Accepted Manuscript

Three-dimensional porous Ni-CNT composite nanocones as high

performance electrocatalysts for hydrogen evolution reaction

Gh. Barati Darband, M. Aliofkhazraei, A. Sabour Rouhaghdam

PII: S1572-6657(18)30672-6
DOI: doi:10.1016/j.jelechem.2018.10.012
Reference: JEAC 12652
To appear in: Journal of Electroanalytical Chemistry
Received date: 18 April 2018
Revised date: 10 July 2018
Accepted date: 6 October 2018

Please cite this article as: Gh. Barati Darband, M. Aliofkhazraei, A. Sabour Rouhaghdam
, Three-dimensional porous Ni-CNT composite nanocones as high performance
electrocatalysts for hydrogen evolution reaction. Jeac (2018), doi:10.1016/
j.jelechem.2018.10.012

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 ACCEPTED MANUSCRIPT

Three-dimensional porous Ni-CNT Composite Nanocones as High

Performance Electrocatalysts for Hydrogen Evolution Reaction

Gh. Barati Darband, M. Aliofkhazraei*, A. Sabour Rouhaghdam

Department of Materials Engineering, Tarbiat Modares University, Tehran, Iran, P.O. Box:

14115-143, Tehran, Iran

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*
Corresponding author: Tel.: +98-912-6905626, Fax: +98-21-66960664, E-mail address:

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maliofkh@gmail.com, khazraei@modares.ac.ir

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Abstract

In this study, a new 3D hierarchical Ni-CNT nanostructure was fabricated using

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electrodeposition method in a bath containing crystal modifier, where its electrocatalytic

activity and stability for hydrogen evolution reaction (HER) were investigated. The resulting
Ni-CNT nanostructures were characterized by different analysis such as XRD, SEM, EDS and
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AFM. The electrocatalytic activity, stability and corrosion resistance of the fabricated Ni-CNT
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as cathode for the HER in 1.0 M potassium hydroxide (KOH) solution were investigated by
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LSV curves, CV and EIS techniques. The results indicated highly active surface area as well
as increased electrical conductivity owing to introduction of CNT into the Ni nanocones
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(NNCs) improving intrinsic catalytic activity for HER. Furthermore, due to their hierarchical
structure, the Ni-CNT nanostructure facilities bubble detachment, effectively reducing the dead
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area resulted from bubbles phenomena. These two features are beneficial for high activity and
stability during HER. This electrode able to afford current densities of 10, 20 and 100 mA/cm2
at the HER overpotentials of 82 and 116 and 207 mV, respectively. High chemical stability of
CNT leads to an increase in the electrocatalytic stability and corrosion resistance of Ni-CNT
hierarchical nanostructure. This research introduces the novel 3D nanocomposite structure for
enhancing electrocatalytic activity for HER.

Keywords: Renewable energy, Hydrogen evolution reaction, Ni-CNT, Electrocatalytic

activity.

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1. Introduction

Providing energy for nine billion estimated people throughout the 21th century has been one
of the most challenging issues [1]. Burning fossil fuels in an irreversible manner has led to
extensive damage to life of human societies. Depletion of fossil fuel sources, greenhouse gas
emissions and consequently, climate changes are the two major problems with the use of non-
renewable fuels. Therefore, finding suitable alternative renewable fuels is among the most
important objectives for the future of human life. Among all the alternatives for the fossil fuels,

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hydrogen has been known as the best energy source due to its minimum pollution to the
atmosphere and high energy density per mass (140 MJ/kg). Hydrogen can be produced through

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different methods; among them, water electrolysis is regarded as the most popular method. One
of the important challenges of the application of water electrolysis for hydrogen production is

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lowering the amount of consumed electricity energy. For water electrolysis treatment,
numerous resistances must be overcome. Two most important resistances in the path of water
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splitting are polarization resistance and emerged resistance due to bubble formation on the
surface of catalyst during the hydrogen evolution reaction (HER). In general, the consumed
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energy during HER can be lowered by choosing cathodes with appropriate electrocatalytic
activity [2]. Among all the cathodes used for HER, Pt exhibits the lowest overpotential;
unfortunately, the practical use of Pt is limited owing to its limited availability and high price
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[3, 4]. Thus, fabrication of a cathode with low price and high electrocatalytic activity leads to
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increasing the efficiency of hydrogen production in water electrolyzing treatment. Universal

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strategies for the electrocatalytic activity improvement are a) increasing the active surface area,
b) increasing the intrinsic electrocatalytic activity, and c) increasing the electrocatalytic
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stability [5]. Nickel and its alloys [6-8] have been known for their high electrocatalytic activity
of HER. Numerous efforts including fabrication of nanowires [9, 10] and nanosheets [11] have
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been made for improving HER efficiency. One of the major drawbacks of the aforementioned
nanostructure for HER is that hydrogen can be evolved only on one dimension of these
nanostructures, which leads to lower electrochemically-active surface area. Among the one
dimensional nanostructures which have attracted a great deal of attention in recent years, are
the nanocones. Nanocones can be fabricated through different methods, where
electrodeposition has found special significance among them due to economical simplicity [12,
13]. With regards to the special structure of nanocones which have nanometric steps on their
surface, it is expected that the active surface area of nanocones structure is increased further in
comparison to nanowire and nanosheets structure and consequently, possesses higher HER

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activity[14]. In addition, most electrocatalysts in the literature are in powder form, which
require to be assembled on a conductive surface in order to be properly utilized [15]. Binder
polymers are usually used throughout the assembly treatment. Usage of polymers reduces the
surface area between the catalyst and the electrolyte, consequently weakening the catalytic
properties. In addition, due to the powder form and the application of binder, the
electrocatalytic stability is decreased at high current densities. Therefore, through
electrodeposition method, the catalyst can be directly deposited on conductive surface without

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any form of binder which results in remarkable properties.

The adhered bubbles on the electrocatalyst surface will reduce the active surface area and

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deteriorate the electrocatalytic activity. One procedure for overcoming the bubble phenomena
is to synthesize the electrode with underwater superareophobic and superhydrophpilic surface

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nature [16]. Despite tremendous progress in the fabrication of modern HER electrocatalysts,
little attention has been given to improvement of electrocatalytic activity by managing the
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bubbles on the surface. Research has proven that fabrication of ultra-rough, vertical
nanoarchitecture surfaces leads to superaerophobicity through creation of discontinuous three-
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phase contact line (TPCL) [17]. Thus, it is expected that the nanocones would exhibit a
superaerophobic structure with improved electrocatalytic activity. On the other hand, Carbon-
based materials such as carbon nanotubes (CNTs) with high mechanical strength and
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exceptional electrical conductivity are used as materials for electrochemical reactions [18]. Due
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to their unique properties such as high corrosion resistance and suitable chemical stability,
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usage of CNTs as good electrocatalyst for HER has been the subject of various research works
in the recent years [19, 20]. Nevertheless, to the best of our knowledge, few studies have been
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carried out on the electrocatalytic activity of Ni-CNT nanostructure with emphasis on

management of bubble phenomena. Therefore, this study aims to utilize all possible strategies
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for enhancing the electrocatalytic activity for HER. As a result, the underwater
superhydrophpilic and superareophobic 3D hierarchical Ni-CNT composite nanostructure was
grown on the Cu substrate. Moreover, it is expected that through introduction of CNTs into the
structure of NNCs, the electrocatalytic activity and stability of the fabricated catalyst will be
improved.

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2. Experimental details

2.1. Film electrodeposition

In this study, the electrodeposition method was used in order to synthesize nanocones on a Cu
substrate. Copper substrates were used in this study for electrodeposition of nickel nanocones
and hierarchical Ni-CNT nanostructure. The specimens were cut in 2×5cm2 dimensions.
Afterwards, they were polished by hard-to-soft sandpapers and degreased in methanol by
ultrasonic bath for 20 min. Next, they were electropolished under 20 mA/cm2 current density

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for 1 min in a solution containing 70 g/L Na2CO3, 10 g/L KOH and 10 g/L sodium dodecyl
sulfate (SDS). Then, the specimens were activated for 20 secs at room temperature in 10 wt%

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HCl solution. Later, they were rinsed with deionized water and immediately placed in the

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electrodeposition bath, which contained 238 g/L NiCl2.6H2O, 31g/L H3BO3 and 200 g/L
ethylenediammonium dichloride (C2H10Cl2N2) as crystal modifier (All of the used chemicals
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were of analytical grade). Moreover, Ni-CNT hierarchical nanostructure was fabricated via
addition of 2 g/L CNT in the bath composition. For wetting and well dispersion of CNTs in the
bath, SDS surfactant was utilized. Prior to electrodeposition, the bath containing crystal
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modifier and CNTs was sonicated to fully disperse the CNTs into the bath. Coating process
was applied in a two-step manner. In step 1, 10 mA/cm2 was employed for 10 min, and in step
2, 50 mA/cm2 was used in order to obtain the structure of nanocones.
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2.2. Structural characterization

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Field emission scanning electron microscope (FESEM) (MIRA3TESCAN-XMU) was used to

study the surface morphology, and EDS analysis was employed for elemental analysis. The
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topology and surface roughness of the samples were analyzed by Atomic Force Microscopy
(AFM) (Ara-A.F.M. Model No. 0101/A: Iran). X-ray diffraction test (Model: X'Pert MPD) was
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employed in order to study the phase composition of the fabricated catalysts.

2.3. Electrochemical characterization

Electrocatalytic activity of the fabricated electrodes was evaluated using linear sweep
voltammetry (LSV) with a scanning rate of 1mV/s, and electrochemical impedance
spectroscopy (EIS) studies in various applied potentials ranging from 100 kHz-100 mHz with
an amplitude of 10 mV. Electrocatalytic stability was analyzed using cyclic voltammetry (CV)
for 1000 cycles and chronopotentiometry techniques. All of the electrochemical studies were
conducted in 1M KOH solution in standard 3-electrode cell in which a Pt electrode was used

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as counter electrode, Ag/AgCl (saturated KCl, 3M) was used as reference electrode, and 1cm2
fabricated catalyst was used as working electrode. All potentials in this study were referred
against reversible hydrogen electrode (RHE). The potential measured against the SCE
electrode was converted to the potential versus the RHE.

3. Results and discussion

3.1. Structural characterization

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Surface morphology of the NNCs and Ni-CNT structures fabricated in the electrolyte
containing crystal modifier was studied using FESEM, and the results are displayed in Fig. 1.

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It can be seen that the NNCs have grown on Ni microcones to form the structure of micro-
nanocones. It is observed that the average root diameter of the nanocones is about 200 nm, with

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the height of about 500 nm and the tip diameters of about 20 nm. It is clear from Fig. 1 that
nanocones have grown in a spiral manner, and nano-steps are present on their surface. Presence
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of these nano-steps on surface of the nanocones can be explained by the growth mechanism of
nanocones. It is believed that formation of these nanocones, as a result of the addition of crystal
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modifier to the electrolyte, can be linked to the growth of screw dislocations. In this process,
Ni ions are preferentially deposited on the screw dislocations surface due to high surface energy
level. This growth continues in the horizontal and vertical directions. It has been reported that
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crystal modifiers in the electrolyte limit the growth in horizontal direction and promote the
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growth in vertical direction; and thus the nanocones are formed [12, 21]. Based on microscopic
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studies by Hang et al. [22], NNCs are perfect single crystals and grow in the [011] direction
and also (111) and (100) crystal planes form nano-steps on nanocones surfaces. It is clearly
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seen in Fig. 1b that the Ni-CNT coatings are formed in the electrolyte containing crystal
modifier, form the 3D nanostructure including NNCs on which CNTs are spread, implying the
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strong bond between the CNTs and NNCs. During the electrodeposition of Ni-CNT
nanostructure, CNTs not only act as active nucleation cites, but also preferentially fill the grain
boundary and prohibit grain growth, resulting in the formation of fine grains structure [23, 24].
It is believed that, due to the electrolyte circulation during coating process, the electrolyte Can
easily penetrate near CNTs cites , and by providing the Ni ions in the vicinity of CNTs, lead to
the reduction of Ni ions and consequently formation of the mentioned structure [24]. The
elemental mappings of Ni and C are shown in Figs. 1c and 1d, respectively, indicating that
CNTs are well dispersed in the NNCs matrix. In order to further investigate and prove the role
of CNTs in the electrodeposition process, the XRD analysis of NNCs and Ni-CNT

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nanostructure were performed, and the results are indicated in Fig. 1e. As shown, in the NNCs
and Ni-CNT nanostructure, only Ni and Cu phases can be detected. It can be said that Cu phase
is originated from the Cu substrate, indicating very low thickness of the coating. Moreover, no
clear diffraction peak of the CNTs was observed in the XRD patterns, probably due to the low
amount of CNTs in the coating, which is not sufficient to be detected by the XRD [25].
According to Scherrer's equation, an inverse relationship exists between crystal size and full
width half maximum (FWHM) [26]. The FWHM results of (111) and (200) diffraction peaks

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related to Ni phase are represented in Table S1 (Supporting information). It can be seen that by
incorporation of CNTs in structure, the FWHM is increased, indicating grain refinement.
Furthermore, AFM analysis was employed in order to study the topology and roughness of

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nanocones structure (Fig. 1f). The structure of the nanocones can be clearly observed in the

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AFM image, and that the height of nanocones is in good agreement with the FESEM results.

3.2. Electrocatalytic activity

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3.2.1. Polarization study
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The electrocatalytic activity of NNCs and Ni-CNT hierarchical nanostructure were evaluated
using the steady-state linear sweep voltammetry) LSV( studies. the Cu foil substrate,
electrodeposited pure Ni electrode and commercial Pt/C catalyst were also tested for purpose
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of comparison. Furthermore, the electrocatalytic activity of the electrodes were fabricated in

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electrolytes containing different CNT concentrations were evaluated. The LSV curves of these
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electrodes are shown in Fig. S1 (supporting information). It is seen that by increasing the CNT
concertation from 0.5 g/L, to 2 g/L, the catalytic activity is increased, and later by further
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increase in CNT concertation to 3 g/L, the catalytic activity is not changed, reaching a nearly-
constant value. Thus, the electrode with 2 g/L CNT was selected for evaluation. The LSV
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curves of different catalysts are illustrated in Fig. 2a. As expected, the Pt/C shows superior
HER activity with approximately zero onset potential, whereas Cu substrate exhibit very low
activity with negligible current density even at high overpotential levels. In contrast, the onset
potential of the prepared Ni-CNT nanostructure for HER is minimum among the other
catalysts, and requires overpotential of 82 mV, 116 mV, and 207 mV to achieve the current
densities of 10, 20 and 100 mA/cm2, respectively. The η10, η20 and η100 for HER in different
studied electrodes are shown in Fig. 2c. These values for Ni-CNT nanostructure are superior
relative to most of the reported values for other nickel-based catalysts for HER (Table 1).
Moreover, another important parameter used for evaluation of the catalytic activity is exchange

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current density (j0) which is calculated form Tafel plots by using the extrapolation method (Fig
S2). The j0 of Ni-CNT normalized to electrochemically active surface area (the calculation of
ECSA is included in the following section) is 0.61 µA/cm2 greater than that of NNCs (0.56
µA/cm2), indicating the better catalytic activity of Ni-CNT electrode. The electrocatalytic
behavior improvement of NNCs relative to Ni film can be associated to active surface area
increase for HER. As can be seen from the FESEM images, NNCs have a 3D structure with
higher active surface area than Ni film. Also most of the electrodes which used for HER have

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high adhesion to bubbles during the electrolysis, due to their underwater aerophilic nature [27,
28]. Hydrogen adsorption on the cathode materials during water electrolysis inhibits the direct
contact between the electrode and the electrolyte, and leads to the formation of a dead area

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between them. Consequently, ohmic drop occurs and HER overpotential is increased.

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Therefore, finding important strategies for easy detachment of H2 bubbles during electrolysis
is one of the best methods for increasing the electrocatalytic activity. Although detachment of
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H2 bubbles can be enhanced by different methods such as ultragravity and ultrasonic
treatments, these methods require high amounts of energy and are not economical. One of the
best procedures for enhancement of bubble detachment is surface nanostructuring [29-32].
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Therefore, it can be expected that by surface nanostructuring and fabrication of underwater

superhydrophilic and superareophobic, the three phase contact line (TPCL) between the formed
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H2 bubbles and the electrode surface will be divided into discontinuous sections, and will result
in a decrease in the contact area between the H2 bubbles and cathode. This leads to the lowering
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of the adhesive force of bubbles to the cathode materials, consequently decreasing in the ohmic
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drop. This concept is schematically shown in Fig. 3a (flat surface, microstructured surface and
nanostructured surface). The detachment behavior of bubbles during HER on fabricated
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nanostructure and flat surface was recorded by Dino lite microscope. All experiments were
conducted in 30 mA/cm2 for comparison purposes. The images of the bubbles at different
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surface morphologies and three different intervals for nanostructure and flat surface are
illustrated in Figs. 3b and 3c, respectively. The distribution of bubble size is also indicated in
the above figures. It is clear that on the Ni nanostructured surface, the formed bubbles are
detached from the surface before growing larger than ≈200 µm in diameter, and the major part
of their size is less than 60 µm. Moreover, it is seen from movie S1 (Supporting Information)
that there are not any adhered bubbles to the surface during HER. It is observed on the flat
surface that the number of bubbles were decreased and their size has been increased. In this
situation, the formed bubbles stick to the surface and hardly detach from the surface. Though
the bubbles with 100 µm in diameter are observed, they will detach only upon reaching 300

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µm in diameter, which is seen from movie S2 (Supporting Information). There are many
baubles adhering to the surface during HER as can be seen in movie S2. Based on these
experiments, it can be concluded that the fabrication of nanostructured surface could be
beneficial for fast detachment of bubbles, and consequently, decrease in required energy for
hydrogen production. Similarly, Li et al. [33] studied the detachment of the bubble during HER
on Pt nanoarray electrode, and observed that fabrication of nanoarray leads to lowering the
bubble size for detachment.

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HER in the alkaline solution involves solid-liquid and solid-gas interfaces reactions. These
reactions can significantly impact the electrocatalytic activity. Thus, understanding the role of

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surface properties in HER activity is very important. Surface wettability is one of the
fundamental properties of the surface which can affect the electrochemical reactions [34] . The

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wettability of nanocones structure and flat Ni was evaluated using static contact angle method.
The contact angles are shown in Fig 4. It is seen that the electrodes exhibit different behavior
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towards the water droplet due to their different surface roughness. It is shown that the contact
angle of flat Ni electrode is 86°, indicating its hydrophobic nature. The contact angle of NNCs
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is smaller than 5°, indicating its extremely hydrophilic nature. Our results indicate that the
structure of NNCs is very favorable for greater electrolyte accessibility, thereby improving
HER activity in alkaline media.
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It is seen in Fig. 2a that the electrocatalytic activity of the coating with CNTs is higher than the
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coating without CNTs. The electrocatalytic activity improvement of Ni-CNT nanostructured

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coating can be ascribed to two factors: 1) coating modification and decrease in grain size and
further increase in active surface area due to addition of CNTs into the coating, and 2)
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improvement in electron transfer between the electroactive species and the cathode. The second
factor is schematically shown in Fig. 5. Wang et al. [35] have fabricated Co-doped iron pyrite
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(FeS2) electrocatalysts on carbon nanotube (Fe1-xCoxS2/CNT) hybrid catalysts for HER, and
concluded that the role of CNTs is to increase the electron transfer. It is also reported elsewhere
that CNT increase the electrocatalytic activity by facilitating the electron transfer [36-38].

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Table 1: Comparison of the HER electrocatalytic efficiency of hierarchical Ni-CNT nanostructure and
other Ni-based catalysts in alkaline solution

Catalysts Electrolyte i η Ref

(mA/cm2) (mV)
Ni-CNT nanostructure 1 M KOH 10 82 This study
20 116
100 207
MoP/CNTs 1 M KOH 10 86 ]39[

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NiCoP/rGO 1 M KOH 10 209 ]40[
Ni-MoS2 1 M KOH 10 98 ]41[

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NiSe2/Ti 1 M KOH 10 96 ]42[
]43[

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Ni/Co-S 1 M KOH 10 102
NiSe/NF 1.0 M KOH 10 96 ]44[
Ni/N/C 0.1 M KOH 10 190 ]45[
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CoFex-CoFe2O4/N- 0.1 M KOH 20 159 ]46[
doped carbon
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nanocomposite
MnNiX 1 M KOH 10 360 ]47[
NiCoMo film 1 M KOH 10 132 ]48[
]49[
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Ni/NiO-CNT 1 M KOH 10 100

NiS nanoframe 1 M KOH 10 94 ]50[
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Ni-C3N4 1M NaOH 10 222 ]51[

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100 356
Ni-Graphene 0.1 M KOH 10 300 ]52[
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Ni- MoS2/Ni foam 1M NaOH 100 207 ]53[

Ni-rGO/Cu 10 91 ]54[
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100 262
Ni-(MoS2/GO) 1M NaOH 10 33 ]55[
100 132
Ni nanoparticle 1 M KOH 10 187 ]56[
/MWCNT

In order to further understand the mechanism of HER on nickel nanocones and Ni-CNT
nanostructure, Tafel polarization curves derived from the LSV curves were utilized (Fig. 2b)

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(the overall Tafel curves of all samples are also represented in Fig S3). It is observed that the
Ni-CNT nanostructure exhibits the lowest slope, indicating that HER has the highest kinetic
on the aforementioned electrode. It is widely accepted that HER in alkaline solution proceeds
via two main mechanisms; Volmer reaction (electrochemical hydrogen adsorption) followed
by Heyrovsky reaction (electrochemical desorption), or Volmer reaction followed by Tafel
reaction (chemical desorption):

H2O + e- → Hads + OH- (Volmer step) (1)

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Hads + H2O + e- → H2 + OH- (Heyrovsky step) (2)

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Hads + Hads → H2 (Tafel step) (3)

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In which Hads is the adsorbed hydrogen on the active surface. In general, three main states can
be assumed during HER: a) initial state (catalyst-water), b) intermediate state (catalyst- H), and
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c) final state (catalyst-H2) followed by detachment of H2 bubbles from the surface. Since the
Tafel slope is an intrinsic property, it can be used to identify the rate determining step (rds). If
the Volmer reaction (i.e. hydrogen adsorption) is the rds, the Tafel slope will be 120 mV/dec.
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If the electrochemical desorption (Heyrovsky step) is the rds, then the Tafel slope will be 40
mV/dec, whereas if the Tafel step is the rds, the Tafel slope would yield 30 mV/dec. It is seen
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that the Tafel slopes of all electrodes are close to 120 mV/dec, indicating that the Volmer step
is the rds.
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In order to evaluate the surface properties of catalysts for improving the electrocatalytic activity
of HER, studies were carried out on the electrochemical double-layer capacitance of the
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electrodes. The electrochemical capacitance can be determined by cyclic voltammetry in non-

faradic potential region at different scan rates. It is assumed that in this potential region, the
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current is associated with double-layer charging. In this region, the average of capacitive
current is proportional to double-layer capacitance, and the average variation of double layer
current density as a function of scanning rate, as follows: [57]:

Jdl,ave = (|𝑗𝑐 | + |𝑗𝑎 | )/2 = Cdl (dE/dt) (4)

In which Cdl is double-layer capacitance, and ja and jc are anodic and cathodic current densities,
respectively. Thus the plot of (|𝑗𝑐 | + |𝑗𝑎 |)/2, as a function of scanning rate, results in a straight
line with a slope equal to Cdl. The CV curves of NNCs electrode and Ni-CNT electrodes in the
non-faradic potential range at different scanning rates as well as the variation of current density

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as a function of scan rate are represented in Fig. 6. It is observed that the electrochemical
double-layer capacitance of Ni-CNT nanostructured electrode and NNCs electrode is Cdl=31.5
mF/cm2 and Cdl=12.3 mF/cm2, respectively. The electrochemically active surface area (ECSA)
was obtained from the electrochemical double-layer capacitance of the studied electrodes
divided by 20 µF/cm2 (specific capacitance of an atomically smooth metal) according to the
following equation[48]:

ECSA= Cdl/Cdl´ (5)

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Considering the average capacitance of double layer for smooth surface equal to 20µF [58],
the real surface area can be obtained by Areal= Cdl/20, and then the roughness factor can be

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obtained through dividing the real surface area by the geometrical surface area (σ=Areal/Ageo).

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The calculated results are summarized in Table S2 (Supporting information). It is seen that the
ECSA value of Ni-CNT electrode is 1575, which is higher than that of NNCs electrode (615),
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suggesting that Ni-CNT has more active sites than NNCs for HER. In addition, the ECSA of
NNCs and Ni-CNT were estimated form the integration of the Ni redox peaks. In this method,
the charges required for the formation of Ni hydroxide are divided by the monolayer charge
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per real surface area, assuming the monolayer charges of Ni is 514 µC cm-2Ni [59, 60]. The
charge required for the formation of Ni hydroxide was calculated using the CV at 10 mV s-1
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scanning rate. The CV curves of NNCs and Ni-CNT are presented in Fig. 6e. In CV curves,
the area between the potential range of -1.1 and -0.6 V vs. SCE represents the required charge
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for the formation of Ni hydroxide, according to the following formula [59]:

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Ni + 2OH- → αNi(OH)2 + 2e-1 (6)

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The estimated ECSA are 820 cm2 for Ni-CNT and 540 cm2 for the NNCs. Thus, similar to the
ECSA calculated form the capacitance estimation, it is seen that the ECSA of Ni-CNT is higher
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than that of the NNCs, suggesting the higher active site of Ni-CNT in comparison with the
NNCS.

In conclusion, the enhanced electrocatalytic activity of Ni-CNT nanostructure catalyst in

comparison with other published Ni-based catalysts can be ascribed to (i) high electrocatalytic
active surface area resulting from special nanocones structure which increase the active surface
area (ii) incorporation of CNT into NNCs and their good dispersion. The incorporation of CNT
will increase the electrical conductivity while decreasing the crystal size and consequently,
electrochemical active surface area. (iii) Highly hydrophilic nature of Ni-CNT catalyst in

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electrolyte solution results in more active sites being exposed to the electrolyte, resulting in
higher catalytic activity. (iv) In situ growth of Ni-CNT nanostructure by electrodeposition
method without any binder on Cu substrate that may hinder the kinetic of ions and electron
transport, allows direct contact of active site with electrolyte, increasing the catalytic activity.
(v) Under water aerophobicity nature of Ni-CNT nanostructure will aid in rapid detachments
of formed bubbles on the surface, consequently increasing the catalytic activity.

3.2.2. Electrochemical impedance spectroscopy

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For a more kinetically study of HER on Ni-CNT nanostructured and the NNCs electrodes as
well as interfacial behavior, their electrocatalytic activity was evaluated by EIS test at three

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different overpotentials which were determined from the LSV curves. The results are shown in

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Figs. 7 a and b. EIS has been used for studying the HER kinetic on various electrodes to great
effect. Various equivalent electrical circuits (EEC), including one-time constant model, two-
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time constant parallel model and two-time constant serial mode which are used generally for
HER studies, were tested for fitting the EIS curves. The two-time constant serial model
exhibited the best results. Here, the double- layer capacitance (Cdl) was replaced by constant
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phase element (CPE) due to the distribution of the relaxation times as a result of surface
inhomogeneities of the coatings. The used EEC is shown in Fig. 7c, and the obtained data are
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also shown in Table 2. It can be observed that the Nyquist curves include two overlapped
semicircles (the magnification of high frequency section are shown in order to represent the
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two time constant of overall EIS curves), indicating the presence of two time constant in which
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the diameter of the first semicircle at high frequency range is not changed with overpotential,
and the diameter of the second semicircle at low frequency range is decreased by increasing
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the overpotential. Decrease in the diameter of the second semicircle, as a result of increase in
overpotential, indicates the polarization resistance reduction and increase of the Volmer
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reaction rate in HER. Thus, the first time constant (CPE1, R1) can be ascribed to surface
porosity, and the second time constant (CPE2, R2) can be associated with HER kinetics.
Variation of one-time constant with overpotential indicates that the HER on nanocones is
controlled by charge transfer, and the detachment steps (Heyrosvsky or Tafel) of H2 bubbles
cannot be the rate-determining steps due to surface nanostructuring [61]. It is seen that at any
given overpotential, the R2 of Ni-CNT nanostructure electrode is lower than that of the nickel
nanocones electrode, indicating the better electrocatalytic activity of Ni-CNT nanostructure
electrode. Furthermore, by increasing the overpotential, the diameter of semicircle at low
frequency range is decreased, implying fast HER kinetics at higher overpotentials. This result

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is in good agreement with the results of polarization curves. According to Table 2, the amount
of the CPE of Ni-CNT nanostructure at all overpotentials is higher than that of the nickel
nanocones electrode; this indicates the better electrocatalytic activity of the Ni-CNT
nanostructure electrode. It is observed in many studies that the amount of CPE is decreased by
increasing overpotential due to blockage of the surface by the adsorbed hydrogen [62-64]. The
variations of CPE as a function of the overpotential of two electrodes are shown in Fig. 7d. It
is observed that the amount of CPE approximately remains constant at different overpotentials.

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This indicates that the hydrogen bubbles are not adsorbed on the electrodes surface, which is
in good agreement with the results of bubble size distribution.

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3.3. Electrocatalytic stability

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In addition to electrocatalytic activity, one other important property of cathode cathodic
materials is their electrocatalytic stability during HER. In this study, chronopotentiometry and
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CV tests were employed in order to characterize the electrocatalytic stability of Ni-CNT
nanostructure electrode, and elucidate the effect of CNT on its electrocatalytic stability. The
corresponding LSV curves both before and after 1000 cycles and chronopotentiometry curves
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are presented in Figs. 8a and b, respectively. As shown after 1000 cycles, there is no significant
change in the CV curve, indicating the appropriate electrocatalytic stability of Ni-CNT
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nanostructure electrode. Additionally, the chronopotentiometry curve of Ni- CNT

nanostructure is indicated in Fig. 8b. As illustrated, the overpotential has remained constant
E

during HER in the Ni-CNT nanostructure. This highlights the improvement in electrocatalytic
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stability by introduction of CNTs to the structure. It is anticipated that CNTs lead to an increase
in the corrosion resistance and the durability of NNCs, consequently the enhancing
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electrocatalytic stability. Furthermore, the electrocatalytic stability of the catalyst was

investigated using multistep chronopotentiometry. The chronopotentiometry measurements
AC

were carried out with current densities increasing from 10 to 100 mA/cm2 with increments of
10 mA/cm2 per 600 s (Fig 8c). It is seen that the potential rapidly changes and then remains
constant at each 600 s, indicating outstanding mass transport properties and mechanical
robustness of Ni-CNT nanostructure catalyst. In addition to CNTs, nanostructuring of the
surface can also affect the electrocatalytic stability. Majority of the incurred damage during
HER have resulted from the interaction between the bubbles and the surface or the bubble
detachment force on the surface. As shown in Fig. 3, through nanostructering of the surface,
the bubbles size is decreased dramatically in comparison to the flat surface. This would reduce
the bubble scratch/drag force, and consequently dampen damage to the surface of the electrode

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[33]. Surface roughness is an important factor that can dramatically influence the
electrocatalytic activity of an electrode. Roughness parameters can be determined by atomic
force microscope (AFM). Thus, AFM analysis can be employed in order to study the variation
of surface roughness following the stability test. In general, electrodes without obvious
morphological changes after stability test possess high electrochemical stability. In the present
work, AFM analysis was conducted both before and after the stability test, while the surface
roughness parameters were also determined before and after the stability test. The 3D images

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of Ni-CNT nanostructure electrode before and after the stability test are shown in Fig. 9.
Additionally, the surface roughness parameters are summarized in Table S3 (Supporting
information). As indicated in Fig. 9, the Ni-CNT nanostructure electrode surface is not changed

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after the stability test, implying good morphological stability during the HER test. This result

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can be deduced from Table S3 (Supporting information), which shows that the surface
roughness parameters have not been changed dramatically following the stability test. As stated
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in the previous sections, the morphological stability of nanostructure surface can be described
through the interaction between the bubbles and the electrode surface during detachment of the
bubbles. There is a relationship between the releasing size of bubbles and the adhesive force
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between the electrode surface and the bubbles [31]. The schematic of different forces during
the bubble detachment is shown in Fig. 10.
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It is seen from the schematic that two different forces are applied on the as-formed bubbles,
E

including buoyancy (Fb) and adhesive force (Fa). The adhesive force equals to the vertical
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component (Fγa) of surface tension (Fγ), according to the following equation:

Fγa = Fa = γ2(r sinα)sinα = 2rγ sin2α (7)

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Where γ is the surface tension coefficient, r is the gas bubble radius, α is the contact angle of
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bubbles and ρ is the electrolyte’s density. It is accepted that when Fa is equal to Fb, then the gas
bubbles leave the surface. Fb is defined as follow:

Fb = ρg/3r3 (4α/ -sin2 α cos α) (8)

If Fa= Fb, by combining the Eqs. 7 and 8, the relationship between the gas bubble radius and
adhesive force can be obtained as below:

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6πγ sin2 α
r=√ 4α (9)
ρgπr3 ( -sin2 α cosα)
π

Based on the aforementioned analysis and Eq. 9, it can be concluded that the releasing size of
small critical bubbles leads to the lowering of adhesive force, consequently lowering the
damage to the surface morphology of the used electrode. The literature reports that dramatic
damage has occurred on the flat surface after continuous bubble evolution due to higher

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adhesive force on the flat surface [33]. The fast detachment of gas bubbles is especially
important at higher current densities when the diffusion process may be the rate-determining

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step. Review of the literature indicates that by using the rotating electrode, gas bubbles can be

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driven out of the surface before they grow in size [65]. However, in this study, it was revealed
that by using the economical electrodeposition method, nanostructured surface could be
synthesized, and the negative effect of gas bubble size diminished.
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3.4. Corrosion behavior
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In order to make real usage out of electrocatalysts in industrial electrolysis, an electrocatalyst

should not only have high electrocatalytic stability over long period, but it should also able to
withstand intermittent power interruptions during cell shutdowns. Electrodes usually stay in
D

depolarized state due to reverse current during power interruptions. If the period of power
E

interruptions is lengthened, the electrode tends to corrode within the working electrolyte.
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Therefore, one of the other important properties of any given electrode in industrial scale is
corrosion resistance. Thus, evaluation of corrosion resistance of the electrocatalyst is essential.
CE

In literature, the electrocatalytic activity of numerous electrodes have been investigated, but
the corrosion resistance of these electrodes has not been studied in detail. In this study,
AC

primarily the effect of CNT on corrosion resistance of NNCs during showdown periods was
studied, and then the effect of electrolysis time on corrosion resistance was investigated by
electrochemical impedance spectroscopy. First, the Ni-CNT electrode and NNCs electrodes
were immersed in 1.0 M KOH solution for 120 h prior to the evaluation of corrosion resistance.
Nyquist, bode and bode-phase plots of Ni-CNT and NNCs are shown in Fig. 11 a. Furthermore,
the utilized electrical equivalent circuit (EEC) for data fitting is represented in Fig. 11c, in
which the Rs is solution resistance, CPEdl is double layer constant phase element and Rct is the
charge transfer resistance. The date extracted from EIS curves are also represented in table S4.
It is observed that the Nyquist curves only have one depressed capacitive semi-circular.

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Similarly, the bode and bode-phase plots also reveal one time constant, indicating that the
corrosion reactions of these electrodes are controlled by charge transfer. The Rct of the Ni-CNT
is 247.5 Ω/cm2, but the Rct of NNCs is 117.6 Ω/cm2, indicating the higher corrosion resistance
of Ni-CNT electrode. Increasing the corrosion resistance due to introduction of CNT in the
coating can be attributed to a decrease in charge transfer, as well as a decrease in transfer of
aggressive ions [66]. Improvements in corrosion resistance due to CNT have been reported in
literature [67, 68]. In addition, in order to evaluate the effect of electrolysis on the corrosion
resistance, constant current density of -100 mA/cm2 was applied to the cell containing Ni-CNT

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electrode as cathode and Pt plate as counter electrode. Hydrogen production was stopped after
different time periods, and the corrosion behavior of the electrode was studied by the EIS

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technique. Fig. 11c shows the Nyquist curves of the studied electrode after 24 and 120 h of

SC
hydrogen production. It is revealed that by imposing the applied current density and hydrogen
production, the charge transfer resistance is lowered form 247.5 Ω/cm2 to 153 Ω/cm2 after 24
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h electrolysis due to absence of corrosion product on the electrode surface after hydrogen
production. Furthermore, it is seen that by increasing the electrolysis time to 120 h, the charge
transfer resistance is increased to 200 Ω/cm2, indicating that at prolonged electrolysis times,
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the corrosion resistance is increased. This results is in good agreement with the results obtained
by Solmaz et al [69], which concluded that corrosion resistance of Ni-Cu electrode is increased
D

by increasing the electrolysis time. Corrosion resistance enhancement after long periods of
electrolysis can be attributed to hydrogen adsorption on electrode surface and formation of
E

metal hydrides [69].

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4. Conclusion
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To summarize, the hierarchical Ni-CNT nanostructure was fabricated by the electrodeposition

method in the electrolyte containing crystal modifier. The electrocatalytic activity, stability and
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corrosion resistance of the fabricated electrodes during HER were evaluated. The results
indicated that fabrication of 3D nanostructures, due to the introduction of crystal modifiers,
leads to increase in the active surface area and easy detachment of the formed H2 bubbles,
consequently improving the electrocatalytic activity. With the addition of CNTs into the
nanostructure, the active surface area is increased further; and due to an increase in the
electrical conductivity as well as the chemical stability as a result of introduction of CNTs, the
electrocatalytic activity, stability and corrosion resistance were enhanced. This electrode
exhibited significant electrocatalytic activity improvement in comparison with other recently

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published Ni-based none-noble metallic electrocatalyst. The authors believe that this 3D
nanostructure can open new avenues in the HER electrocatalyst studies.

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corrosion behavior of NiCu coatings with long-term electrolysis in alkaline solution,

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international journal of hydrogen energy 34(5) (2009) 2089-2094.

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Figure captions:
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Figure 1: a) FESEM images of NNCs b) Ni-CNT hierarchical structure, c) elemental mapping

of Ni, d) elemental mapping of C e) XRD pattern of NNCs and Ni-CNT hierarchical structure,
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and f) AFM image of nanocones structure.

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Figure 2: a) LSV curves of different studied electrode, in 1.0 M KOH solution, b) Tafel
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polarization curves derived from the LSV curves for different electrodes, and c) η 10, η 20 and
η100 for different electrodes.
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Figure 3: a) Schematic of the bubbles detachment behavior of different structures, b) bubbles

images at different intervals during the hydrogen evolution on nanocones structure, and c)
bubbles images at different intervals during the hydrogen evolution on the flat surface.

Figure 4: contact angle of a) Ni-CNT electrode and b) flat Ni electrode.

Figure 5: Schematic of the mechanism of electrocatalytic enhancement by introduction of

CNTs into the structure.

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Figure 6: a) CVs of Ni-CNT nanostructure, b) mean capacitive current at a specific potential

as a function of scanning rate in the non-Faradaic region at different rates of Ni-CNT, c) CVs
of NNCs electrodes, d) mean capacitive current at a specific potential as a function of scanning
rate in the non-Faradaic region at different rates of NNCs and e) CV curves of Ni-CNT and
NNCs, in 0.5 M NaOH solution with a scan rate of 10 mV/s at 298 K.

Figure 7: The Nyquist curves of a) Ni-CNT nanostructure, b) NNCs at different overpotentials,

c) used electrical equivalent circuit for fitting the EIS curves, and d) variation of CPE as a

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function of overpotential.

Figure 8: a) CV curve after 1000 cycles of Ni –CNT hierarchical structure, b)

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chronopotentiometry curves of Ni-CNT hierarchical structure and c) multistep

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chronopotentiometry curves of Ni-CNT hierarchical structure.

Figure 9: 3D AFM images of a) the as prepared Ni-CNT nanostructure surface, and b) after
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the stability test.

Figure 10: Schematic of different forces during bubble detachment on the Ni-CNT
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nanostructure surface.

Figure 11: The Nyquist, bode and bode-phase curves of a) NNCs and Ni-CNT electrode after
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120 h immersion b) Ni-CNT electrode after different period of electrolysis and c) the electrical
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equivalent circuit used for fitting the EIS curves.

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