Nano Energy 82 (2021) 105750

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Nano Energy
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Hierarchical Co and Nb dual-doped MoS2 nanosheets shelled micro-TiO2

hollow spheres as effective multifunctional electrocatalysts for HER, OER,
and ORR
Dinh Chuong Nguyen a, Thi Luu Luyen Doan a, Sampath Prabhakaran a, Duy Thanh Tran a,
Do Hwan Kim b, Joong Hee Lee a, c, *, Nam Hoon Kim a, **
a
Department of Nano Convergence Engineering, Jeonbuk National University, Jeonju, 54896 Jeonbuk, Republic of Korea
b
Division of Science Education, Jeonbuk National University, Jeonju, 54896 Jeonbuk, Republic of Korea
c
Carbon Composite Research Center, Department of Polymer-Nano Science and Technology, Jeonbuk National University, Jeonju, 54896 Jeonbuk, Republic of Korea

A R T I C L E I N F O A B S T R A C T

Keywords: Heteroatom doping engineering has emerged as an intriguing strategy to enhance electrocatalytic efficiency.
Co,Nb dual-doping effects Herein, a multiple transition metal doping approach is developed through the incorporation of both Co and Nb
Hollow core-shell spheres into hierarchical MoS2 ultrathin nanosheets directly grown on micro-TiO2 hollow spheres (Co,Nb-MoS2/TiO2
Multifunctional catalyst
HSs) to boost the hydrogen evolution (HER), oxygen evolution reaction (OER), and oxygen reduction reaction
Water splitting
Oxygen reduction reaction
(ORR). The Co and Nb dual-doping effects modify the electronic structure of the host MoS2 towards maximizing
the HER, OER, and ORR performance. Additionally, the unique hollow spherical structure and heterostructured
synergistic effects between the TiO2 core and MoS2 shell provide effective channels for electron transfer and large
surface area with abundant exposed void spaces for ion diffusion/penetration. Therefore, the Co,Nb-MoS2/TiO2
HSs catalyst demonstrates extraordinary activity and stability with small overpotentials of 58.8 and 260.0 mV at
10 mA cm− 2 for the HER and OER, respectively. When employed as both cathodic and anodic electrode in an
electrolyzer, the catalyst requires an operating voltage of 1.57 V to achieve 10 mA cm− 2. The catalyst also ex­
hibits great potential for the ORR with high onset potential of + 0.96 V and half-wave potential of +0.87 V, as
well as direct four-electron transfer process.

1. Introduction Accordingly, the design of alternative multifunctional electrocatalysts

In recent years, many different research efforts have been under­
taken in the energy field, especially for renewable energy conversion
and storage techniques, such as water splitting, metal-air batteries, and
fuel cells, to meet the urgent demand in the near future for green energy.
These technologies are primarily realized via the three major HER, OER,
and ORR reactions [1,2]. Unfortunately, the sluggish kinetics and high
overpotential of these reactions result in the practical efficiency of the
related energy systems becoming much inferior, as compared with the
theoretical efficiency [3,4], and thus efficient electrocatalysts are
needed. Even though noble metals (e.g. Pt) or transition metal oxides (e.
g. RuO2 or IrO2)-based catalysts have demonstrated excellent catalytic
activity, their high cost, insufficient stability, and poor electrical con­
ductivity are critical barriers for large-scale practical application [5,6].
that meet the requirements of cost-effectiveness, high catalytic effi­
ciency, and good stability for the HER, OER, and ORR is an important
task, but so far remains a great challenge.
In recent years, layered molybdenum dichalcogenide (MoS2) has
received considerable attention in the catalysis field by reason of its
great advantages, such as unique two-dimensional layered graphene-
like structure, and excellent electrochemical and mechanical proper­
ties [7–11]. Previous studies have proven that MoS2 not only has high
electrocatalytic activity for the HER [8,11], but also serves as a prom­
ising low-cost electrocatalyst for both the ORR and OER [12,13]. In
general, natural semiconducting material with low electrical conduc­
tivity and poor exposed active edge sites owing to the irregular reag­
gregation and agglomeration of MoS2 induces unsatisfactory
performance to meet the practical requirements [14–16]. Therefore, a

* Corresponding author at: Department of Nano Convergence Engineering, Jeonbuk National University, Jeonju, 54896 Jeonbuk, Republic of Korea.
** Corresponding author.
E-mail addresses: jhl@jbnu.ac.kr (J.H. Lee), nhk@jbnu.ac.kr (N.H. Kim).

https://doi.org/10.1016/j.nanoen.2021.105750
Received 7 November 2020; Received in revised form 18 December 2020; Accepted 4 January 2021
Available online 7 January 2021
2211-2855/© 2021 Elsevier Ltd. All rights reserved.
D.C. Nguyen et al.
unique approach is needed to seek an effective route to optimize the
catalytic activity of MoS2-based catalysts towards replacing noble metal
catalysts.
Among the tremendous efforts that have been made, transition metal
doping has been considered an effective pathway to promote the elec­
trochemical properties of MoS2, due to its ability to adjust the electronic
structure of MoS2 and optimize the electron density of Mo and S,
resulting in the increase of conductivity and new active sites [17,18]. Shi
et al. reported that the doping of transition metals dramatically
enhanced the HER activity of MoS2 through exposing more active sites
and modifying the 3d electron configuration, leading to a positive shift
of about − 0.13 V vs. RHE in the onset overpotential, and far higher
turnover (15.44 s− 1 at 300 mV) than that of the pure MoS2 reported
elsewhere [19]. In another study, Xiong et al. reported significant in­
crease in the HER and OER performances of the MoS2 towards efficient
water splitting through Co-doping engineering, demonstrating that
effective Co-doping resulted in a minimized bandgap of Co-doped MoS2
(~ 0 eV), which is beneficial to catalyze both the HER and OER reactions
[20]. Noticeably, the doping of secondary elements, such as Co, Fe, and
Nb, into MoS2 not only effectively regulates the electronic structure
towards HER efficiency, but also provides additional OER active sites to
boost OER performance [21,22]. In addition, Wang et al. have per­
formed computational research on the substitutional doping of different
transition metals for MoS2, demonstrating that the atoms doping can
strongly interact with the S-vacancy, as well as adjust the electronic
structure of MoS2, leading to improvement of the ORR activity of MoS2
[23]. Considering the above-mentioned reasons, it is reasonable to
expect the development of multifunctional catalysts via transition
metal-doped MoS2 materials.
In addition to improving intrinsic activity, the development of het­
erostructures based on MoS2 and a conductive/stable backbone is also
emerging as another effective way to improve catalytic performance.
Evidence has been reported that the contactable surface area of the MoS2
for reactants/electrolyte ions could be extended through hetero­
structural form by alleviating the bulky aggregates. Titanium dioxide
(TiO2), with the excellent merits of cheap price, richness, nontoxicity,
environmental friendliness, superior chemical stability/durability, and
excellent physicochemical properties [24–26], has been extensively
utilized in many different electrochemical applications, especially as a
popular catalyst support [27–29]. Liang et al. has reported that
three-dimensional (3D) heterostructured catalysts containing TiO2 and
MoS2 nanosheets (NSs), as core and shell parts, respectively, showed
dramatic HER performance, in comparison with the pure MoS2 NSs [30].
This study highlighted that the very rough TiO2 layer core not only
provided a large amount of favorable sites for the growth of MoS2
without agglomerated form, but during the HER process also acted as an
electron transfer layer for smooth charge transfer. Among various
morphologies of TiO2 support materials, hollow TiO2 sphere has a large
and curved growth surface to benefit MoS2 loading, and offers an
effective transport path to improve the mass transfer property of the
material [31,32]. As compared to solid particles, the porous hollow
structures possess lower density and mass requirements, and these fea­
tures are significant for cost reduction [33]. Although there have various
efforts to improve the electrocatalytic activities of MoS2, no data has
been available on inducing multifunctionality to MoS2 via combining
co-doping engineering and constructing MoS2-based heterostructures
towards the HER, OER, and ORR applications.
Herein, we have developed a novel multi-shelled hollow structure
containing Co and Nb dual-doped MoS2 NSs directly grown on TiO2
hollow microspheres (denoted as Co,Nb-MoS2/TiO2 HSs) as highly
active and cost-effective multifunctional electrocatalysts. The spherical
hollow structure with ultrathin NSs attached on the surface can enlarge
the contact area for electrolyte/reactant, promote the electrolyte/reac­
tant–electrode diffusion/penetration process, and enhance the charge
transfer ability. In addition, the Co, Nb-dual doping adjusted the unique
electronic structure of the MoS2 towards improving intrinsic catalytic
2
Nano Energy 82 (2021) 105750
activity and enhanced the electrochemically active surface area (ECSA).
Moreover, the strong electronic interactions between the inner TiO2
hollow sphere and outer Co,Nb-MoS2 layer at the interface significantly
improved electrical conductivity, thereby providing favorable kinetic
for lower overpotential values of electrochemical reactions. Therefore,
the Co,Nb-MoS2/TiO2 HSs has the ability to simultaneously catalyze the
HER, OER, and ORR with high electrocatalytic performance. The cata­
lyst only required overpotential (η) of 58.8 mV for the HER, and 260.0
mV for the OER, to achieve 10 mA cm− 2, which is superior to most of the
efficient HER and OER catalysts reported recently. In addition, the fast
and favorable kinetics were demonstrated through small Tafel slopes of
40.2 and 65.0 mV dec− 1 for HER and OER, respectively. When applied
as two electrodes of the electrochemical water splitting device, the Co,
Nb-MoS2/TiO2 HSs was capable of driving 10 and 50 mA cm− 2 at small
operating voltage values of 1.57 and 1.88 V, respectively, and achieved
stable gaseous production for 60 h with a retention of 89.2%. The pos­
itive onset potential (Eonset) and half-wave potential (E1/2) of + 0.96 and
+ 0.87 V, respectively, with desirable 4-electron transfer pathway, were
also found for the Co,Nb-MoS2/TiO2 HSs towards the ORR. Furthermore,
the catalyst showed good stability under the ORR condition with a
current density retention of 96.65% after 60,000 s along with excellent
alcohol tolerance, which even outperformed the commercial Pt/C
catalyst.
2. Experimental section
2.1. Chemical reagents
Sodium lauryl sulfate (CH3(CH2)11OSO3Na, ≥ 98.5%), potassium
persulfate (K2S2O8, ≥ 99%), methanol (CH3OH, ≥ 99.9%), styrene
(C8H8CH=CH2, ≥ 99%), ethanol (CH3CH2OH, ≥ 99.8%), hexadecyl­
amine (CH3(CH2)15NH2, 98%), ammonium hydroxide (NH4OH, 28.0%
NH3 in H2O), titanium isopropoxide (Ti[OCH(CH3)2]4, 99.9%), cobalt
nitrate hexahydrate (Co(NO3)2.6H2O, ≥ 98%), ruthenium oxide (RuO2,
99.9%), niobium chloride (NbCl5, 99%), ammonium tetrathiomolybdate
((NH4)2MoS4, 99.97%), potassium hydroxide (KOH, ≥ 85%), nafion (5
wt%), platinum on carbon (Pt/C, 20 wt%), and nickel foam were pur­
chased from Sigma Co. (USA).
2.2. Synthesis of Co,Nb-MoS2/TiO2 hollow spheres
Firstly, Co and Nb dual-doped-MoS2 NSs were directly deposited on
the PS@TiO2 spherical surface via a hydrothermal reaction, which can
be described as follows. Firstly, 5 mL of 0.05 M (NH4)2MoS4 solution was
mixed with 20 mL ethanol solution containing 0.06 g of PS@TiO2
spheres (see Supporting information) under magnetic stirring for 1 h.
Next, 10 mL ethanol solution of Co(NO3)2.6H2O (6 mM) and NbCl5 (3
mM) was added into that solution under stirring for 3 h. The obtained
solution was then poured into 50 mL Teflon-lined stainless steel auto­
clave. The hydrothermal reaction was performed at 200 ◦ C for 6 h. After
that, the centrifugation method was used to collect the Co,Nb-MoS2/
PS@TiO2 spheres, followed by rinsing with ethanol/distilled water, and
finally drying at 60 ◦ C overnight.
To convert the Co,Nb-MoS2/PS@TiO2 spheres to Co,Nb-MoS2/TiO2
HSs, the Co, Nb-MoS2/PS@TiO2 precursor was annealed at 650 ◦ C with
heating rate of 1 ◦ C min− 1 in Ar atmosphere (200 sccm) for 3 h (Scheme
1).
Individual TiO2 hollow spheres (TiO2 HSs), Co-doped MoS2/TiO2
hollow spheres (Co-MoS2/TiO2 HSs), Nb-doped MoS2/TiO2 hollow
spheres (Nb-MoS2/TiO2 HSs), MoS2/TiO2 hollow spheres (MoS2/TiO2
HSs), and Co,Nb-MoS2 NSs materials were also fabricated via the
method described above for comparison.
2.3. Material characterization
The morphological and structural characteristics of materials were
D.C. Nguyen et al.
Scheme 1. Schematic showing the synthesis procedure of Co,Nb-MoS2/TiO2 HSs.
investigated using field-emission scanning electron microscopy (FE-
SEM) and energy-dispersive X-ray analysis (EDAX) through a Supra 40
VP instrument (Zeiss Co., Germany). Transmission electron microscopy
(TEM) and high-resolution TEM (HR-TEM) were carried out by H-7650
instrument (Hitachi Ltd., Japan) in the Jeonju center of KBSI, to examine
the structure of materials in detail. X-ray diffraction (XRD) analysis was
used to identify the crystalline structure and chemical components using
a D/Max 2500V/PC (Rigaku Co., Japan) in the 2θ range (10− 90)◦ , with
Cu Kα radiation (λ = 0.154 nm) at the Center for University-Wide
Research Facilities (CURF) in Jeonbuk National University, Korea The
elemental composition and valence state of elements on the surface of
materials were observed via X-ray photoelectron spectroscopy (XPS)
analysis on a Theta Probe instrument (Thermo Fisher Scientific Inc.,
USA). The specific surface area of materials was found via the Bru­
nauer–Emmett–Teller (BET) method through an ASAP 2020 Plus system
(Micromeritics Instrument Corp., USA).
2.4. Electrochemical characterization
Electrochemical properties of the materials were assessed on an
electrochemical workstation (CH660D, CH Instruments Inc., USA) in­
tegrated into a standard three-electrode configuration, in which
graphite rod and Ag/AgCl were used as counter electrode and reference
electrode, respectively. To fabricate the working electrode, 5 mg of
catalyst was dissolved in 500 µL of isopropanol solution. After adding
20 µL of Nafion (5 wt%), the mixed solution was sonicated for 30 min to
obtain a homogeneous catalyst ink, followed by pipetting on a piece of
nickel foam (NF, 1 cm × 1 cm) for the HER, OER, and overall water
splitting test, or on a polished RDE surface (diameter ~ 3 mm) for the
ORR test. All potential values were calibrated to reversible hydrogen
electrode (RHE), according to the Nernst equation [33]:
ERHE = EAg/AgCl + 0.059∙pH + E0Ag/Agcl
where E0Ag/AgCl = 0.198 V (vs. NHE). Additionally, the reaction kinetics
were evaluated from Tafel plots with the Tafel equation:
η = blog|J| + a
where η is the overpotential (mV), b reflects the Tafel slope (mV dec− 1),
J is the current density (mA cm− 2), and a reflects the exchange current
density.
For the HER and OER experiments, the electrolyte was nitrogen (N2)-
saturated 1.0 KOH solution. Linear sweep voltammetry (LSV) was per­
formed at 5 mV s− 1 with iR-correction according to the following
Nano Energy 82 (2021) 105750
equations [34]:
EiR− = Eraw − EiR (3)
corrected
EiR = J × Rs (4)
where Rs is series resistance (Ω).
Cycle voltammetry (CV) was performed at various scan rates of 5, 10,
15, 20, 25, and 30 mV s− 1, in the potential region 0.92–1.01 V vs. RHE,
to calculate the double layer capacitance (Cdl). Charge–transfer resis­
tance (Rct) of materials was identified by electrochemical impedance
spectroscopy (EIS) at an open circuit potential in the frequency range
105 to 10− 2 Hz with an amplitude of 5 mV. The long-term stability of
materials was estimated through chronoamperometric measurement at
current responses of 10 and 50 mA cm− 2 for both the HER and OER for
30 h. Multistep chronoamperometry was also carried out at potential
range of 0.058-0.198 V for the HER, and 1.49–1.59 V for the OER, with
increment of 0.01 V per 500 s.
To evaluate the catalytic performance towards overall water split­
ting, a hand-made electrolyzer was assembled using the as-synthesized
catalyst-loaded NF as cathode and anode (mass loading of
5 mg cm− 2). The LSV and chronoamperometric measurements were run
in N2-saturated 1.0 M KOH solution. The amount of generated gaseous
during the experiment process was collected via a drainage collection
process. The Faradaic efficiency (FE) for both the HER and OER was
calculated according to the following equation [30]:
n × F × ngas
FE = (5)
J×t
where, n is the transferred electron number, F is the Faraday constant
(96,485 cmol− 1), ngas is the amount of O2 or H2 produced (mmol), and t
is the time for the constant oxidation/reduction current (s).
In the case of ORR investigation, CV measurement was conducted in
(1)
N2- and O2-saturated 0.1 M KOH, while LSV was performed in only O2-
saturated 0.1 KOH medium. A 10 mV s− 1 scan rate was applied for both
CV and LSV test. In addition, LSV was performed by varying the rotating
speed as 400, 800, 1200, 1600, and 2000 rpm to clarify the ORR
(2) mechanism. The electron transfer number (n) was determined based on
the Koutechy–Levich equation, as reported elsewhere [35,36]. Chro­
noamperometry was also used to probe the stability and methanol
tolerance of the materials in ORR operation. Moreover, rotating
ring-disk electrode (RRDE) measurement also conducted for the Co,
Nb-MoS2/TiO2 HSs and Pt/C. Based on the RRDE result, the n and
percentage of produced hydrogen peroxide (H2O2) consistent with ORR
3
D.C. Nguyen et al.
reaction were determined via the following equations [37,38]:
Jd
n=4 × (6)
Jd + JNr
Jr
%H2 O2 = 2 × N
(7)
Jd + JNr
where N reflects the collection efficiency of the RRDE, taken as 0.42; Jd
and Jr reflect the disk and ring current, respectively.
3. Results and discussion
3.1. Morphological and structural characterization
FE-SEM and energy-dispersive X-ray (EDAX) analyses were used to
verify the morphology and elemental composition of the materials.
Fig. S1a and b show SEM images of PS at different magnifications, which
reveal the spherical structure, along with the average diameter of ~
350 nm, together with very smooth surface. A typical EDAX pattern of
the PS (Fig. S1c) indicates existence of C and O elements in the material,
demonstrating that the obtained microspheres are PS. The SEM images
of PS@TiO2 (Fig. S1d and e) show that the initial spherical structure is
almost intact; however, the diameter of PS@TiO2 has increased to ~
390 nm, providing favorable evidence of the coating of thin TiO2 shell
Fig. 1. (a) and (b) SEM images, and (c) EDAX spectrum of the Co,Nb-MoS2/TiO2 HSs; (d) TEM image of the TiO2 HSs; (e) and (f) TEM images of the Co,Nb-MoS2/
TiO2 HSs at low and high magnifications, respectively; (g) HR-TEM image of the Co,Nb-MoS2 shell (Inset: SAED pattern of the Co,Nb-MoS2 shell); and (h–o) EDS
elemental mapping images of the Co,Nb-MoS2/TiO2 HSs.
4
Nano Energy 82 (2021) 105750
layer (~ 20 nm) on the PS microsphere surface. In addition to C and O
elements, Ti element is also observed in the EDAX spectrum of the
PS@TiO2 in Fig. S1f, further confirming the formation of core–shell
PS@TiO2 microspheres. Interestingly, the PS@TiO2 surface is much
rougher than that of its PS counterpart, which can provide abundant
nano-voids as chambers for high MoS2 NSs loading with full edge/active
sites exposure [15]. The low-magnification SEM image of the Co,
Nb-MoS2/PS@TiO2 (Fig. S2a) indicates the good preservation of the
spherical structure after hydrothermal treatment. In addition, it also
exhibits the presence of dense NSs on the sphere surface. A magnified
SEM image (Fig. S2b) clearly shows that all PS@TiO2 spheres were fully
covered with uniform and thin Co,Nb-MoS2 NSs, forming a hierarchical
core–shell structure. Moreover, the average diameter of the spheres is
found to be around ~ 480 nm, which is about 90 nm higher than that of
the pure PS@TiO2, effectively demonstrating the formation of the outer
layer. The EDAX pattern of the Co,Nb-MoS2/PS@TiO2 in Fig. S2c also
confirms the presence of Co, Nb, Mo, S, Ti, O, and C elements. After
annealing, the Co,Nb-MoS2/TiO2 HSs (Fig. 1a and b) is similar to the Co,
Nb-MoS2/PS@TiO2 in terms of the unique spherical structure and
diameter. Nevertheless, the C element was not found in the EDAX
spectrum (Fig. 1c), proving the complete conversion of PS@TiO2 into
TiO2 HSs. Growing Co,Nb-MoS2 NSs on the entire TiO2 skeleton is ex­
pected to maximum the surface contact of Co,Nb-MoS2 NSs with the
electrolyte/reactant, as well as promote the possible utilization of
D.C. Nguyen et al. Nano Energy 82 (2021) 105750

catalytic active sites, leading to the increase of electrocatalytic perfor­
mance. Furthermore, such unique core–shell structure can offer an
effective pathway for electron transportation from the TiO2 core to the
surrounding Co,Nb-MoS2 NSs, thus effectively boosting the electrode
kinetics of electrochemical reactions. Through the EDAX analysis, the
atomic percentage of particular elements contained in the Co,
Nb-MoS2/TiO2 HSs material was found to be 12.5, 27.1, 7.35, 15.07,
2.91, and 1.42 at% for Ti, O, Mo, S, Nb, and Co, respectively. SEM
analysis was also conducted for the Co,Nb-MoS2 NSs for comparison
(Fig. S3), and exhibits the aggregation of numerous NSs into the form of
compact/stacked layered structure, suggesting deficiency in the surface
site exposure [16].
TEM analysis was then conducted for the as-synthesized materials to
examine their morphological characteristics in detail. The TEM images
of the PS and PS@TiO2 microspheres (Fig. S4) show their solid feature
with average diameter of ~ 350 and ~ 390 nm, respectively; thus, the
thickness of outer TiO2 layer is found to be ~ 20 nm, which agrees well
with SEM observation. Fig. 1d shows the TEM image of the TiO2 HSs,
which distinctly exhibits its hollow structure with a uniform size and
thickness behavior. The formation of such hollow structure can be
attributed to the decomposition of the inner PS sphere under high
temperature during calcination treatment. Likewise, the bright/dark
contrast characteristics of the Co,Nb-MoS2/TiO2 HSs material (Fig. 1e)
prove its structured hollow spherical form. In addition, TEM images of
the Co,Nb-MoS2/TiO2 HSs also indicate the ultrathin secondary NSs
uniformly grown on the surface of TiO2 HSs platform, demonstrating the
successful formation of unique core–shell Co,Nb-MoS2/TiO2 HSs. The
average diameter was found to be ~ 480 nm for the Co,Nb-MoS2/TiO2
HSs with an ~ 390 nm core of TiO2 and ~ 45 nm shell of Co,Nb-MoS2
layer. A closer observation of the shell layer (Fig. 1f) reveals the very
rough and wrinkled characteristics of the Co,Nb-MoS2 NSs, with only
single and few-layer NSs (around 1–4 layers) attached to the surface of
the TiO2 HSs substrate. The HR-TEM image taken from the shell region
(Fig. 1g) identifies lattice fringes with interlayer spacing of 0.27 and
0.64 nm, which are in good agreement with the (100), and (002) planes
of MoS2, respectively [39]. In addition, the selective area electron
diffraction (SAED) pattern of the layer shell (Inset Fig. 1g) displays
several bright circular rings that are assigned to the (100), (103), and
(110) planes of MoS2, suggesting that the outer part contains MoS2
phase [39]. It is notable that no signal related to the compounds of Co or
Nb is observed from the HR-TEM image and SAED pattern, implying that
both Co and Nb may act only as effective dopants to boost the

Fig. 2. (a) N2 adsorption–desorption curves of the Co,Nb-MoS2/TiO2 HSs, Co,Nb-MoS2 NSs, and TiO2 HSs, and the corresponding pore-size distribution curves
(inset); (b) XRD patterns of the materials; (c) XPS survey spectra of the materials [(1) MoS2/TiO2 HSs, (2) Co-MoS2/TiO2 HSs, (3) Nb-MoS2/TiO2 HSs, and (4) Co,Nb-
MoS2/TiO2 HSs]; and (d–i) High-resolution XPS spectra of the Ti2p, O1s, Mo3d, S2p, Nb3d, and Co2p for the MoS2/TiO2 HSs, Co-MoS2/TiO2 HSs, Nb-MoS2/TiO2 HSs,
and Co,Nb-MoS2/TiO2 HSs, respectively.

5
D.C. Nguyen et al.
electrochemical property of MoS2. Fig. 1h–o show the results of the
Energy dispersive X-ray spectroscopy (EDS) mapping that was also
carried out for an individual Co,Nb-MoS2/TiO2 HSs. The Co, Nb, Mo,
and S elements are mainly found in the shell area, in which the Mo and S
possess much stronger signals than those of the Co and Nb, which is
attributed to the lower concentration of both Co and Nb associated with
their doping role. High densities of Ti and O2 elements are observed at
the center of the hollow sphere, confirming the core–shell architecture
with Ti and O in the core, and Co, Nb, Mo, and S elements in the shell
area. On the other hand, EDS line scan profiles (Fig. S5a–h) depict the
strong signals of the Co, Nb, Mo, and S elements in the outer area,
whereas the signals of Ti and O elements are mainly observed in the
inner area, reconfirming the unique core–shell configuration of the Co,
Nb-MoS2/TiO2 HSs material.
To reflect the potential of the Co,Nb-MoS2/TiO2 HSs for electro­
catalytic applications, we evaluated its specific surface area using Bru­
nauer–Emmett–Teller (BET) gas sorptometry analysis. Fig. 2a shows that
the N2 adsorption–desorption isotherm of the Co,Nb-MoS2/TiO2 HSs
possesses the full features of the type IV isotherm with a pronounced
hysteresis loop, suggesting the presence of mesoporous structure. The
Co,Nb-MoS2/TiO2 HSs shows a large specific surface area of 198.8 m2
g− 1, which is beneficial for the catalysis process, along with pore size
distribution located in the range (1.9–2.5) nm (Inset of Fig. 2a), indi­
cating its excellent mesoporous nature. Such mesoporous structure has
the advantage of high void channel exposure to facilitate electrolyte ion
diffusion/penetration, as well as gaseous product detachment, thereby
improving the reaction rate during the catalysis process [40,41].
Remarkably, the specific surface area of both the TiO2 HSs (162.0 m2
g− 1) and Co,Nb-MoS2 NSs (71.2 m2 g− 1) counterparts are significantly
lower than the Co,Nb-MoS2/TiO2 HSs (Fig. 2a), implying the important
roles of the core–shell structure in enhancing the surface area. This is
because of the agglomeration phenomenon of the pure Co,Nb-MoS2 NSs
was restricted via growth on the TiO2 HSs backbone, as seen in the SEM
and TEM imagery. Furthermore, ultrathin, very rough, and wrinkled
features of the Co,Nb-MoS2 shell layer significantly improve the surface
area of the Co,Nb-MoS2/TiO2 HSs material. XRD measurements were
conducted for the PS, PS@TiO2, TiO2 HSs, MoS2/TiO2 HSs, Co-MoS2/­
TiO2 HSs, Nb-MoS2/TiO2 HSs, and Co,Nb-MoS2/TiO2 HSs materials.
Fig. S6 shows the XRD patterns of the PS, PS@TiO2 microsphere, and
TiO2 HSs. The broad diffraction peak at 2θ of 20◦ of both the PS and
PS@TiO2 sample can be assigned to the amorphous structures of the PS
spheres. In addition, a series of additional peaks at 2θ of 25.2, 37.8, 48.0,
53.9, 55.0, 62.6, 68.7, 70.3, and 75.1◦ , which agree with the (101),
(004), (200), (105), (211), (204), (116), (220), and (215) crystalline
planes of TiO2 (PDF#021-1272) [42], are also found for the PS@TiO2,
proving the successful formation of the outer TiO2 layer. After anneal­
ing, only the diffraction XRD peaks of TiO2 phase are observed in the
TiO2 HSs, implying that under high thermal condition, the inner PS
spheres are fully decomposed, agreeing well with the TEM observations.
For the case of the MoS2/TiO2 HSs, Co-MoS2/TiO2 HSs, Nb-MoS2/TiO2
HSs, and Co,Nb-MoS2/TiO2 HSs materials (Fig. 2b), besides the char­
acteristic peaks of the TiO2 phase, the other peaks located at 2θ of 14.4,
32.6, 33.5, 39.5, 49.7, 58.3, 60.1, and 72.7◦ for all materials can be
attributed to the (002), (100), (101), (103), (105), (110), (008), and
(203) crystalline planes of the hexagonal MoS2 phase (PDF#037-1492)
[43], meaning that the majority of phase composites are TiO2 and MoS2.
No obvious peaks related to the possible crystal phases of Co- or
Nb-based compounds are observed from the Co-MoS2/TiO2 HSs,
Nb-MoS2/TiO2 HSs, and Co,Nb-MoS2/TiO2 HSs, which correspond with
the SAED and HR-TEM results, reconfirming the doping roles of Co and
Nb into the MoS2 structure [18,22]. Furthermore, the weak (002)
diffraction peak indicates that the as-prepared MoS2 using the current
synthesis strategy has an ultrathin two-dimensional (2D) layered
structure [44], similar to graphene structure, as demonstrated in the
SEM and TEM observations.
We conducted Raman spectroscopy measurement for the Co,Nb-
6
Nano Energy 82 (2021) 105750
MoS2/TiO2 HSs to further investigate its structural characteristics
(Fig. S7). As seen, two Raman peaks at 382.1 and 404.8 cm− 1 assigned
properly with the E12g in-plane and A1g out-of-plane vibrational modes
of the MoS2 are clearly observed from Raman spectrum [45], as
compelling evidence for the formation of MoS2 phase in the Co,
Nb-MoS2/TiO2 HSs structure.
XPS analysis was also conducted for the materials to further clarify
their structural details and chemical composition. The survey XPS
spectra of the Co,Nb-MoS2/TiO2 HSs, Co-MoS2/TiO2 HSs, Nb-MoS2/
TiO2 HSs, and MoS2/TiO2 HSs materials (Fig. 2c) exhibit the predomi­
nant existence of peaks at ca. 161.8, 228.9, 458.8, and 530.4 eV, which
index well to the S2p Mo3d, Ti2p, and O1s orbitals, respectively,
reconfirming the formation of pure phase MoS2 and TiO2 in our work.
Additionally, the appearance of minor peaks at ca. 207.0 and 782.6 eV,
which are assigned to the Nb3d and Co2p orbitals, in the Co,Nb-MoS2/
TiO2 HSs, Co-MoS2/TiO2 HSs, and Nb-MoS2/TiO2 HSs proves the suc­
cessful incorporation of Co and Nb into the MoS2 structure. Fig. 2d–i
provide the high-resolution XPS spectra of the Ti2p, O1s, Mo3d, S2p,
Co2p, and Nb3d core-level, respectively. The Ti2p region (Fig. 2d) can
be deconvoluted into two peaks of Ti2p3/2 and Ti2p1/2 at ca. 458.8 and
464.6 eV, respectively, which is a characteristic of the Ti 4+ oxidation
state in TiO2 [30]. In addition, the appearance of the O1s peaks (Fig. 2e)
at ca. 530.3 and 531.7 eV corresponding to the metal–oxygen bonding
and the chemisorbed oxygen, such as the adsorbed OH- group, respec­
tively, confirms the formation of TiO2 phase by using the present syn­
thesis approach [46]. As compared to the Ti2p in pure TiO2 (Fig. S8a),
the binding energies of the Ti2p in the Co,Nb-MoS2/TiO2 HSs show a
slightly positive shift of ca. 0.28 eV, representing the strong electronic
interactions at the interface of TiO2-core and Co,Nb-MoS2-shell, which
are advantageous to electron transfer from TiO2 to Co,Nb-MoS2 for the
catalysis process [47,48]. For the Mo3d spectrum (Fig. 2f), three peaks
located at ca. 225.6, 228.2, and 231.4 eV, assigned to Mo–S, Mo4+
3d5/2, and Mo4+ 3d3/2, respectively, demonstrate the presence of
MoS2 phase in the as-synthesized material [49]. Meanwhile, the
remaining fitted peaks at ca. 232.5 and 235.6 eV match the Mo6+ 3d5/2
and Mo6+ 3d3/2 from the MoO3 phase, which might originate from an
oxidized surface [50]. All the Mo–S, Mo4+ 3d5/2, and Mo4+ 3d3/2 are
negatively shifted by ca. 0.4 eV, in contrast to those of the single Co,
Nb-MoS2 NSs (Fig. S8c), further evidencing that the formation of the
Co,Nb–MoS2/TiO2 HSs core–shell structure enhances the electrical
conductivities. In the case of the high-resolution XPS spectrum of the
S2p (Fig. 2g), binding energy values at ca. 161.8 and 163.4 eV are
consistent with the S2- 2p3/2 and S2- 2p1/2 of the Mo–S bonds,
respectively [51]. The binding energies of the Mo3d and S2p peaks for
the Co-MoS2/TiO2 HSs clearly show negative shifts of about 0.4 and
0.35 eV, respectively, as compared with the undoped MoS2/TiO2 HSs.
Likewise, the binding energies of the Mo3d and S2p peaks for the
Nb-MoS2/TiO2 HSs are 0.6 and 0.42 eV lower than that of the undoped
MoS2/TiO2 HSs, respectively. This result proves the increase in elec­
tronic density of the host MoS2 after being doping by the Co or Nb [52].
More importantly, the Mo3d and S2p peaks of the Co,Nb-MoS2/TiO2
HSs have more negative shifts than those of the Co-MoS2/TiO2 HSs
and Nb-MoS2/TiO2 HSs counterparts, thereby proving that the dual Co
and Nb doping can further enrich the electronic density of MoS2. In the
Nb3d region of the XPS spectra for Nb-MoS2/TiO2 HSs and Co,
Nb-MoS2/TiO2 HSs (Fig. 2h), the peaks located at ca. 203.6 and
204.9 eV should be assigned to the Nb1+ 3d5/2 and Nb1+ 3d3/2,
respectively [53], while the other fitted peaks at 208.5 and 211.2 eV are
well consistent with high oxidation states of Nb5+ 3d5/2 and Nb5+
3d3/2, respectively [54], indicating the coexistence of Nb1+ and Nb5+
oxidation states. Fig. 2i provides the high-resolution XPS spectrum of
Co2p, which displays two major sets of binding energies at ca. 778.7 and
794.4 eV, corresponding to the Co3+ 2p3/2 and Co3+ 2p1/2, respec­
tively, and ca. 781.6 and 797.4) eV, which match well with the Co2+
2p3/2 and Co2+ 2p1/2, respectively [54]. Therefore, these results
demonstrate that both Co and Nb are successfully doped into MoS2
D.C. Nguyen et al. Nano Energy 82 (2021) 105750

structure, resulting in an increase of electronic densities in MoS2, thus
inducing the decrease of empty d-orbitals density towards weakening
the adsorption ability of the OH group and H atom [55–57]. Such
weakened OH adsorption and H binding can expedite OH/H desorption,
as well as promote the release process of products from the catalysis
surface, and thus intrinsically improve the catalytic activities towards
the HER, OER, and ORR [58,59].
3.2. Electrocatalytic performance
The electrocatalytic activities of the Co,Nb-MoS2/TiO2 HSs were
initially investigated for the HER in alkaline condition. Fig. 3a and b,
respectively, show the iR-corrected polarization curves and comparison
of η at 10 and 50 mA cm− 2 (denoted as η10 and η50, respectively) for the
Co,Nb-MoS2/TiO2 HSs HSs, Co-MoS2/TiO2 HSs, Nb-MoS2/TiO2 HSs,
MoS2/TiO2 HSs, Co,Nb-MoS2 NSs, TiO2 HSs, and the commercial Pt/C
catalyst. The LSV result shows that the pure TiO2 HSs exhibits poor HER
behavior with the high η10 and η50 of 272.0 and 404.1 mV, respectively,
suggesting the major role of the Co,Nb-MoS2 NSs in constructing the
electrocatalytic behavior of the Co,Nb-MoS2/TiO2 HSs. Although the
catalytic activities of the Co,Nb-MoS2 NSs (η10 = 170.0 mV and η50
= 265.5 mV) for the HER are higher than those of the TiO2 HSs, its
catalytic efficiency is still insufficient to provide desirable performance.
This can be probably attributed to the low density of the active edge/site
exposure related to the agglomerated structure of the Co,Nb-MoS2 NSs,
as observed in the SEM result. In contrast, the rationally designed hi­
erarchical Co,Nb-MoS2/TiO2 HSs core–shell structure led to significantly
enhanced catalytic activities. Excellent HER behavior was found for the
Co,Nb-MoS2/TiO2 HSs with very small η10 and η50 of 58.8 and 111.6 mV,
respectively. On the other hand, the Co,Nb-MoS2/TiO2 HSs shows
impressively enhanced catalytic activities, when compared with the
MoS2/TiO2 HSs (η10 = 222.0 and η50 = 322.2 mV), indicating that the
Co and Nb doping is favorable for the HER. In particular, the signifi­
cantly positive shifts of η for the Co, Nb dual-doping compared with
those of the single Co-MoS2/TiO2 HSs (η10 = 123.2 and η50
= 196.5 mV), and Nb-MoS2/TiO2 HSs (η10 = 200.0 and η50
= 300.2 mV) demonstrate the further enhanced catalytic ability of the
MoS2/TiO2 HSs via both Co and Nb incorporation. To the best of our
knowledge, the excellent HER activities of the Co,Nb-MoS2/TiO2 HSs are
superior to most of the recently non-noble metal HER catalysts reported
elsewhere in term of η10 (Fig. 3c and Table S1). To further understand
the HER kinetics, Tafel slopes of the materials were calculated according
to the Tafel Eq. (1), along with the linear region of Tafel plots (Fig. 3d).
The Tafel slope of 40.2 mV dec− 1 was found for the Co,Nb-MoS2/TiO2
HSs, suggesting that the material follows a Volmer–Heyrovsky mecha­
nism, in which the reaction rate is limited by the Heyrovsky step [60,

Fig. 3. (a) iR-corrected polarization curves obtained at a scan rate of 5 mV s− 1 for the Co,Nb-MoS2/TiO2 HSs, Co-MoS2/TiO2 HSs, Nb-MoS2/TiO2 HSs, MoS2/TiO2
HSs, TiO2 HSs, Co,Nb-MoS2 NSs, and Pt/C in the 1.0 M KOH electrolyte; (b) Comparison of η10 and η50 for the as-synthesized samples; (c) Comparison of η10 for the
Co,Nb-MoS2/TiO2 HSs and other reported HER catalysts; (d) Tafel plots of the as-synthesized samples; (e) Chronoamperometric curves of the Co,Nb-MoS2/TiO2 HSs
at applied potentials of 58.8 and 111.6 mV for 30 h; (f) Polarization curves before and after chronoamperometric test; (g) The SEM and TEM (inset) images of the
post-HER Co,Nb-MoS2/TiO2 HSs material; and (h–o) Corresponding EDS elemental mapping of the post-HER Co,Nb-MoS2/TiO2 HSs.

7
D.C. Nguyen et al. Nano Energy 82 (2021) 105750

61]:
−
H2 O + e →H + ∗
OH −
H∗ + H2 O + e− →H2 + OH −
The Tafel slopes for the Co-MoS2/TiO2 HSs, Nb-MoS2/TiO2 HSs, Co,
Nb-MoS2 NSs, and MoS2/TiO2 HSs of 81.2, 134.9, 107.8, and
116.5 mV dec− 1, respectively, also confirm the Volmer–Heyrovsky
mechanism while using these catalysts for the HER reaction, and the
electrochemical H2 gas desorption may be a rate-determining step. For
the case of the TiO2 HSs, the Tafel slope of 135.0 mV dec− 1 suggests the
Volmer step limits the rate of reaction, leading to inferior HER behavior
in this material [62]. Even though the value of Tafel slope for the Co,
Nb-MoS2/TiO2 HSs is slightly higher in comparison with that of the Pt/C
(38.9 mV dec− 1), it looks to be relatively smaller than those of recently
reported efficient HER catalysts (Table S1). The lowest Tafel slope value
of the Co,Nb-MoS2/TiO2 HSs reveals its more favorable and faster HER
kinetics, thereby resulting in better H2 production. In addition to the
excellent catalytic HER activities, the Co,Nb-MoS2/TiO2 HSs also ex­
hibits good durability and stability. Chronoamperometric curves for the
Co,Nb-MoS2/TiO2 HSs (Fig. 3e) show a current density retention of ⁓
97.3% at a small applied η of 58.8 mV, and ⁓ 85.2% at a high applied η
of 111.6 mV, during 30 h of continuous operation, demonstrating its
superior stability towards HER. There is no obvious change in the po­
larization curve after 30 h stability test at high operating potential,
(8)
when compared with the initial one (Fig. 3f), suggesting that during
long-term operation, its catalytic behavior is retained well. Also, η10 and
(9)
η50 of the Co,Nb-MoS2/TiO2 HSs (Inset of Fig. 3f) show only slightly
positive shifts of about 6.4 and 20.9 mV, respectively, after the chro­
noamperometry test over 30 h, further demonstrating the high dura­
bility of the catalyst for the HER.
The SEM and TEM images of the post-HER Co,Nb-MoS2/TiO2 HSs
(Fig. 3g) confirm that Co,Nb-MoS2/TiO2 HSs still has spherical structure
with little re-aggregation of NSs on the TiO2 surface. The SEM image
(Fig. 3h) and EDS elemental mapping (Fig. 3i–o) for the post-HER Co,
Nb-MoS2/TiO2 HSs clearly reveal the uniform distribution of inner Ti
and O elements and outer Co, Nb, Mo, and S elements throughout the
hollow sphere region, further validating the good structural stability of
the catalyst for the HER. The high-resolution XPS spectra of the post-
HER catalyst (Fig. S9a–f) are almost unchanged after stability test,
implying the retained composition of the Co,Nb-MoS2/TiO2 HSs during
the HER. To evaluate the HER stability of the Co,Nb-MoS2/TiO2 HSs at
different operating potentials, we performed multi-step chro­
noamperometry with operating potential ranging (58.8–198.4) mV.
Fig. S10 shows that the current density driven by the Co,Nb-MoS2/TiO2
HSs remains the same value during 500 s at each applied potential

Fig. 4. (a) iR-corrected polarization curves obtained at a scan rate of 5 mV s− 1 for Co,Nb-MoS2/TiO2 HSs, Co-MoS2/TiO2 HSs, Nb-MoS2/TiO2 HSs, MoS2/TiO2 HSs,
TiO2 HSs, Co,Nb-MoS2 NSs, and RuO2 in 1.0 M KOH electrolyte; (b) Comparison of η10 and η50 for the as-synthesized samples; (c) Comparison of η10 for Co,Nb-MoS2/
TiO2 HSs and other recently reported efficient OER catalysts; (d) Tafel plots of the as-synthesized samples; (e) Chronoamperometric curves of Co,Nb-MoS2/TiO2 HSs
at applied potentials of 1.49 V and 1.59 V for 30 h each; (f) Polarization curves before and after the chronoamperometric test; (g) SEM and TEM (inset) images of the
post-OER Co,Nb-MoS2/TiO2 HSs; and (h–o) Corresponding EDS elemental mapping of the post-OER Co,Nb-MoS2/TiO2 HSs.

8
D.C. Nguyen et al.
throughout the test, meaning that the Co,Nb-MoS2/TiO2 HSs is highly
stable under continuous change of applied potential during the HER.
This test reconfirms the good durability and stability of the Co,Nb-MoS2/
TiO2 HSs towards the HER, which is extremely important for industrial
application.
The OER performance of the Co,Nb-MoS2/TiO2 HSs was assessed by
LSV measurement at 5 mV s− 1 in 1.0 KOH medium. For comparison, the
OER activity of Co-MoS2/TiO2 HSs, Nb-MoS2/TiO2 HSs, MoS2/TiO2 HSs,
Co,Nb-MoS2 NSs, TiO2 HSs, and RuO2 catalyst were also evaluated
under the same conditions. Fig. 4a and b show that the Co,Nb-MoS2/
TiO2 HSs reveals the best OER activity with small η10 and η50 of 260.1
and 361.0 mV, respectively, which are even lower than those of the
state-of-art RuO2 catalyst (η10 = 293.2 mV and η50 = 394.5 mV). Both
Co,Nb-MoS2 NSs (η10 = 319.5 mV and η50 = 447.0 mV) and TiO2 HSs
(η10 = 501.6 mV and η50 = 616.5 mV) possess poorer OER activities
than the Co,Nb-MoS2/TiO2 HSs. Moreover, the OER catalytic activities
of the undoped MoS2/TiO2 HSs (η10 = 447.5 mV and η50 = 556.1 mV),
the Co-MoS2/TiO2 HSs (η10 = 317.5 mV and η50 = 375.7 mV), and the
Nb-MoS2/TiO2 HSs (η10 = 407.9 mV and η50 = 510.4 mV) are defi­
nitely inferior in comparison with the Co,Nb-MoS2/TiO2 HSs. Thus, the
LSV results demonstrate that the chemical coupling effect of TiO2 HSs
core and Co,Nb-MoS2 NSs shell, together with the Co and Nb co-doping
effects, contribute to the remarkable OER activities of the Co,Nb-MoS2/
TiO2 HSs. More interesting, the OER activities of the Co,Nb-MoS2/TiO2
HSs almost outperform those of the recently reported OER catalysts in
terms of η10 and η50, as seen in Fig. 4c. The OER kinetics of the catalysts
are analyzed through Tafel plot measurement, in which the Tafel slope
of the Co,Nb-MoS2/TiO2 HSs is found to be 65.0 mV dec− 1, lower than
that of the Co-MoS2/TiO2 HSs, Nb-MoS2/TiO2 HSs, MoS2/TiO2 HSs, Co,
Nb-MoS2 NSs, and TiO2 HSs of 125.9, 165.8, 175.5, 147.6, and
187.9 mV dec− 1, respectively. The smallest Tafel slope of the Co,Nb-
MoS2/TiO2 HSs implies its fastest OER rate compared with its counter­
parts, consistent with the higher OER activities of this material (Fig. 4d).
This is further evidenced when the Tafel slope of the Co,Nb-MoS2/TiO2
HSs is compared to that of other OER catalysts recently reported else­
where (Table S2), implying its potential as a superior OER catalyst in
practical OER application. The long-term durability and stability have
been recognized as necessary parameters for the OER catalyst in
commercialization. To evaluate the stability of the Co,Nb-MoS2/TiO2
HSs for OER, chronoamperometric measurement was adopted at low
and high operating voltages of 1.49 and 1.59 V, respectively. The
chronoamperometric curves (Fig. 4e) exhibit stable current density after
30 h of continuous catalysis with 95.7% and 87.6% initial current
density retention at low and high applied potentials, respectively,
evidencing the robust stability of the catalyst towards the OER.
Furthermore, a negligible change for the polarization curves of the Co,
Nb-MoS2/TiO2 HSs after 30 h stability test at high operating potential in
comparison with the initial one (Fig. 4f) reconfirms the excellent sta­
bility of the Co,Nb-MoS2/TiO2 HSs for OER. After operating under
chronoamperometric condition, positive shifts of about 4.62 and
11.8 mV are found for η10 and η50 of the Co,Nb-MoS2/TiO2 HSs (Inset of
Fig. 4f), respectively, implying the good retention of OER activity during
long-term continuous OER. The structural stability of the Co,Nb-MoS2/
TiO2 HSs for OER is demonstrated by SEM, TEM, and XPS analyses.
Fig. 4g distinctly shows that the post-OER Co,Nb-MoS2/TiO2 HSs display
the maintenance of the initial hollow sphere structure with well-ordered
ultrathin Co,Nb-MoS2 shell after OER catalysis. SEM image and EDS
elemental mapping of the post-OER Co,Nb-MoS2/TiO2 HSs (Fig. 4h–o)
indicate the uniform distribution of the Co, Nb, Mo, S, Ti, and O ele­
ments over the selected region, in which Co, Nb, Mo, and S are still
located in the shell part, while the core part contains Ti and O elements,
further verifying the intact core–shell architecture. Fig. S11 provides the
high-resolution XPS spectra of the Co2p, Nb3d, Mo3d, S2p, Ti2p, and
O1s for the post-OER Co,Nb-MoS2/TiO2 HSs. The core-level peaks of the
Ti2p, Co2p, and Nb3d after the OER test are almost similar to those of
the as-synthesized one, demonstrating the retained Co, Nb, and TiO2
9
Nano Energy 82 (2021) 105750
phases. For the case of the Mo3d, the Mo4+ 3d5/2 and Mo4+ 3d3/2 peaks
show decrease in their intensities after the OER test, whereas the peak
intensity of the Mo6+ increases, suggesting that MoS2 phase is partially
transformed into MoO3, due to the oxidation process that occurs during
the OER [63]. Moreover, after the OER stability test, the core-level
metal–oxygen peak of the O1s also increases, along with the reduction
of the S2p peak, implying the MoS2 oxidation under the anodic condi­
tion in alkaline media. Furthermore, the robust stability of the Co,
Nb-MoS2/TiO2 HSs for the OER was verified through the multi-step
chronoamperometric measurement at operating potential range be­
tween 1.49 V and 1.65 V. There is no significant change in the current
density of the Co,Nb-MoS2/TiO2 HSs at 1.49 V in the first 500 s, and the
same chronoamperometric responses are observed in the remaining
steps of the test (Fig. S12), indicating its OER activities are retained well
under the continuous change of the applied potentials. Thus, the ach­
ieved result further demonstrates the great potential of the material to
be employed as efficient and stable OER catalyst for industrial
application.
Fig. 5a shows the lab-made water splitting device utilizing the Co,
Nb-MoS2/TiO2 HSs-loaded NF as both cathodic and anodic electrodes
that the excellent activity and superior stability of the Co,Nb–MoS2/
TiO2 HSs for HER and OER inspired us to construct. A reference elec­
trolyzer device assembled by Pt/C-loaded NF cathode and RuO2-loaded
NF anode electrodes was also prepared for comparison. The polarization
curves in Fig. 5b show that the catalytic performance of the bifunctional
Co,Nb-MoS2/TiO2 HSs catalyst for overall water splitting is comparable
to that of the Pt/C//RuO2 electrolyzer. The Co,Nb-MoS2/TiO2 HSs-based
device requires cell voltages of 1.59 V and 1.88 V to reach current
density of (10 and 50 mA cm− 2, which is only 0.06 V and 0.09 V higher
than those of the Pt/C//RuO2-based device, respectively (Fig. 5c)),
clearly demonstrating the good performance of the Co,Nb-MoS2/TiO2
HSs-based electrolyzer. Such exciting performance is superior to that of
many efficient bifunctional electrocatalysts for water splitting that have
previously been developed (Fig. 5d and Table S3). In addition, the Co,
Nb-MoS2/TiO2 HSs-based device exhibits a rapid reaction kinetic, and
only requires an operating voltage of 2.16 V to achieve 100 mA cm− 2,
which is even smaller in contrast to that of the Pt/C//RuO2 cell of
2.25 V. The long-term stability of the Co,Nb-MoS2/TiO2 HSs for overall
water splitting was examined via chronoamperometry at high operating
voltage of 1.59 V. After 60 h of continuous electrolysis, the current
density driven by the Co,Nb-MoS2/TiO2 HSs is almost stable with a
current retention of ⁓89.2%, better than that of the Pt/C//RuO2-based
electrolyzer of ⁓65.8% at 30 h (Fig. 5e), evidencing the good stability of
the Co,Nb-MoS2/TiO2 HSs under water splitting condition. Water
displacement method was used to collect gaseous species produced from
the Co,Nb-MoS2/TiO2 HSs-based electrolyzer, and the results show that
the molar ratio of H2 to O2 agrees well with 2–1. More interestingly, both
experimental amounts of H2 and O2 gas fit well with the theoretical
amount during full water splitting (Fig. 5f), thereby generating high
faradaic efficiencies of 99.6% and 99.8% for the HER and OER,
respectively.
Fig. 5g provides the EIS spectra of the EIS measurement that was
conducted for different materials to clarify the origin of the excellent
electrocatalytic property of the Co,Nb–MoS2/TiO2 HSs. The Nyquist
plots of the EIS spectra were fitted with an equivalent circuit model
(Inset in Fig. 5g) to calculate Rct. The Rct of the Co,Nb-MoS2/TiO2 HSs is
found to be only 0.55 Ω, which is significantly lower than that of the Co,
Nb-MoS2 NSs (0.73 Ω), and TiO2 HSs (0.95 Ω), suggesting that the
core–shell structure with strong electronic interactions between TiO2
HSs-core and Co,Nb-MoS2-shell creates a lower resistance connection to
accelerate fast ion/electron transfer ability. In comparison with the
pristine MoS2/TiO2 HSs (0.85 Ω), Co-MoS2/TiO2 HSs (0.60 Ω), and Nb-
MoS2/TiO2 HSs (0.77 Ω), the smaller Rct of the Co,Nb-MoS2/TiO2 HSs
also indicates the important roles of both Co and Nb incorporation for
promoting the charge transfer process at the catalyst–electrolyte inter­
face, consistent with its enhanced catalytic performance.
D.C. Nguyen et al. Nano Energy 82 (2021) 105750

Fig. 5. (a) The optical image of a lab-made electrolyzer with Co,Nb-MoS2/TiO2 HSs as cathode and anode electrodes; (b) Polarization curves of the Co,Nb-MoS2/TiO2
HSs(+/− ) and Pt/C (+) // RuO2 (− ) cell; (c) Comparison of cell voltage at 10 and 50 mA cm− 2 for the Co,Nb-MoS2/TiO2 HSs (+/− ) and Pt/C (+) // RuO2 (− ) cell;
(d) Comparison of cell voltage at 10 mA cm− 2 for the Co,Nb-MoS2/TiO2 HSs (+/− ) and other efficient bifunctional electrocatalysts reported recently; (e) Chro­
noamperometric curves of the Co,Nb-MoS2/TiO2 HSs (+/− ) and Pt/C(+)//RuO2(− ) electrolyzers at voltages of 1.59 and 1.53 V, for 60 h each, respectively; (f) The
theoretically calculated and experimentally measured O2 and H2 with time at 100 mA cm− 2; (g) EIS results of the as-synthesized samples with an equivalent electrical
circuit (inset); (h) Comparison of the CV curves at 10 mV s− 1 of the samples; (i) Cdl values of the samples (1) Co,Nb-MoS2/TiO2 HSs, (2) Co-MoS2/TiO2 HSs, (3) Nb-
MoS2/TiO2 HSs, (4) MoS2/TiO2 HSs, (5) Co,Nb-MoS2 NSs, and (6) TiO2 HSs.

In addition, the ECSA was determined to further explain the
enhanced electrocatalytic performance of the Co,Nb-MoS2/TiO2 HSs. In
this work, the ECSA value was deduced from Cdl calculated by the CV
measurement (Fig. S13). Fig. 5h compares the CV cycle for the materials
at 10 mV s− 1. It can be seen that the CV cycle of Co,Nb-MoS2/TiO2 HSs
has a larger area than its counterparts, indicating the exposure of a
better active area in the Co,Nb-MoS2/TiO2 HSs material. Based on the
calculation of line slope in Fig. 5i, the Cdl values for the Co,Nb-MoS2/
TiO2 HSs, Co-MoS2/TiO2 HSs, Co,Nb-MoS2 NSs, Nb-MoS2/TiO2 HSs,
MoS2/TiO2 HSs, and TiO2 HSs are found to be 23.7, 22.4, 15.2, 6.4, 4.5,
and 2.2 mF cm− 2, respectively. In this regard, the Co,Nb-MoS2/TiO2
HSs possesses the highest Cdl value, and thus produces the largest ECSA,
suggesting the enhancement of catalytic active sites provided by the
unique structure of the Co,Nb-MoS2/TiO2 HSs and the doping effects of
Co and Nb dopants.
In other regards, the ORR performance of the Co,Nb-MoS2/TiO2 HSs
was also examined in alkaline condition using a basic three-electrode
system, in which the Co,Nb-MoS2/TiO2 HSs-loaded RDE acted as a
working electrode. In the CV measurements (Fig. 6a), the Co,Nb-MoS2/
TiO2 HSs clearly shows an oxygen reduction peak starting at ~ 0.96 V in
O2-saturated 0.1 M KOH solution, while no reduction peak can be
observed from the CV cycle in N2-saturated electrolyte, reflecting the
high catalytic activities of the Co,Nb-MoS2/TiO2 HSs towards the ORR.
The LSV measurements was then conducted for the materials. Fig. 6b
and c show that the Co,Nb-MoS2/TiO2 HSs demonstrates exceptional
ORR activities with an Eonset and E1/2 at + 0.96 and + 0.86 V, far higher
than those of the Co-MoS2/TiO2 HSs (0.92 V and 0.81 V), Nb-MoS2/TiO2
HSs (0.76 V and 0.67 V), MoS2/TiO2 HSs (0.74 V and 0.63 V), Co,Nb-
MoS2 NSs (0.81 V and 0.71 V), and TiO2 HSs (0.71 V and 0.62 V). These
results suggest that the formation of unique core–shell architecture and
the successful incorporation of both Co and Nb are the primary factors
for dramatically expediting the ORR performance. Although the Eonset
and E1/2 of the Co,Nb-MoS2/TiO2 HSs are slightly lower than those of Pt/
C of 0.97 V and 0.87 V, it is noteworthy that the ORR activities of the Co,
Nb-MoS2/TiO2 HSs can be favorably compared with those of recently
reported ORR catalysts (Table S4), further demonstrating the competi­
tive activities of the Co,Nb-MoS2/TiO2 for the ORR. The Tafel plots
(Fig. 6d) demonstrate that the Co,Nb-MoS2/TiO2 HSs possesses the small
Tafel slope value of 56.1 mV dec− 1, which is only 1.6 mV dec− 1 higher
than that of the Pt/C (54.5 mV dec− 1), suggesting that the advantages of
the morphological and electronic structural properties of the Co,Nb-
MoS2/TiO2 HSs not only improve the ORR activities, but also enhance
the ORR kinetics. The superior kinetics of the Co,Nb-MoS2/TiO2 HSs is
further demonstrated, since it is compared to those of the Co-MoS2/TiO2

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D.C. Nguyen et al. Nano Energy 82 (2021) 105750

Fig. 6. (a) CV curves of the Co,Nb-MoS2/TiO2 HSs in N2- and O2-saturated 0.1 M KOH solution; (b) Polarization curves of the materials; (c) Comparison of the Eonset
and E1/2 of the materials; (d) Tafel plots of the materials; (e) Polarization curves of the Co,Nb-MoS2/TiO2 HSs at various rotating speeds; (f) Koutecky–Levich plots of
the Co,Nb-MoS2/TiO2 HSs and n value (inset); (g) Comparison of the polarization curves of the Co,Nb-MoS2/TiO2 HSs before and after 1000 CV cycles; (h) Chro­
noamperometric curves of the Co,Nb-MoS2/TiO2 HSs and Pt/C catalyst at operating potentials of 0.86 and 0.87 V, for 60,000 s each, respectively; (i) Methanol
crossover tests for the Co,Nb-MoS2/TiO2 HSs and Pt/C catalyst under the influence of 1.0 M methanol addition. [(1) Co,Nb-MoS2/TiO2 HSs, (2) Co-MoS2/TiO2 HSs,
(3) Co,Nb-MoS2 NSs, (4) Nb-MoS2/TiO2 HSs, (5) MoS2/TiO2 HSs, (6) TiO2 HSs, and (7) Pt/C)].

HSs (76.5 mV dec− 1), Nb-MoS2/TiO2 HSs (93.5 mV dec− 1), MoS2/TiO2
HSs (100.1 mV dec− 1), Co, Nb-MoS2 HSs (86.4 mV dec− 1), and TiO2
HSs (113.9 mV dec− 1). The ORR mechanism of the Co,Nb-MoS2/TiO2
HSs was further investigated through LSV measurement at various
rotating rates of 400, 800, 1200, 1600, and 2000 rpm. The LSV curves in
Fig. 6e show a quick increase in the limited diffusion current density of
the Co,Nb-MoS2/TiO2 HSs since the rotation speed increases, implying
an effective diffusion process during the ORR catalysis. Based on the
Koutecky–Levich (K–L) equation, the K–L plots obtained from the Co,
Nb-MoS2/TiO2 HSs (Fig. 6f) indicates n ≈ 3.96 in the potential range of
(+ 0.31 to + 0.66) V, implying a direct 4e- pathway occurring during
the ORR in 0.1 M KOH. In order to further investigate the ORR mech­
anism of the Co,Nb-MoS2/TiO2 HSs, we carried out RRDE test of the Co,
Nb-MoS2/TiO2 HSs along with the Pt/C for comparison. The RRDE po­
larization curves of the Co,Nb-MoS2/TiO2 HSs and Pt/C are given in
Fig. S14a, which clearly exhibits that the disk current is far higher than
that of the corresponding ring current. Based on the RRDE test result and
the Eqs. (6) and (7), the n and H2O2 percentage of Co,Nb-MoS2/TiO2 HSs
are found to be between 3.89 and 3.95 and 9.2–11.9% in the 4.0–6.0 V
potential range, respectively, which is almost comparable to the Pt/C
(3.91–3.99 and 4.56–5.84%) (Fig. S14b and c). Therefore, the obtained
results corroborate that the ORR process mainly occurs through a direct
4e- pathway for the Co,Nb-MoS2/TiO2 HSs, consistent with the RDE test
results. Moreover, the long-term durability and stability of the Co,Nb-
MoS2/TiO2 HSs towards ORR is investigated by cycling stability test in
O2-saturated 0.1 M KOH solution. After cycling test, the E1/2 value is
only 24 mV lower than that of the initial one, indicating no obvious
change in the ORR performance of the Co,Nb-MoS2/TiO2 HSs before and
after 1000 cycles (Fig. 6g). This is favorable evidence for the good
durability and stability of the Co,Nb-MoS2/TiO2 HSs towards ORR. In
addition, chronoamperometry was also carried out for the Co,Nb-MoS2/
TiO2 HSs to further probe its stability (Fig. 6h). The Co,Nb-MoS2/TiO2
HSs maintains 96.65% of its initial current density after 60,000 s of
continuous ORR at operating potential of 0.86 V, superior to that of the
Pt/C catalyst (a retention of only 88.78% activity at 30,000 s). The SEM
images of the post-ORR Co,Nb-MoS2/TiO2 HSs (Fig. S15a and b) show
that its initial morphology is still well retained after 60,000 s stability
test. The EDAX pattern of the post-ORR Co,Nb-MoS2/TiO2 HSs still in­
dicates the presence of the required elements, such as Co, Nb, Mo, S, Ti,
and O (Inset of Fig. S15b).
The TEM image in Fig. S15c displays the good preservation of the
hierarchical core–shell structure with hollow spherical feature of the
post-ORR Co,Nb-MoS2/TiO2 HSs. A set of lattice fringes with interplanar
distances of 0.64 and 0.27 nm are observed from the HR-TEM image
(Fig. S15d), which correspond with the (002), and (100) planes of the
MoS2, respectively, proving that after a continuous ORR operation in

11
D.C. Nguyen et al.
alkaline medium, the MoS2 phase is still stable. In addition, the EDS
elemental mapping images (Fig. S15e–l) of the post-ORR Co,Nb-MoS2/
TiO2 HSs display the uniform distribution of the Ti and O elements at the
core region, while the Mo, S, Co, and Nb elements are distributed at the
shell area, further verifying its core–shell structure is retained well.
Thus, the SEM, TEM, and EDS analyses clearly show the good
morphological stability of the material under long-term operation. The
excellent alcohol tolerance of the Co,Nb-MoS2/TiO2 HSs was assessed by
adding 1.0 M methanol to 0.1 M O2-saturated KOH solution during the
ORR process. The chronoamperometric test (Fig. 6i) indicates that after
the methanol addition into electrolyte, the current response of the Pt/C
catalyst immediately increases, due to effective methanol oxidation at
its surface, while the Co,Nb-MoS2/TiO2 HSs presents no clear current
change, indicating the great potential of this catalyst as cathodic catalyst
in direct methanol fuel cell application.
In order to exclude the NF influence on the electrocatalytic perfor­
mance, we adhered the as-synthesized Co,Nb-MoS2/TiO2 HSs sample
onto glassy carbon (GC) electrode (label as Co,Nb-MoS2/TiO2 HSs/GC)
instead of the NF and conducted LSV measurement under electro­
catalytic HER and OER conditions for the obtained electrode along with
pure GC and pristine NF for comparison (Fig. S16a and b) [64,65]. As
seen, the pure GC and pristine NF exhibit very poor HER and OER
performance, suggesting the key contribution of the host Co,
Nb-MoS2/TiO2 HSs in achieving extraordinary catalytic activity. It is
well known that onset overpotential is an important descriptor reflected
properly the catalytic activity of materials, and thus to evaluate
correctly the catalytic activity of the Co,Nb-MoS2/TiO2 HSs, we deter­
mined onset overpotential values of the Co,Nb-MoS2/TiO2 HSs/GC and
Co,Nb-MoS2/TiO2 HSs/NF samples based on start point of the Tafel
slope. Fig. S16c and d show that the onset overpotential of Co,
Nb-MoS2/TiO2 HSs/GC is found to be 44.2 and 248.3 mV for the HER
and OER, respectively, which is almost comparable with the Co,
Nb-MoS2/TiO2 HSs/NF (29.7 and 228.6 mV), corroborating the excel­
lent catalytic activity of Co,Nb-MoS2/TiO2 HSs - in other words, the NF
substrate has little influence on the electrocatalytic properties when
compared with the host Co,Nb-MoS2/TiO2 HSs. Furthermore, the CV
measurement at different scan rates was also performed for the NF
(Fig. S16e) to evaluate its ECSA through determination of Cdl. The result
in Fig. S16f reveals that the NF reaches Cdl of 1.52 mF cm− 2, which is
15.6 time lower than that of the Co,Nb-MoS2/TiO2 HSs/NF, suggesting
the much smaller ECSA of NF than that of the Co,Nb-MoS2/TiO2
HSs/NF. This also implies that the enhanced exposure of accessible
active sites for reactants and/or electrolyte originates mainly from the
host Co,Nb-MoS2/TiO2 HSs; the NF substrate thus possesses negligible
contribution to the total catalytic performance.
In addition, we also examined the HER, OER, and ORR performance
of Co,Nb-MoS2/TiO2 HSs prepared under different molar ratio of the
reactant Co(NO3)2 and NbCl5, including 2:1, 1:1, and 1:2 (denoted as 1-
Co,Nb-MoS2/TiO2 HSs, 2-Co,Nb-MoS2/TiO2 HSs, and 3-Co,Nb-MoS2/
TiO2 HSs, respectively) to investigate the influence of Co and Nb doping
content on the catalytic performance. The HER polarization curves of
these samples in Fig. S17a show that the 1-Co,Nb-MoS2/TiO2 HSs
sample possesses an optimal HER catalytic activity along with smaller η
and Tafel slope value than for the others (Fig. S17b and c). Likewise,
Fig. S17d–f reveal the better OER catalytic activity of the 1-Co,Nb-
MoS2/TiO2 HSs sample as compared to the others. Furthermore, the 1-
Co,Nb-MoS2/TiO2 HSs also demonstrates the best ORR catalytic activity
with a lowest Eonset and E1/2 value (Fig. S17g–i). Therefore, the above-
obtained results clearly indicate dependence of the electrocatalytic ac­
tivity of Co,Nb-MoS2/TiO2 HSs on the Co and Nb doping content; the Co,
Nb-MoS2/TiO2 HSs with the molar ratio of Co:Nb = 2:1 shows the
optimal electrocatalytic performance for all HER, OER, and ORR.
Furthermore, to provide deep insight into the origin of the catalytic
enhancement, we performed theoretical calculations based on density
functional theory (DFT). In this work, the DFT calculations were carried
out with Vienna ab initio simulation package (VASP), together with the
12
Nano Energy 82 (2021) 105750
application of Perdew–Burke–Ernzerhof functional for exchange-
correlation energy. Fig. 7a and b show the top view and side view of
the atomic structure for the pristine MoS2 layer, and Co and Nb dual-
doped MoS2 layer, respectively, along with some important parame­
ters, such as formation energy, and atomic distance. Electronic band
structure of the Co,Nb-doped MoS2 and the sets of its counterparts, as
well as their interaction ability with adsorbents were identify by density
of states (DOS) calculations [66,67]. Fig. 7c compares DOS result of the
Co,Nb-doped MoS2 with Co-doped MoS2, Nb-doped MoS2, and single
MoS2. As seen, the electronic states of the Co,Nb-doped MoS2 are close to
Fermi level, and are significantly higher than for its counterparts,
implying faster charge transfer and lower activation energy for inter­
mediate adsorptions of Co,Nb-doped MoS2 [17]. The increased elec­
tronic states around the Fermi level is mainly due to the
co-incorporation of Co and Nb, causing the enhanced electron transfer
and intermediate adsorption ability, and thus the catalytic activity.
Moreover, it is well-known that adsorption free energies of hydrogen
(∆GH*) is a key parameter in reflecting HER activity; in general, an
excellent HER electrocatalyst demonstrates an optimal ∆GH* value
around 0 eV [68]. Accordingly, to further understand the synergistic
effects deriving from MoS2 and Co, Nb dual doping for the HER, ∆GH* on
Mo, S, Co, and Nb centers in MoS2 and Co,Nb-doped MoS2 were calcu­
lated and compared in Fig. 7d. The pure MoS2 possesses a high ∆GH*
values of 2.525 and 1.733 eV for Mo and S sites, respectively. Whereas,
after incorporation of Co and Nb into MoS2 structure, the ∆GH* values of
Mo and S centers are significantly reduced to 0.055 and 1.687 eV,
respectively, demonstrating remarkable enhancement of HER activity.
In particularly, the adsorption free energy of H on Mo center in Co,
Nb-doped MoS2 is very close to 0 eV, consistent with its good HER
performance. Noticeably, the ∆GH* values of the Co (0.969 eV) and Nb
(0.303 eV) sites in Co,Nb-doped MoS2 are also close to 0 eV, suggesting
that Co and Nb may act as additional active sites in this structure. Thus,
the computational studies corroborate a much better HER activity of the
Co,Nb-doped MoS2 than that of the pure MoS2, which are consistent well
with experimental results.
4. Conclusions
In summary, we have developed a novel Co,Nb-MoS2/TiO2 HSs
hybrid material with mesoporous nanosheet-shelled heterostructure via
a simple and effective strategy. Benefiting from the synergistic effects of
valuable factors, including the unique hollow core–shell structure con­
taining strong electronic interactions between the core part and shell
layer, the Co and Nb dual-doping effects, and the ultrathin and meso­
porous characteristics of the MoS2 NSs, the catalytic performance of the
Co,Nb-MoS2/TiO2 HSs towards the HER, OER, and ORR reactions is
significant improved. As a result, the Co,Nb-MoS2/TiO2 HSs displays
good activities for the simultaneous HER and OER in alkaline condition
with the HER and OER η10 values of 58.8 and 260.0 mV, respectively.
The electrolyzer with symmetric cell based on the Co,Nb-MoS2/TiO2 HSs
as both cathode and anode electrodes can drive 10 mA cm− 2 at an
operating voltage of 1.59 V, which is superior to that of the recently
reported bifunctional electrocatalysts. In addition, the Co,Nb-MoS2/
TiO2 HSs demonstrates efficient electrocatalytic activities for the ORR
with high Eonset value of + 0.96 V, E1/2 of + 0.86 V, and a direct 4e-
pathway in 0.1 M KOH media. Our work paves a way for the effective
improvement of the intrinsic catalytic activities of MoS2-based nano­
material towards HER, OER, and ORR via the doping effect to upgrade
its advantaged properties, thus leading to it being suitable for multi­
functional applications in the forthcoming critically needed green en­
ergy conversion and storage technologies.
CRediT authorship contribution statement
Dinh Chuong Nguyen: Methodology, writing-original draft, vali­
dation, validation visualization. Thi Luu Luyen Doan: Methodology,
D.C. Nguyen et al.
Fig. 7. (a and b) Schematic illustration for the atomic structure of MoS2, H-Mo (MoS2), Co,Nb-MoS2, and H-Mo (Co,Nb-MoS2) with top and side view as well as their
corresponding structural parameters; (c) Calculated DOS curves for MoS2, Co-MoS2, Nb-MoS2 and Co,Nb-MoS2; and (d) The Gibbs free energy of H* (ΔGH*) for (1) H-
Co(Co,Nb-MoS2), (2) H-Nb(Co,Nb-MoS2), (3) H-Mo(Co,Nb-MoS2), (4) H-S(Co,Nb-MoS2), (5) H-Mo(MoS2), and (6) H-S(MoS2).
investigation, formal analysis. Sampath Prabhakaran: Density-
functional theory calculation. Duy Thanh Tran: Writing- reviewing
and editing. Do Hwan Kim: Density-functional theory calculation,
writing- reviewing and editing. Joong Hee Lee: Conceptualization, data
curation, writing- reviewing and editing, supervision. Nam Hoon Kim:
Conceptualization, writing- reviewing and editing, supervision, project
administration.
Declaration of Competing Interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
Acknowledgments
This research was supported by the Basic Science Research Program
(2019R1A2C1004983) and the Regional Leading Research Center Pro­
gram (2019R1A5A8080326) through the National Research Foundation
funded by the Ministry of Science and ICT of Republic of Korea.
Appendix A. Supporting information
Supplementary data associated with this article can be found in the
online version at doi:10.1016/j.nanoen.2021.105750.
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