nanomaterials

Article
Nanocomposite Synthesis of Nanodiamond and
Molybdenum Disulfide
Youngjun Kim, Dukhee Lee, Soo Young Kim , Eunah Kang * and Chang Keun Kim *
School of Chemical Engineering and Material Science, Chung-Ang University, Seoul 06974, Korea
* Correspondence: [email protected] (C.K.K.); [email protected] (E.K.);
Tel.: 82)-2-820-5324 (C.K.K.); 82)-2-820-6684 (E.K.)




Received: 7 June 2019; Accepted: 26 June 2019; Published: 27 June 2019


Abstract: A chemically conjugated nanodiamond (ND)/MoS2 nanocomposite was synthesized

with amine-functionalized MoS2 and acyl chloride-coordinated ND. The chemical structure and
morphology of the nanocomposite were characterized to examine the dispersion of MoS2 on the ND
platform. The results revealed that the degree of dispersion was enhanced with increasing ratio of
MoS2 nanosheets to ND. Moreover, the nanosheets consisted of several molecular interlayers that
were well-dispersed on the ND platform, thereby forming a nanophase. The efficient electrocapacity
of the ND/MoS2 nanocomposite was considerably greater than that of the MoS2 electrode alone.
Furthermore, the nanophase distribution of MoS2 on ND with a graphitic shell provided a large
surface area and reduced the diffusion distance of ions and electrons. Therefore, the nanophase
electrode showed higher electrochemical capacitance than that of the MoS2 electrode alone.

Keywords: nanocomposite; MoS2 ; nanodiamond

1. Introduction
Numerous novel materials and composites including two-dimensional (2D) materials have
been exploited with the aim of enhancing electrocapacity, which can be applied for biosensing
platforms and electrocatalytic performance. A 2D layered material can be defined as an unsupported
crystalline solid with molecular layer thickness characterized by intralayer storage for heat, charge,
and light transport [1–4]. This transport occurs in the presence of intralayer covalent bonds and
intercalation-based interaction [5]. Specifically, MoS2 as a 2D transition metal dichalcogenide (TMD)
exhibits the unique characteristic of charge confinement in the 2D layer in the absence of interlayer
interaction along the z-axis [6]. Functional features of 2D MoS2 layers include high thermal and chemical
stability for functionalization [7,8], large surface area [4], good mobility [9], and intercalation-based
physical interaction [10,11]. For final functional performance, the construction of an electrode and
nanophase distribution of an aggregation-free 2D MoS2 molecular layer are critical to induce maximal
functional features.
Carbon-based materials including fullerenes, graphene, and carbon nanotubes, are considered as
fundamental platform materials of energy conversion and storage, owing to their thermal stability,
conductivity, and mechanical properties [12–15]. Furthermore, the electron buffering capability of
these materials stems from their high surface-to-volume ratio and the unsaturated carbon u bonds.
Physicochemical characteristics can reduce oxygen adsorption on a catalyst surface, thereby improving
the material performance. In general, the porous structure of carbon materials is characterized
by a multiscale nanocage and a high surface-to-volume ratio that provide electron transfer and
electrocatalytic active sites. These advantages have often been applied to nanocomposites with metal
to induce synergistic functional effects, including solar cells, batteries, and supercapacitors [16–20].

Nanomaterials 2019, 9, 927; doi:10.3390/nano9070927 www.mdpi.com/journal/nanomaterials

 X-ray photoeletron spectroscopy (XPS; ThermoFisher Scientific Co., Waltham, MA, USA)
measurements were also conducted with an Al Kα energy source. The spectra were analyzed using
Avantage software (version 1.6, Thermo Fisher Scientific, Waltham, MA, USA). Transmission
electron microscopy (TEM) images were obtained with a JEM-2100F electron microscope (JEOL,
Tokyo, Japan).
Nanomaterials 2019,For sample preparation, 10 μL each of ND, MoS2, and ND/MoS2 nanocomposite2was
9, 927 of 11
dropped on Formvar/Carbon on a 200 mesh grid (TED PELLA Co., Redding, CA, USA.) and dried
for 10 min at 60 °C in an oven.
Nanodiamonds (NDs) among carbon platforms have received less attention than some of the other
carbon materials
2.3. Cyclic Voltammetrydue to theMeasurements
(CV) high costs and low conductivity of these materials as electric functional
materials [21,22]. However, NDs possess excellent physical properties, including high adsorption [23],
highA dispersion of ND/MoS
surface-to-volume 2 nanocomposite (1 mg/mL) was prepared in Nafion solution (0.5% in
ratio [24], chemical modality on the graphitic shell surface [25], and a nanocage
DI
within agglutinate [26]. Moreover, theDroplets
water) for electrode fabrication. of capability
dispersive the dispersion
of NDs (10inμL) were environments
aqueous placed on themakes
glassyit
carbon
possibleworking electrode
to integrate and to(diameter 3 mm) to
extend materials and dried
other at 80 °Cemployment,
functional for 1 h. Cyclic voltammetry
including (CV)
biomedical
measurements (potential: −0.8 to 0.2 V, scan rate: -0.2 to 1.0 V) were performed
applications as well as electronic functions [27]. NDs serve as a supporting platform that can augment using a
three-electrode system (reference electrode: Ag/AgCl, counter
the functional efficiency of the other incorporated pair of 2D materials. electrode: platinum wire (57 mm in
length, OD 0.5 mm),
Therefore, working
in this study electrode:
a ND/MoS ND/MoS 2 or MoS2 deposited glassy carbon electrode). Two
2 nanocomposite by subsequent functionalization was
sets
synthesized and characterized. An ND with a graphiticDigi-Ivy,
of measurements using a potensiostat (DY2322, Austin,
shell around TX, USA)
its surface werestable
provides also
performed at potentials
sites for chemical rangingImmediate
modification. from 0.05 to 0.5 V·s reaction
chemical
−1 and scan rates of
between the0.05,
acyl0.1, and 0.5
chloride V/s. The
of NDs and
corresponding CV plots were recorded in a 0.1 M KOH solution (15 ml).
amine-functionalized MoS2 was intended to form aggregation-free MoS2 nanosheet dispersion onFive cycles in 2 sets were
the
performed
ND supportto(Scheme
obtain 1). a voltamogram.
This nanophaseAfter stabilization
dispersion of MoS2from repeated
in several cycles,on
interlayers anthe
oxidation and
ND platform
reduction
was examinedcurvefrom
in each
the second set of
viewpoint of aphysical
working electrode wasand
characteristics shown for data
potential presentation.
electrofunctionality.

Scheme 1. Schematic showing conformation of the nanodiamond (ND)/MoS nanocomposites.

Scheme 1. Schematic showing conformation of the nanodiamond (ND)/MoS22nanocomposites.
2. Experimental Methods
3. Results and Discussion
2.1. Nanocomposite Formation of MoS2 and Nanodiamonds
UV–vis absorption spectra were obtained for the MoS2 nanosheets, ND-COCl, and ND/MoS2
nanocomposite
ND-COOHs with ratios
(40 mg) of 1:1,
gifted from1:2, 1:4, and 1:8 (Seoul,
Nanoresource (FigureKorea)
1). Typical MoS2 with
were mixed excitation
100 mL absorption
of thionyl
peaks, which
chloride occurred
(Samcheon at 630 and
Chemical Co.,690 nm,Korea)
Seoul, were attributed
and 0.5 mL toofthe direct gap transitions
dimethylformamide at the K(DMF)
anhydrous point
[30–32] These
in a 250. mL indicate the lowest
round-bottomed optical
flask. The band gapwere
ND-COOHs of thewell-dispersed
MoS2 nanosheets for 15(i.e.,
min~1.8 eV) sonication
of bath that were
changed,
under an owing
ice bath.to The
the quantum confinement
ND dispersion in thewas
for acylation sheets. Changes
stirred for 24 h inatthe ◦ C under
70 UV absorbance were
a N2 purge.
evaluated for the
After reaction, theMoS 2/ND nanocomposite
dispersion with ratios
was washed repeatedly fiveoftimes
1:1 towith
1:8. tetrahydrofuran
The optical absorbance
anhydrous peaks of
(THF)
and the NDs, separated by centrifugation, were dried at 60 ◦ C in an air-circulated oven.
For exfoliation, the mixture of pristine MoS2 (120 mg, <2 µm; Sigma-Aldrich Chemicals, St Louis,
MO, USA) and N-vinyl-2-pyrrolidone (60 mL) was sonicated with condition of 55% power amplitude
and 3 s pulse (VC750, Sonics Vibra-cell) for 8 h under circulation at 7 ◦ C [28]. After exfoliation,
the large MoS2 was separated by centrifugation (4000 rpm, 5 min), and the supernatant was extracted.
This supernatant was then filtered through a syringe filter (0.45 µm, HP045AN, Advantec, Taipei,
Taiwan) and centrifuged (14,600 rpm, 10 min). Afterward, the settled MoS2 nanosheets were washed
with isopropanol and centrifuged repeatedly until the yellow color of N-vinyl-2-pyrrolidone became
colorless. The nanosheets were then dried for 24 h at 40 ◦ C under vacuum.
The MoS2 nanosheets (1 mg/mL) were dispersed in DMF. For chemical conjugation, 200 µL of
cystamine (5 mg/mL) in DMF was added to 1 mL of the MoS2 dispersion. This dispersion mixture
was then sonicated for 1 h under an ice bath. After sonication, the mixture was left to stand at room
Nanomaterials 2019, 9, 927 3 of 11

temperature for 24 h. Then, functionalized MoS2 was washed repeatedly three times with DMF,
separated by centrifugation at 14,600 rpm, and completely dried at 60 ◦ C in a vacuum oven.
Acylated NDs (1 mg/mL) and amine-functionalized MoS2 nanosheets in DMF were dispersed
with 5 min of bath sonication. The dispersion of acylated ND and amine-functionalized MoS2 with
desired ratios (1:1, 1:2, 1:4, and 1:8) was mixed by sonication under an ice bath for 30 min, and shaken
with a vortex for 24 h. After the reaction, the composite was washed and completely dried at 60 ◦ C in a
vacuum oven.

2.2. Characterization of ND/MoS2 Nanocomposites

The ultraviolet (UV) absorption of ND-COCl, MoS2 nanosheet, and ND/MoS2 nanocomposite
was measured with a V-670 UV-Vis/NIR spectrophotometer (JASCO Corp., Tokyo, Japan). These
measurements were performed under the following conditions: scanning speed: 200 nm/min, data
interval: 1 nm, UV-Vis bandwidth: 1.0 nm, near-infrared (NIR) bandwidth: 2.0 nm, and wavelength:
350–900 nm [29]. The dispersions (0.2 mg/2 mL) of the nanosheets and the nanocomposite in deionized
(DI) water were placed, respectively, in a synthetic quartz cuvette (light path: 1 cm, Hellma Analytics,
Müllheim, Germany). Measurement of Fourier transform infrared spectroscopy (FT-IR; Nicolet 6700,
Thermo Scientific., Waltham, MA, USA) ranged from 4000–500 cm−1 of wavelength and was performed
subsequently on the chemical reactant, ND, and MoS2 . IR samples were prepared using the standard
method of KBr pellet (7 mm in diameter). The materials of 0.5–1 mg were added with a portion of KBr
(7 mg).
X-ray photoeletron spectroscopy (XPS; ThermoFisher Scientific Co., Waltham, MA, USA)
measurements were also conducted with an Al Kα energy source. The spectra were analyzed
using Avantage software (version 1.6, Thermo Fisher Scientific, Waltham, MA, USA). Transmission
electron microscopy (TEM) images were obtained with a JEM-2100F electron microscope (JEOL, Tokyo,
Japan). For sample preparation, 10 µL each of ND, MoS2 , and ND/MoS2 nanocomposite was dropped
on Formvar/Carbon on a 200 mesh grid (TED PELLA Co., Redding, CA, USA.) and dried for 10 min at
60 ◦ C in an oven.

2.3. Cyclic Voltammetry (CV) Measurements

A dispersion of ND/MoS2 nanocomposite (1 mg/mL) was prepared in Nafion solution (0.5% in
DI water) for electrode fabrication. Droplets of the dispersion (10 µL) were placed on the glassy
carbon working electrode (diameter 3 mm) and dried at 80 ◦ C for 1 h. Cyclic voltammetry (CV)
measurements (potential: −0.8 to 0.2 V, scan rate: −0.2 to 1.0 V) were performed using a three-electrode
system (reference electrode: Ag/AgCl, counter electrode: platinum wire (57 mm in length, OD 0.5 mm),
working electrode: ND/MoS2 or MoS2 deposited glassy carbon electrode). Two sets of measurements
using a potensiostat (DY2322, Digi-Ivy, Austin, TX, USA) were also performed at potentials ranging
from 0.05 to 0.5 V·s−1 and scan rates of 0.05, 0.1, and 0.5 V/s. The corresponding CV plots were recorded
in a 0.1 M KOH solution (15 ml). Five cycles in 2 sets were performed to obtain a voltamogram. After
stabilization from repeated cycles, an oxidation and reduction curve in each second set of a working
electrode was shown for data presentation.

3. Results and Discussion

UV–vis absorption spectra were obtained for the MoS2 nanosheets, ND-COCl, and ND/MoS2
nanocomposite with ratios of 1:1, 1:2, 1:4, and 1:8 (Figure 1). Typical MoS2 excitation absorption
peaks, which occurred at 630 and 690 nm, were attributed to the direct gap transitions at the K
point [30–32]. These indicate the lowest optical band gap of the MoS2 nanosheets (i.e., ~1.8 eV) that
were changed, owing to the quantum confinement in the sheets. Changes in the UV absorbance were
evaluated for the MoS2 /ND nanocomposite with ratios of 1:1 to 1:8. The optical absorbance peaks
of MoS2 /ND nanocomposite appeared in the same region as those of the MoS2 nanosheets. It was
indicated that chemically conjugated MoS2 /ND nanocomposite maintained the optical characteristics
Nanomaterials 2019, 9, x FOR PEER REVIEW 4 of 11

Nanomaterials 2019, 9, 927 4 of 11

MoS2/ND nanocomposite appeared in the same region as those of the MoS2 nanosheets. It was
indicated that chemically conjugated MoS2/ND nanocomposite maintained the optical characteristics
of the
the nanosheets.
nanosheets.The
Theintensity
intensityofofthe
thebands
bandsinin
thethe
spectra were
spectra augmented
were withwith
augmented the increasing ratio ratio
the increasing
of the nanocomposite, as shown in Figure 1 [33].
of the nanocomposite, as shown in Figure 1 [33].

Figure 1. UV−vis absorbance spectra of MoS2 nanosheets, ND, and ND/MoS2 nanocomposites with
Figure 1. UV−vis absorbance spectra of MoS2 nanosheets, ND, and ND/MoS2 nanocomposites with
ratios of 1:1, 1:2, 1:4, and 1:8.
ratios of 1:1, 1:2, 1:4, and 1:8.
Chemical conjugation of the nanocomposite and functional groups of intermediate products was
Chemicalviaconjugation
characterized of the nanocomposite
FT-IR spectroscopy and functional
to identify sequential groups of of
chemical modification intermediate products
the acyl chloride
was characterized
comprising via FT-IRMoS
ND (ND–COCl), spectroscopy to identify sequential chemical modification of the acyl
2 -NH2 , and MoS2 /ND nanocomposites (Figure 2). The oxidative
chloride comprising ND (ND–COCl),
treatment formed a carbonyl group (C=O) and a2-NH MoS 2, and
hydroxyl MoS(-OH),
group 2/ND nanocomposites (Figure
occurring as absorption peaks2). The
oxidative
at 1718 andtreatment −1
3400 cm formed a carbonyl
on the surface group (C=O)ND,
of the carboxylated and a hydroxyl
respectively. group
The (-OH),
graphitic shelloccurring
around as
absorption peaks
the crystalline ND atwas1718 and 3400
attributed cm absorption
to the −1 on the surface
bandsof the carboxylated
associated with C=CND, bond respectively.
bending at The
1625 cm−1 .shell
graphitic Afteraround the crystalline
acyl chlorination, ND with NDanwas acylattributed
chloride bondto the absorption
(C-Cl) was formed,bands associated with
corresponding
to thebond
stretching peak −1 , whereas no peak for ND-COOH was observed [34]. The results
C=C bending atat1625
593 cm
cm−1 . After acyl chlorination, ND with an acyl chloride bond (C-Cl) was
indicatedcorresponding
formed, that the carboxylated
to the ND surface peak
stretching was activated
at 593 cm by−1the acyl chloride
, whereas no peak group
for for an amine was
ND-COOH
reactive reaction. The functionalization
observed [34]. The results indicated that the of MoS 2 with
carboxylated ND surface was activated bywith
cysteamine hydrochloride was characterized the acyl
comparison
chloride of thefor
group cysteamine
an amine hydrochloride. For the amine-functionalized
reactive reaction. The functionalization MoSof2 , an N−H
MoS deformation
2 with cysteamine
vibration peak and
hydrochloride wasancharacterized
NH2 stretchingwith vibration peak, derived
comparison of thefrom the chemical
cysteamine conjugation with
hydrochloride. For the
cysteamine hydrochloride, occurred at 1604 and 3390 cm −1 , respectively [35]. This indicated the
amine-functionalized MoS2, an N−H deformation vibration peak and an NH2 stretching vibration
successful
peak, modification
derived from theofchemical
amine-functionalized
conjugation with MoS2cysteamine
, where amine groups were positioned
hydrochloride, occurred aton1604the and
surface of−1MoS2 nanosheets. The formation of an amide bond (NHCO) between the acyl chloride of
3390 cm , respectively [35]. This indicated the successful modification of amine-functionalized
ND and the functionalized MoS2 nanosheets was confirmed via FT-IR spectroscopy of the ND/MoS2
MoS2, where amine groups were positioned on the surface of MoS2 nanosheets. The formation of an
nanocomposites. The spectra obtained for the nanocomposites exhibited characteristics of both
amide bond (NHCO) between the acyl chloride of ND and the functionalized MoS2 nanosheets was
ND-COCl and the functionalized nanosheets. The absorption bands associated with the ND/MoS2 peak
confirmed via FT-IR spectroscopy of the ND/MoS2 nanocomposites. The spectra obtained for the
were attributed to hydroxyl bond stretching and an amide bond (NHCO) at 3400 cm−1 and 1632 cm−1 ,
nanocomposites exhibited characteristics of both ND-COCl and the functionalized nanosheets. The
respectively. Furthermore, the relatively strong absorbance band region resulted probably from the
absorption
overlappingbands associated
of bands associated with
withtheC=C ND/MoS 2 peak were attributed to hydroxyl bond stretching
vibration and C=O stretching [36,37].
and an amide bond (NHCO) at 3400 cm−1 and 1632 cm−1, respectively. Furthermore, the relatively
strong absorbance band region resulted probably from the overlapping of bands associated with
C=C vibration and C=O stretching [36,37].
Nanomaterials 2019, 9, 927 5 of 11
Nanomaterials 2019, 9, x FOR PEER REVIEW 5 of 11

Figure 2.2. FT-IR

Figure FT-IR spectra
spectra ofofthe
theMoS 2 2bulk,
MoS bulk,cysteamine,
cysteamine,amine-functionalized
amine-functionalizedMoSMoS 2 2(MoS
(MoS2 -NH
2-NH22),),
carboxylated ND, acyl chloride of ND, and ND/MoS nanocomposite with ratio of
carboxylated ND, acyl chloride of ND, and ND/MoS2 2 nanocomposite with ratio of 1:1.1:1.

The
Thechemical
chemicalstructure
structureof ofthe
theND/MoS
ND/MoS22nanocomposite,
nanocomposite,comparedcomparedwith withthat
thatofofND-COCl,
ND-COCl,was was
determined
determinedfrom fromthe themeasured
measured XPS
XPS spectra,
spectra,as shown
as shown in Figure 3a–f.3a–f.
in Figure The The
C1s C1speaks of ND-COCl
peaks of ND-COCl and
ND/MoS
and ND/MoS 2 were decon-voluted
2 were deconvolutedinto four
into component
four component peakspeaks
usingusing
Gaussian fittingfitting
Gaussian at 284.8at (C-C), 286.0
284.8 (C-C),
(C-O), 287.2 (C=O), and 289 (-COOH) eV, respectively [38,39]. The C=O
286.0 (C-O), 287.2 (C=O), and 289 (-COOH) eV, respectively [38,39]. The C=O peak at 287.2 eV for peak at 287.2 eV for ND-COCl
was generated
ND-COCl wasfrom both acyl
generated chloride
from both acyland chloride
some portion of the portion
and some carboxylofgroup. The C=O
the carboxyl peakThe
group. at 287.2
C=O
eV arose from the amide group after chemical conjugation
peak at 287.2 eV arose from the amide group after chemical conjugation of ND/ND/MoS 2 nanocomposites.
of ND/ND/MoS2 After
chemical conjugation
nanocomposites. Afterbetween ND-COCl
chemical conjugationand amine-functionalized
between ND-COCl MoS , the intensity of the peak
and2 amine-functionalized MoS at2,
286.0 V (C-O) increased significantly relative to that of the peak at 287.2 V (C=O)
the intensity of the peak at 286.0 V (C-O) increased significantly relative to that of the peak at 287.2 V . The results indicate
that
(C=O)unreacted acyl chloride
. The results indicate would decompose
that unreacted intochloride
acyl carboxylwould
groupsdecompose
during the intowashing process
carboxyl and
groups
from
duringcontact with moisture.
the washing processThe andO1from peakscontact
of ND-COCl and ND/MoS
with moisture. The 2O1 at 531.8
peaksand of 533.1
ND-COCl eV were and
attributed to C=O and COC/COH, respectively. The intensity
ND/MoS2 at 531.8 and 533.1 eV were attributed to C=O and COC/COH, respectively. of the ND/MoS 2 peak increased relative
The intensity of
to that
the of the ND-COCl
ND/MoS peak, indicating
2 peak increased relative to thatthat ofthethe
unreacted
ND-COCl acyl chloride
peak, groupthat
indicating wastheconverted
unreacted to acyl
the
carboxyl
chloridegroup groupafter
waschemical
converted conjugation with thegroup
to the carboxyl MoS2 nanosheets
after chemical (Figure 3b,e). The with
conjugation Cl 2pthepeaks MoSof2
the ND-COCl were deconvoluted into two conventional binding energies
nanosheets (Figure 3b,e). The Cl 2p peaks of the ND-COCl were deconvoluted into two conventional of 200.3 eV (Cl 2p 3/2 ) and
201.9 eV (Cl
binding 2p 1/2 ).ofThis
energies 200.3indicated
eV (Cl 2p that3/2)ND-COOH
and 201.9 eV was (Clfunctionalized by an acyl
2p 1/2). This indicated chloride
that ND-COOH groupwas on
the surface [36]. Deconvolution of the Cl 2p peaks, corresponding to
functionalized by an acyl chloride group on the surface [36]. Deconvolution of the Cl 2p peaks, ND/MoS 2 generated peaks at
200.3 eV (Cl
corresponding 3/22p ) and 201.9 eV (Cl
to ND/MoS2 generated 1/2 2p ), have resulted from the physical adsorption
peaks at 200.3 eV (Cl 2p 3/2) and 201.9 eV (Cl 2p 1/2), have of remnant
chloride
resultedions fromontothe the ND surface
physical and nanocage
adsorption of remnant [34,36].
chloride ions onto the ND surface and nanocage
Figure
[34,36]. 4 shows the XPS spectra of the MoS 2 and ND/MoS2 nanocomposite. Two strong peaks
for the Mo 3d peak of MoS2 are observed at 229.85 for doublet Mo 3d5/2 and 232.98 eV for and Mo
3d3/2 (Figure 4a). The peaks, corresponding to the S 2p1/2 and S 2p3/2 orbital of divalent sulfide ions
(S2 −) occur at binding energies of 163.85 and 162.65 eV, respectively, as shown in Figure 4b. The results
are consistent with the values reported for a MoS2 crystal [35,40–42]. The XPS spectra of ND/MoS2
also revealed typical MoS2 crystalline characteristics with chemically induced shifting. Furthermore,
the peak position moved from 229.85 to 229.53 eV for Mo 3d5/2 and from 232.98 to 232.64 eV for Mo
3d3/2 , respectively. Chemically induced shifts were also observed for ND/MoS2 S 2p, with the peaks
shifting from 162.65 to 162.44 eV for S 2p3/2 and 163.85 to 163.71 eV for S 2p1/2 peaks [43]. This indicated
that the chemical shift of the ND/MoS2 nanocomposite to lower binding energy than that of MoS2
resulted from chemical conjugation with ND.
 Nanomaterials 2019, 9, 927 6 of 11
Nanomaterials 2019, 9, x FOR PEER REVIEW 6 of 11

Figure 3. Spectra obtained via X-ray photoelectron spectroscopy. The spectra show the C1s peaks, O1s
Figure 3.2019,
Nanomaterials Spectra obtained
9, x FOR via X-ray photoelectron spectroscopy. The spectra show the C1s peaks,7 of 11
PEER REVIEW
peaks, and Cl2p peaks, respectively, of the (a)–(c) ND-COCl and (d)–(f) ND/MoS2 nanocomposites.
O1s peaks, and Cl2p peaks, respectively, of the (a)–(c) ND-COCl and (d)–(f) ND/MoS2
nanocomposites.

Figure 4 shows the XPS spectra of the MoS2 and ND/MoS2 nanocomposite. Two strong peaks for
the Mo 3d peak of MoS2 are observed at 229.85 for doublet Mo 3d5/2 and 232.98 eV for and Mo 3d3/2
(Figure 4a). The peaks, corresponding to the S 2p1/2 and S 2p3/2 orbital of divalent sulfide ions (S2−)
occur at binding energies of 163.85 and 162.65 eV, respectively, as shown in Figure 4b. The results
are consistent with the values reported for a MoS2 crystal [35,40–42]. The XPS spectra of ND/MoS2
also revealed typical MoS2 crystalline characteristics with chemically induced shifting. Furthermore,
the peak position moved from 229.85 to 229.53 eV for Mo 3d5/2 and from 232.98 to 232.64 eV for Mo
3d3/2, respectively. Chemically induced shifts were also observed for ND/MoS2 S 2p, with the peaks
shifting from 162.65 to 162.44 eV for S 2p3/2 and 163.85 to 163.71 eV for S 2p1/2 peaks [43]. This
indicated that the chemical shift of the ND/MoS2 nanocomposite to lower binding energy than that
of MoS2 resulted from chemical conjugation with ND.

Figure 4. Spectra obtained via X-ray photoelectron spectroscopy. The spectra show Mo 3d peaks and S
Figure 4. Spectra obtained via X-ray photoelectron spectroscopy. The spectra show Mo 3d peaks and
2p peaks of the (a)–(b) MoS2 nanosheets and (c)–(d) ND/MoS2 nanocomposites.
S 2p peaks of the (a)–(b) MoS2 nanosheets and (c)–(d) ND/MoS2 nanocomposites.

The morphologies of MoS2 , ND, and ND/MoS2 nanocomposites (Figure 5) were evaluated with
The morphologies of MoS2, ND, and ND/MoS2 nanocomposites (Figure 5) were evaluated with
TEM. The MoS2 nanosheets was featured as average size of 300–400 nm along the long axis (Figure 5a,b).
TEM. The MoS2 nanosheets was featured as average size of 300–400 nm along the long axis (Figure
The MoS2 nanosheets had a crystalline structure, and several molecular layers were stacked or folded in
5a,b). The MoS2 nanosheets had a crystalline structure, and several molecular layers were stacked or
a planar form [44]. Furthermore, the NDs were well-dispersed with small agglutinins ranging from 80 to
folded in a planar form [44]. Furthermore, the NDs were well-dispersed with small agglutinins
200 nm (Figure 5c,d). The ND/MoS2 nanocomposite with chemical conjugation showed morphological
ranging from 80 to 200 nm (Figure 5c,d). The ND/MoS2 nanocomposite with chemical conjugation
showed morphological features that several molecular layers of thin MoS2 nanosheet enveloped ND
agglutinins (Figure 5e–h). Amine-functionalized MoS2 nanosheets and NDCOCls were chemically
reacted through surface contact, suggesting that the ND/MoS2 nanocomposite was successfully
synthesized (Figure 5e–h).
 The morphologies of MoS2, ND, and ND/MoS2 nanocomposites (Figure 5) were evaluated with
TEM. The MoS2 nanosheets was featured as average size of 300–400 nm along the long axis (Figure
5a,b). The MoS2 nanosheets had a crystalline structure, and several molecular layers were stacked or
folded in a2019,
Nanomaterials planar
9, 927form [44]. Furthermore, the NDs were well-dispersed with small agglutinins 7 of 11
ranging from 80 to 200 nm (Figure 5c,d). The ND/MoS2 nanocomposite with chemical conjugation
showed morphological features that several molecular layers of thin MoS2 nanosheet enveloped ND
features that(Figure
agglutinins several 5e–h).
molecular layers of thin MoS2 MoS
Amine-functionalized nanosheet enveloped
2 nanosheets andND agglutinins
NDCOCls were(Figure 5e–h).
chemically
Amine-functionalized MoS
reacted through surface contact,2 nanosheets and NDCOCls were chemically reacted through
suggesting that the ND/MoS2 nanocomposite was successfullysurface
contact, suggesting
synthesized (Figurethat the ND/MoS2 nanocomposite was successfully synthesized (Figure 5e–h).
5e–h).

Figure 5.5.FE-TEM
FE-TEM image
image of (a)–(b)
of (a)–(b) MoS2 nanosheet,
MoS2 nanosheet, (c)–(d) ND, (c)–(d) ND,ND/MoS
and (e)–(h) and (e)–(h) ND/MoS2
2 nanocomposites.
nanocomposites.
Cyclic voltammograms of the MoS2 nanosheet and ND/MoS2 are shown in Figure 6a–f. For
both electrodes, the rectangularity of the CV plots decreased slightly, corresponding to the reversible
reactions of Mo2+ /Mo3+ associated with OH- anions [45]. The possible redox reaction is given as
follows [46]:
ND/MoS2 + OH- ↔ ND/MoSOH + e-

ND/MoSOH + OH- ↔ ND/MoSO + H2 O + e-

On the same material set, scan rates of 0.05, 0.1, and 0.5 V/s, respectively, and range of potential
voltage was differently applied to −0.8 to −0.2 V and −0.2 to 1.0 V. The shape and magnitude of
the voltamogram was transitioned from a peak-like shape (Figure 6a–c) to quasi-rectangular shape
(Figure 6d–f) depending on the scan rate and potential voltage. The quasi-rectangular shape typically
indicates constant and time dependent concentration gradient of an electroactive surface where the
electrode radius was typically smaller than diffusion layer [47]. Each CV graph is characterized
by a quasi-rectangular shape, consistent with dual behavior, such as the electrical double layer
capacitance [48]. MoS2 nanosheets constitute the minimum area of the CV plot, whereas 1:8 and 1:6
ND/MoS2 constitutes the maximum area, which corresponds to the enhanced capacitance. The CV
curve of the ND/MoS2 nanocomposites reveals the higher current response and large working area of
these composites, compared with those of the MoS2 nanosheet only (Figure 6). The results suggest
that the addition of nanodiamonds enhances the electrochemical activity and increases the specific
capacitance of MoS2 electrode alone [29,35].
The superior electrical performance of the ND/MoS2 nanocomposite electrode, compared with
that of the MoS2 electrode alone, resulted from the unique nanostructure of the composite electrode.
Moreover, the large surface area and the nanosized MoS2 phase of the ND/MoS2 composites may have
resulted in significant reduction of the diffusion length associated with ion and electron transfer during
the oxidation/reduction process. The electrode nanoscale phase makes these composites promising for
various applications. Specifically, the NDs acted as nanoscale supports to functionalize synergistically
the MoS2 sheets, which served as a three-dimensional highly conductive current collector. The featured
architecture of the ND/MoS2 nanocomposites possessing a large specific surface of the electrode
typically indicates constant and time dependent concentration gradient of an electroactive surface
where the electrode radius was typically smaller than diffusion layer [47]. Each CV graph is
characterized by a quasi-rectangular shape, consistent with dual behavior, such as the electrical
double layer capacitance [48]. MoS2 nanosheets constitute the minimum area of the CV plot, whereas
1:8 and 1:6 ND/MoS2 constitutes the maximum area, which corresponds to the enhanced
Nanomaterials 2019, 9, 927 8 of 11
capacitance. The CV curve of the ND/MoS2 nanocomposites reveals the higher current response and
large working area of these composites, compared with those of the MoS2 nanosheet only (Figure 6).
The results
enables rapidsuggest that the addition
and simultaneous of and
electron nanodiamonds enhances
ion transport, the electrochemical
thereby leading activity and
to excellent electrochemical
increases theperformance
capacitive specific capacitance
[42]. of MoS2 electrode alone [29,35].

Figure 6. Cyclic voltammograms of the MoS nanosheet and ND/MoS2 nanocomposite with ratio of
Figure 6. Cyclic voltammograms of the MoS2 2nanosheet and ND/MoS2 nanocomposite with ratio of
1:1, 1:2, 1:4, and 1:8. Scan rates of 0.05, 0.1, and 0.5 V/s were employed for potentials ranging from
1:1, 1:2, 1:4, and 1:8. Scan rates of 0.05, 0.1, and 0.5 V/s were employed for potentials ranging from
(a)–(c) −0.8 to 0.2 V and (d)–(f) −0.2 to 1.0 V.
(a)–(c) -0.8 to 0.2 V and (d)–(f) -0.2 to 1.0 V.
4. Conclusions
The superior electrical performance of the ND/MoS2 nanocomposite electrode, compared with
that ofAthe
chemically conjugated
MoS2 electrode alone,ND/MoS nanocomposite
resulted2 from the uniquewas synthesized
nanostructure ofwith amine-functionalized
the composite electrode.
MoS 2 and acyl chloride-coordinated NDs. The chemical structure and
Moreover, the large surface area and the nanosized MoS2 phase of the ND/MoSmorphology of2 the nanocomposite
composites may
wereresulted
have characterized, and the results
in significant revealed
reduction thatdiffusion
of the the MoS2 length
nanosheets were well-distributed
associated with ion and on the ND
electron
platform, thereby forming a nanophase. Nanophase distribution of MoS2 on ND with a graphitic shell
may provide a large surface area and reduce the diffusion distance of ions and electrons. Therefore,
the augmented electrochemical capacitance of the nanophase electrode was induced, compared to that
of the MoS2 electrode alone.

Author Contributions: For research articles was prepared and supported by conceptualization. S.Y.K.; data
curation, D.L.; writing—original draft preparation, Y.K.; and supervision, E.K. and C.K.K.
Funding: This research was supported by Basic Science Research Program through the National Research
Foundation of Korea (NRF) funded by the Ministry of Education (NRF-2018R1D1A1B07042982). This research
was supported by the Chung-Ang University Research Scholarship Grants in 2018.
Conflicts of Interest: The authors declare no conflict of interest.
Nanomaterials 2019, 9, 927 9 of 11

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