trodes charge resistance values where lower than bare/GCE, MoS2 and
graphene modified GCEs. This might be due to electrode-electrolyte
interface is considerably reduced after MoS2 mixed with graphene
nanosheets.77
As observed, electrocatalytic activity of MoS2 /graphene modi-
fied GCE showed increased reduction peak current when compared
to MoS2 modified GCE, graphene modified GCE and bare GCE
for 200 μM of MP (Fig. 11A). These results are clearly indicated
the MoS2 incorporated graphene showed greater electrochemically
 B854 Journal of The Electrochemical Society, 165 (16) B848-B861 (2018)

Figure 10. (A) DPV responses of AchE/NH2 -CNTs/Ag-N-F-MoS2 /GCE in 0.1 M PBS solution with 4 mM ATCl after incubation in (A) a-h: 0, 10−10 , 5 ×
10−10 , 10−9 , 5 × 10−9 , 10−8 , 10−7 , 10−6 mg.mL−1 of monocrotophos for 15 min (C) a-h: 0, 5 × 10−9 , 10−8 , 5 × 10−8 , 10−7 , 10−6 , 10−5 , 10−4 mg.mL−1
of chlorpyrifos for 15 min. (B and D) Calibration curves for monocrotophos and chlorpyrifos determination. Error bars are coefficient of variation across three
respective experiments, adapted with permission from Ref. 74 Copyright 2018, Elsevier.

active surface area than the control, likely due to the synergetic effect
between MoS2 and graphene sheets.77 CVs obtained for different con-
centration of MP in PBS solution at MoS2 /graphene modified GCE
showed reduction peak current changed linearly with increasing the
concentration of MP (Fig. 11B).77 Moreover, real samples (apple,
kiwi, tomato and cabbage) were also used for MP detection. Results
for the apple sample shown in Fig. 12a.77 The concentration depen-
dence on linear calibration graph for apple sample is given as Fig. 12b.
The limit of detection (LOD) and linear ranges were given in Table I.77
WS2 based detection.—Electrochemically exfoliated WS2 (a
monolayer of W atoms sandwiched between S atoms), has been creat-
ing more interest in electrochemical sensor applications. The bandgap
of the WS2 monolayer reaches 1.9 eV. Hydrogen peroxide (H2 O2 ) was
used as a pesticide in 1998 for plants, fruits and vegetable crops; in
high concentrations it can be corrosive.78 Recently, lab-on-chip (LOC)
device reported using t-BuLi exfoliated (1T phase) WS2 for H2 O2
detection and compared with other 1T phase TMD materials such
as MoS2 , MoSe2 and WSe2 . The (1T phase) WS2 based LOC device
sensing performance was greater than other 1T phase TMD materials
(Fig. 13).79 In addition, the relative standard deviation (RSD) value
obtained for the WS2 based H2 O2 sensor system was 17.6%,79 which
indicated good reproducibility of the sensor system.79,80 The interfer-
ence study was carried out with WS2 based LOC device at the 2 mM
of H2 O2 concentration. Ascorbic acid (35.2%), uric acid (37.5%) and
dopamine (61.8%) were considered as interference molecules which
showed notable response.79 Taking this into consideration for real
sample applications, 88.5% of signal recovery is attained with 10%
human serum in PBS electrolyte, indicating it’s applicability for real
sample analysis.79 The LOD and linear ranges were given in Table I.

Table I. Comparative study on the pesticides detection capacity of 2D layered materials by electrochemical analysis method.

Enzymatic/Non
2D layered materials Enzymatic Method Pesticide Linear range LOD Reference
AchE-NH2 -CNT/Ag-N-F-MoS2 /GCE Enzymatic DPV Monocrotophos 0.4 pM–4 nM 0.2 pM 74
AchE-NH2 -CNT/Ag-N-F-MoS2 /GCE Enzymatic DPV Chlorpyrifos 0.15 nM–3 μM 3 pM 74
MoS2 -Graphene/GCE Non-Enzymatic Amperometry Methyl parathion 0.01 μM–1905 μM 3.23 μM 77
1T-WS2 /LOC device Non-Enzymatic Chronoamperometry H2 O2 20 nM–2 mM 2 nM 79
1T-WS2 /GA/AChE-BSA/GCE Enzymatic Chronoamperometry Fenitrothion 1–1000 nM 2.86 nM 57
MIP/Fe@AuNPs/2D-hBN/GCE Non-Enzymatic DPV Cypermethrin 0.1 pM–10 nM 30 fM 27

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 Journal of The Electrochemical Society, 165 (16) B848-B861 (2018)
Figure 11. (A) CV obtained at bare GCE (b), MoS2 /GCE (c), graphene/GCE
(d), MoS2 -graphene/GCE (e) in 100 mM PBS containing 200 μM MP and
(a) is representing the CV of MoS2 -graphene/GCE in absence of MP. (B)
CV obtained at MoS2 -graphene/GCE in 100 mM PBS containing different
concentration of MP (a = 50, b = 100, c = 150, d = 200, e = 250, f = 300,
g = 350, h = 400, i = 450 and j = 500 μM), adapted with permission from
Ref. 77 Copyright 2017, Springer Nature.
Nasir et al. also demonstrated t-BuLi exfoliated 1T phase
TMDs/GA/AChE/BSA/GCE based electrochemical biosensor for fen-
itrothion pesticide detection.57 The 1T phase WS2 modified biosensor
had higher electrochemical activity than other TMD materials such as
(MoS2 , MoSe2 , and WSe2 ). This observation was consistent with ear-
lier results.79 The LOD and linear ranges were given in Table I. This
good performance was linked to the excellent electron transfer ability
of 1T phase WS2 based biosensor for enhancing electrochemical sig-
nal (Fig. 14).57 The t-BuLi exfoliated 1T phase WS2 was effectively
separated from the bulk material as evident from the greater separa-
tion of E1 2g and A1g vibration modes observed for WS2 material when
simultaneously compared with other TMD materials (MoS2 , MoSe2 ,
WSe2 ). WS2 was sensitively separated than other TMD materials as
illustrated in Raman spectra (Fig. 15).57 The efficient conversion of
WS2 might be reason for significant percentage of oxidized form of
tungsten (W6+ ). From the X-ray photoelectron spectroscopy (XPS),
it was evident that the W based TMDs have higher binding energies
than Mo based TMDs. Due to that reason, it was effectively converted
from 2H polymorph to 1T polymorph upon t-BuLi exfoliation as pre-
viously reported.40 It was also noted that sulfur based Mo, W materials
performed greater than selenide based Mo, W materials.
hBN based detection.—hBN based nanocomposites are propitious
2D materials because of their multifunctional applications in sensors,
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B855
Figure 12. (a) Amperometric response of MoS2 -graphene/GCE used differ-
ent concentration of MP detected in apple sample solution. (b) The linear
calibration plot for MP determination in apple sample. Applied potential volt-
age is −0.60 V vs. Ag/AgCl, adapted with permission from Ref. 77 Copyright
2017, Springer Nature.
molecular electronics and catalysis.81–84 Especially, it received more
attention in biomedical applications such as bio-imaging and drug de-
livery systems due to stable water dispersion and less cytotoxicity.85
Based on its structure and property, 2D hBN is known as white
graphene, with physicochemical properties such as high thermal sta-
bility and conductivity, huge mechanical strength, and large surface
area.86,87 Additionally, large band-gap creates transparent property in
visible and IR regions.88,89 Metal nanoparticles or carbon nanoma-
terials loaded 2D hBN nanosheets have received great attention in
selective and sensitive pesticide detection.86–89
It was demonstrated that Fe@Au NPs/2D hBN nanosheets with
molecular imprinted polymer (MIP) for electrochemical sensing of
cypermethrin (CYP) pesticide. The CV peaks of Fe@Au NPs/2D
hBN/GCE was observed at about 60 mV of potential difference (Ep)
as seen in Fig. 16A (curve c).27 Meanwhile comparisons with 2D
hBN/GCE and bare GCE, 110 mV and 150 mV (Ep) of potential
difference were observed as seen at Fig. 16A (curve a&b).27 This study
revealed that Fe@Au NPs/2D hBN/GCE had more electrocatalytic ac-
tivity than 2D hBN/GCE and bare GCE (Fig. 16A).27 Fe@Au NPs/2D
hBN had fast charge transfer property and reduction of mass transfer
ability due to synergistic effect between the 2D hBN and Fe@Au NPs.
Furthermore, MIP polymer was used with above electrodes for CYP
pesticide analysis. DPV peaks were consistent with above CV peaks
 B856 Journal of The Electrochemical Society, 165 (16) B848-B861 (2018)

Figure 13. (a) and (b) Schematic representation of LOC setup for H2 O2 detection. (c) Photograph for experimental setup with S$1 coin for scale. Experimental
condition: PBS 10 mM, 7.4 pH was injected into the microfluidic channel at a flow rate of 40 μL min−1 . Simultaneously H2 O2 injected into the channel at a flow
rate of 50 μL min−1 . (d) Chronoamperometric response of TMDs based LOC devices upon injection of 200 μM H2 O2 , adopted with permission from Ref. 79
Copyright 2017, American Chemical Society.

(Fig. 16B).27 Fig. 16C indicated the effective linear responsibility for
CYP pesticide detection using the proposed MIP Fe@AuNPs/2D-
hBN/GCE sensor. The LOD value of proposed sensor was 3.0 ×
10−14 M. In addition, this sensor when used on samples showed high
stability, selectivity, reusability and repeatability.27 The comparison of
various 2D layered materials based electrochemical pesticides sensors
and their analytical parameters are compared in Table I. From the ta-
ble, it was interesting to note that MIP/Fe@AuNPs/2D-hBN modified
GCE had lowest LOD value up to 30 fM level. Herewith, we think that
hBN based non-enzymatic electrode may be recommended for very
low level pesticides detection than other 2D layered TMD materials
(MoS2 , MoSe2 , WSe2 , WS2 ) based on enzymatic or non-enzymatic
modified GCE electrodes.
Future Prospects
2D layered materials are receiving huge interest in wearable elec-
trochemical sensor applications because of their layer by layer atoms
arrangement with unique electrical and electrochemical properties.
Recently, Choi et al. demonstrated MoS2 based wearable sensors
attached to human skin matrix for possible health monitoring pur-
pose (Fig. 17).90 It was predicted that flexible and wearable electro-
chemical sensors will be a promising trend for on-site (bio) chemical
detection.91–96 The wearable electrochemical sensors provide results
directly from wearer’s body. Most of the reported biosensors have
been studied primarily on enzyme modified electrodes for pesticide
detection.97,98 In addition, enzymatic based wearable sensor devices
are all non-invasive and could detect lactate, uric acid, glucose, alcohol
in sweats, tears, saliva and interstitial fluids,93–95,99–102 which have been
focused on healthcare monitoring applications.103–108 There are grow-
ing demand for wearable electrochemical sensors for highly hazardous
chemicals detection in food and environmental samples. For this pur-
pose, Mishra et al. developed a flexible glove based electrochemical
biosensor for real time MP detection. These kind of sensor devices
will play main role on-the-hand multiplexed pesticides detection in
diverse fields (Fig. 18).109 Consequently, there are also opportunity
to use paper or polymer based flexible and wearable non-enzymatic
electrochemical sensors and it may provide a scalable, low-cost and
on-site pesticides detection in food samples.110 It reminds that in the
17th century, Emperor “Shah Jahan” used some nifty celadon plates
which said to split into pieces or change color if the food served on
them contains poison (right now this plate was located at Taj Mahal
Museum, Agra, India).111 These kinds of visual devices or tools are
necessary for easy identification and detection of various contami-
nants for industry and consumers with low-cost. We envision that 2D
layered materials may find real applications in manufacturing flexible
and wearable enzymatic/non-enzymatic electrochemical sensor de-
vices to detect ultra-trace analytes present in the sample matrix with
high sensitivity and selectivity in the years to come.

Challenges and Outlook

Figure 14. Chronoamperometric responses of TMDs with successive addition
of acetylthiocholine (ATCh) in 10 mM PBS. GC (glassy carbon electrode); GA
(glutaraldehyde); AChE (acetylcholinesterase); BSA (bovine saline albumin)
adopted with permission from Ref. 57 Copyright 2017, American Chemical
Society.
It is worth not mention that stability of 2D materials depends on
their atoms arrangements, which can be differentiate from one to an-
other. For instance, graphene is highly stable against oxidation,112
whereas, silicene and phosphorene get oxidized in air and found
to be chemically poor stable.113,114 Moreover, most of the 2D ma-
terials are easily undergoing oxidation in ambient conditions can
therefore present number of challenges during synthesis, character-
ization, active device fabrication and testing.115 Atomically thin 2D
layered materials exhibit high sensitivity to oxidation because of their

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 Journal of The Electrochemical Society, 165 (16) B848-B861 (2018) B857

Figure 15. A 514.5 nm argon excitation laser used Raman spectra for t-BuLi exfoliated MoS2 , MoSe2 , WS2, WSe2 , adapted with permission form Ref. 57
Copyright 2017, American Chemical Society.

unsaturated valencies, higher surface area, atomic-level defects etc.115
For example, exfoliated 2D layered MoS2 is highly hygroscopic na-
ture and lead to absorb moisture from air and formed water on the
surface seems to decrease the electron mobility and increase the sheet
resistivity.116–118 Kiriya et al. demonstrated air-stable MoS2 using ben-
zyl viologen (BV) as the surface charge transfer donor (Fig. 19A).118
After such modification, these devices showed high carrier mobil-
ity and superconducting transition property for monolayer of MoS2 .
In addition, these devices showed no environmental degradation and
oxidation under air atmosphere (Fig. 19B).118
2D materials synthesis and applications are still at an early stage
and electrochemical exfoliation synthesis must be further explored
to different types of materials. Most of the electrochemically exfoli-
ated TMDs resulted as multilayers both in aqueous solution contain-
ing surfactant and organic solvents.119 O’Neill et al. reported 40%
yield for MoS2 by controlling the sonication time, resulting in con-
centrations upto 40 mg/mL.120 To the best of our knowledge, there
is no complete data available about yield of the products by sin-
gle layer percentage and yield by single layer weight for electro-
chemically exfoliated TMDs. The product yield by weight for all
2D layered materials should be evaluated and reported. To date, ab-
sorption coefficient values were suggested only for few 2D layered
materials, i.e., MoS2 (3400 mL/mg/m), WS2 (2756 mL/mg/m) and BN
(2367 mL/mg/m).121
Low quantity of samples were only produced using electrochem-
ical exfoliation of synthetic or natural bulk materials.57,79 Synthesis
of layered materials (2D crystals) with high purity from simple pro-
cess has to be developed and it will play vital role for taking the
2D layered materials into direct applications. So far, electrochemical
exfoliation methods produced a random array of 2D crystals with a
variety of thickness, sizes, and defects which limits the scalability and
reproducibility for industrial level production.122,123 To produce large
scale TMDs with large surface area and high quality crystals in a scal-
able and reproducible manner may require an alternative production
strategy to achieve pure 2D materials.
Limitations
2D materials with surface passivation layers have been shown
to be responsible for inherent electrochemical properties which are
some of limitations to sensor applications. Because, inherent electro-
chemical property of the layered materials would vary from synthetic
experimental procedures such as applied voltage, pH and nature of
electrolyte.33 It should be emphasized that much adversity remains
in clear identification of reaction mechanisms and observed electro-
chemical properties. Some of the reasons for this complexity of 2D
materials is that its oxide layer can undergo parallel reactions.33,115 In
addition, the number of layers will also affect the properties of TMDs

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 B858 Journal of The Electrochemical Society, 165 (16) B848-B861 (2018)

Figure 16. (A) CV response of (a) bare GCE, (b) 2D-hBN/GCE, (c) Fe@AuNPs/2D-hBN/GCE; Redox probe: 1.0 mM [Fe(CN)6 ],3− scan rate: 200 mV/s. (B)
differential pulse voltammogram (DPV) response of (a) MIP bare GCE, (b) MIP 2D-hBN/GCE, (c) MIP Fe@AuNPs/GCE, and (d) MIP Fe@AuNPs/2D-hBN/GCE
in PBS containing 10 nM CYP concentration, (C) DPV response of different concentration of CYP at MIP Fe@AuNPs/2D-hBN/GCE in PBS solution (pH 10),
adapted with permission from Ref. 27 Copyright 2018, The Electrochemical Society.

Figure 17. (a) A schematic diagram of MoS2 based transistor for organic light emitting diode (OLED) display. (b) Optical images of dynamic operation on
human wrist using external circuit; representative letter “M”, “O”, “S”, “2” are sequentially changed on skin during addressing the skin matrix line, adapted with
permission from Ref. 90 Copyright 2018, American Association for the Advancement of Science.

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 Journal of The Electrochemical Society, 165 (16) B848-B861 (2018) B859

Figure 18. On-site glove based pesticide detection. (A and C) Photographs during methyl parathion (MP) detection on contaminated surfaces of (A) (i) apple,
(ii) tomato, (iii) grape, and (iv) green pepper, In addition MP detection on (C) (i) glass, (ii) wood, (iii) stainless steel, and (iv) plastic. (B and D) SWV conditions:
voltage range, +0.30 to +1.20 V vs. Ag/AgCl. (E) Enzyme based electrochemical biosensor integrates with lab-on-glove used for pesticide detection and wireless
data transmission to a smartphone device, adapted with permission from Ref. 109 Copyright 2017, American Chemical Society.

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 B860 Journal of The Electrochemical Society, 165 (16) B848-B861 (2018)
Figure 19. (A) Schematic illustration of a benzyl viologen (BV) doped MoS2 device used for surface charge transfer studies. (B) Transfer characteristic curves
of the BV doped and undoped device, and after the BV doped device was kept in air for 1 day at VDS = 1 V. The inset shows an optical microscope image of the
device, consisting of trilayer MoS2 , adapted with permission from Ref. 118 Copyright 2014, American Chemical Society.
significantly, so it has to be controlled for reliable electro-catalytic
and device performance.124 As reported previously, the phase change
will affect the MoS2 electronic property completely. For instances,
2H-MoS2 (semiconductor) will turn to metallic when it present
as IT-MoS2 which is more catalytic active for hydrogen evolution
reaction.124 Obviously, metallic nature is more beneficial for electro-
chemical sensor applications. It is mandatory to develop new tools
and methods to predict the phase changes of TMDs materials and
associated physical/chemical properties.125 Despite their drawbacks
as mentioned above, current trend on synthesis and applications of
2D materials will continue due their potential applications in sensors,
actuators, energy and other electromechanical devices.
Conclusions
In summary, we have discussed the structural properties and elec-
trochemical synthesis of 2D layered materials and their potential appli-
cation for pesticides detection. It was interesting to note that many 2D
layered materials exfoliated by facile electrochemical method were
low cost and high yield. 2D layered materials have high electro-
chemical activities which depend on their atom arrangement, crystal
structure, size and defects. These unique structures of 2D layered
materials provide anisotropic basal and edge planes created potent
electrochemical activity. Specifically, WS2 has been demonstrated to
be electrochemically active for the detection of pesticide due to 1T
phase. WS2 was effectively separated compared to other TMD ma-
terials. Additionally, there is also increasing interest on the inherent
electrochemical property of layered materials, whereby the metal NPs
or enzymes can undergo electrochemical oxidation, reduction or re-
dox reaction happen in real time, which improve their electrochemical
activities. Such materials can effectively detect the electrochemically
active substances in solution. Significant tests have also been carried
out to create electrocatalytic systems for pesticides detection. Here,
we discussed various strategies for activation and improving pesti-
cides detection on 2D layered materials, including amplifying the
disclosure of active sites, assembling enzyme or NPs doping based
2D layered hybrids on electrocatalyst support. Given the fact that pris-
tine 2D layered materials are vastly ambidextrous in terms of atom
arrangement and physical structure. One can trust that efforts toward
further improving the electrochemical activities of these new genera-
tion 2D layered materials will place them in the forefront of research.
In addition, doping and enzyme modifications of the surface/edges
of 2D layered materials will lead to highly sensitive and selective
pesticide detection.
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Acknowledgments
We acknowledge the Department of Science and Technology
(DST), Science and Engineering Research Based (SERB), Govern-
ment of India for financial support. Award No.: ECR/2016/001446.
Additional thanks for technical writing support to Kari Jordan, Depart-
ment of Biological Systems Engineering, University of Wisconsin-
Madison, Madison, Wisconsin, USA.
ORCID
Ashok K. Sundramoorthy https://orcid.org/0000-0002-8512-9393
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