Research Article

pubs.acs.org/acscatalysis

Covalently Connected Carbon Nanotubes as Electrocatalysts for

Hydrogen Evolution Reaction through Band Engineering
Shubhadeep Pal,† Mihir Sahoo,‡ Vineesh T. Veettil,† Kiran K. Tadi,† Arnab Ghosh,§,∥
Parlappalli Satyam,§ Ravi K. Biroju,† Pulickel M. Ajayan,⊥ Saroj K. Nayak,*,‡
and Tharangattu N. Narayanan*,†
†
TIFR-Centre for Interdisciplinary Sciences (TCIS), Tata Institute of Fundamental Research, Hyderabad 500075, India
‡
School of Basic Sciences, Indian Institute of Technology, Bhubaneswar, Odisha 751013 India
§
Institute of Physics (IoP), Bhubaneswar, Odisha 751005, India
See https://pubs.acs.org/sharingguidelines for options on how to legitimately share published articles.

∥
Department of Physics, Indian Institute of Technology, Kharagpur 721302, India
Downloaded via HEBREW UNIV OF JERUSALEM on September 20, 2018 at 16:01:57 (UTC).

⊥
Department of Materials Science & Nanoengineering, Rice University, Houston, Texas 77005-1892, United States
*
S Supporting Information

ABSTRACT: Controlled assembly of mesoscopic structures

can bring interesting phenomena because of their interfaces.
Here, carbon nanotubes (CNTs) are cross-coupled via a C−C
bonding through Suzuki reaction resulting in three-dimensional
(3D) CNT sponges, and these 3D CNTs are studied for their
efficacy toward the electrocatalytic hydrogen evolution reaction
(HER) in acidic mediumone of the promising methods for
the production of a renewable energy source, hydrogen. Both
single and multiwall CNTs (SWCNTs and MWCNTs) are
studied for the development of 3DSWCNTs and 3DMWCNTs, and these 3D CNTs are found to be HER active with small
reaction onset potentials and low charge-transfer resistances unlike their uncoupled counterparts. First-principle density
functional calculations show that the combination of electron acceptor and donor bonded to the CNT network can provide a
unique band structure modulation in the system facilitating the HER reaction. This study can provide possibilities for band
engineering of CNTs via functionalization and cross-coupling reactions.
KEYWORDS: hydrogen evolution reaction, carbon nanotubes, electrocatalysis, Suzuki coupling, density functional theory,
band engineering

1. INTRODUCTION 4H+ → 2H2) in acidic medium, is tested. The coupling is found

Structural integrity, compactness, and favorable mesoporosity
of carbon nanotubes (CNTs) have fascinated researchers for
their applications in electronic interconnections and electro-
chemical energy storage/conversion devices.1,2 Attempts
toward the formation of covalent junctions among CNTs, to
make their three-dimensional (3D) seamless structures, have
been intensely pursued in the past few years, and a few of these
attempts have succeeded to bring large-scale connectivity
among CNTs.3 The implementation of boron-, sulfur-, or
phosphorus-based atomic welding using chemical vapor
deposition is one such attempt reported by the authors to
deliver covalently connected low-density CNT sponges.4
Furthermore, considering multiwalled CNTs (MWCNTs) as
analogues of compact organic macro-molecules, the authors
have reported the interconnection of individual MWCNTs via
the Suzuki reaction assisted C−C coupling.5
In the present study, the theoretical possibility for the
formation of Suzuki-coupled CNTs via a benzene molecule is
verified, and the impact of such a coupling in an electro-
chemical reaction, hydrogen evolution reaction (HER, 4e− +
to be changing the density of states (DOS) of individual CNTs
in favor of the HER reaction, and it also improves the
adsorption of the H+ ions, resulting in an overall improvement
in the electron-transfer kinetics. Heterogeneous electron
transfer (HET) studies on the coupled CNTs are conducted
to check the veracity of the theoretical predictions, and the
Suzuki coupling is achieved on different CNTs, including two
different types of metallic MWCNTs (different dimensions:
both longer and shorter and also CNTs obtained from two
different vendors) and semiconducting single-wall CNTs
(SWCNTs, (7,6)). These studies are in tune with the
predictions that the coupling can improve the HET kinetics
of HER. Further in this study, the roles of residual impurities
are taken into account by successive washing of the samples
and further blocking the metallic catalytic sites using potassium
thiocyanate (KSCN).6
Received: January 5, 2017
Revised: March 7, 2017
Published: March 8, 2017

© 2017 American Chemical Society 2676 DOI: 10.1021/acscatal.7b00032

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It has been unequivocally established in the literature that
functions of CNTs in catalysis is either as “true catalysts” or
catalyst supports.7 However, electrocatalytic activities of metal-
free CNTs are highly debated in the literature.6,8 Metals are
indispensable for the growth of CNTs, and their complete
removal from CNTs even after multiple washing processes is
questionable.9 Hence residual impurities impart the catalytic
efficiency of most of the CNT-based “metal-free” catalysts
reported.10 However, there is a huge demand for the
replacement of precious-metal- and noble-metal-based conven-
tional catalysts for the viable use of sustainable futuristic energy
systems. Recently, Jiang et al. reported that residual metallic
impurities become pronounced on CNTs with two to three
walls, whereas the effect of metallic impurities is much lower in
SWCNTs/MWCNTs.6 Furthermore, they have proven that the
intrinsic activity of CNTs is related to the quantum properties
such as charge transfer via tunneling. It is in general agreed that
the apparent increase in the electrochemical activities of nitric
acid treated SWCNTs is due to the presence of edge like tips
produced via the cutting of the CNTs during the acid
treatment.11 However, such effects are negligible in MWCNTs,
and hence, metal-free MWCNTs will be inactive in electro-
catalytic reactions. The role of oxygen-containing functional
groups in electrocatalysis of CNTs was studied by Gooding et
al., and they showed that the oxygenated species (particularly
−COOH) in SWCNTs render favorable electrochemical
properties.12,13 Subsequently, however, it was shown that
oxygenated species in graphite and MWCNTs slows down the
HET rates, and the enhanced activities reported by others
might be caused by the iron-based impurities present in the
samples.13 The enhanced activity of oxygenated metallic
SWCNTs toward oxygen reduction reaction was reported to
be the result of formation of strained sites formed during the
oxidation treatment.14 Heteroatom-doped CNTs (e.g., boron,
nitrogen) and other graphitic systems were also reported to
enhance catalytic activities toward various reactions because of
the modification of spin and charge density distributions of
adjacent carbon atoms.15
Here a new insight into the manipulation of electrocatalytic
activities of CNTs is brought by the covalent C−C coupling
modification through Suzuki reaction. Electrophilic (halogen-
ation) and nucleophilic (boric acid functionalization) “metal-
free” CNTs were developed via chemical functionalization, and
palladium assisted cross-coupling reaction is employed to make
interconnected CNTs. (Note: Metals are removed by
successive washing in nitric acid at elevated temperatures (60
°C), and the residual metals (Fe, Co, and Ni) are quantified in
parts per million (ppm) level.) The chemical treatment resulted
in a stable suspension of coupled-CNTs without their
aggregation through extended π−π stacking, another challenge
in the practical applications of CNTsthe lack of surfactants-
free inks.16 The HER catalytic activities of CNTs on each stage
of functionalization is also tested. Though the effect of various
functional groups in CNTs toward catalysis is reported
previously,14 covalently linked CNTs are not studied for their
catalytic efficacies. Furthermore, a generalized picture toward
the modification of catalytic activities of CNTs by coupling,
irrespective of their dimensional variations and electronic
properties, is depicted here. The theoretical study presented
here also shows the possibilities of enhancing the catalytic
activities of CNTs through functionalization via band engineer-
ing but without adversely affecting the electronic properties of
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CNTs, another bottleneck in the development of CNT-based
devices.17
2. EXPERIMENTAL SECTION
2.1. CNT Purification and Suzuki Coupling. As-
purchased CNTs (100 mg) are refluxed in a round-bottom
flask containing nitric acid (HNO3, 5 mg/mL), at a temperature
of ∼120 °C for purification. Two types of MWCNTs are used
for the present study. The MWCNTs obtained from Cheap-
Tubes.com have a 10−30 μm length and a 20−30 nm diameter,
and those obtained from Sigma-Aldrich have a 5−7 μm length
and a 110−170 nm diameter. SWCNTs are obtained from
Sigma-Aldrich and have a diameter of 0.7−1.1 nm and chirality
(7,6). SWCNT (7,6) (Sigma-Aldrich, no. 704121) was
synthesized using a Co−Mo catalyst containing <10 wt %
metal impurities (>90 wt % carbon). All the CNTs are treated
with HNO3 to remove the residual impurities within the tubes,
and this will eventually functionalize the walls with −COOH
and −OH groups. Further functionalization steps and Suzuki
coupling procedure are as follows:5 The functionalized tubes
are dispersed and stirred in 50 mL of thionylchloride (SOCl2)
in 2 mL of 1,2-dichlorobenzene (C6H4Cl2) solvent at 80 °C for
1 day. This will leads to the halogenation of CNTs
(chlorination). A portion of the chlorinated CNTs are further
treated with benzene 1,4-diboronic acid (C6H4[B(OH)2]2) via
Suzuki reaction. In this reaction, 40 mg of chlorinated tubes is
mixed in 30 mL of toluene (C7H8) containing 160 mg of
cesium carbonate (Cs2CO3) and 20 mg of C6H4[B(OH)2]2
under inert (N2) atmosphere. After 1 h of mixing, 30 mg of
tetrakis (triphenylphosphine) palladium (0) (Pd[(C6H5)3P]4)
is added to this mixture. This mixture is kept under stirring at a
temperature of ∼100 °C for 5 days. A spongy-like CNT residue
is obtained after this reaction protocol (a photograph of the
residue is shown in Supporting Information Figure S1), and
this is similar to that reported by the authors previously for
MWCNTs sponges (here called 3D SWCNT/3D MWCNT).5
The 3D material is washed with methanol (CH3OH) and type I
DI water for several times via vacuum filtration. This will help
to remove the unreacted chlorinated tubes through water
washing. Then the 3D CNTs are thoroughly sonicated in
dimethylformamide (DMF, C3H7NO) and isopropyl alcohol
(IPA, C3H7OH) mixture (1:1) to remove the residual organic
components. The 3D CNTs are dried and treated with water
and then dispersed in water/IPA mixture (3:1) for further
analysis.
2.2. Structural Characterization. CNTs are characterized
using JEOL JEM 2010 field emission gun transmission electron
microscope (TEM) with an accelerating voltage of 200 kV.
Residual metal levels in the CNTs are analyzed by ICPE- 9820
instrument from Shimadzu company. FTIR is measured in
transmittance mode on a Bruker (model: Alpha) spectrometer.
Renishaw inVia micro Raman spectrometer with 532 nm and
633 nm laser excitations is used at 50× objective lens for 10 s
acquisition.
2.3. Electrochemical Studies. All the electrochemical
studies are carried out at room temperature using a Biologic
potentiostat model SP-300. Electrochemical experiments are
conducted in three-electrode systems using Ag/AgCl (saturated
KCl) as reference electrode and platinum (Pt) as counter
electrode (graphite is also used as counter electrode to check
the possibilities of Pt effects via the Pt leaching out during the
study while using a Pt counter electrode, and similar results are
obtained). In order to prove this, all the electrochemical
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Figure 1. (A) Schematic of the Suzuki coupling of CNTs (structures developed using ChemDraw, theoretically stabilized structure is shown in the
later section). (B) TEM image of an uncoupled crossed CNTs (MWCNTs). (C) Suzuki coupled MWCNTs (3D MWCNT, small particles
decorated on MWCNTs are Pd nanoparticles); inset shows the TEM image of a washed 3D MWCNT which removed most of the Pd nanoparticles
(unwashed 3D MWCNT junctions are shown in Supporting Information). (D) High-resolution TEM image of a T-junction of 3D MWCNT
(washed) showing the continuous lattice fringe formation due to covalent coupling. (E) MWCNT dispersion in water/IPA mixture (3:1) after a
week. (F) 3D MWCNT dispersion in water/IPA mixture (3:1) after a week. (G,H) TEM images of the coupled SWCNTs (3D SWCNT).

impedance spectroscopy (EIS) studies are shown using a
graphite counter electrode. The working electrode is a modified
3 mm glassy carbon electrode (GCE), and the electrolyte used
is 0.5 M H2SO4. The working electrode is polished thoroughly
by an alumina polishing pad with aluminum nanoparticle (<50
nm) paste. Then the electrode has been sonicated in ethanol
for 5 min to remove the surface impurities. After drying the
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electrode in an IR lamp, the CNT ink has been coated on the
prepared electrode. The catalyst ink has been prepared by
sonicating 2 mg of the material in 1 mL of water/IPA mixture
(3:1). Other intermediate/control material inks are also
prepared in the same way. Three microliters of this ink is
drop casted on 3 mm GCE for all electrochemical measure-
ments. GCE has a geometrical surface area of ∼0.07 cm2, and
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Figure 2. Micro-Raman spectra of (A) SWCNTs, MWCNTs and their 3D structure. (B) Comparison of SWCNTs and 3DSWCNTs at 532 nm
laser. (C) Comparison of SWCNTs and 3DSWCNTs at 633 nm laser. (D) 3D SWCNT upon heating and cooling using a heating cell and in situ
Raman data collection. The RBM modes of 3D SWCNT show reversible changes until 450 °C.
hence, 85.7 μg cm−2 material is deposited for each measure-
ment (loading kept constant in all the types of samples). The
modified electrodes are dried in ambient condition. Prior to the
electrochemical reaction studies, the electrodes are preactivated
in HER solution in a potential window of 0 V to −1 V (Ag/
AgCl) for 25 cycles in a scan rate of 50 mV/s. The linear sweep
voltammetry (LSV) is taken in a scan rate of 10 mV s−1. All the
plots are then converted to a reversible hydrogen electrode
(RHE) as reference.
2.4. Theoretical Studies. Perdew−Burke−Ernzerhof
(PBE)18,19 exchange correlation is used for the structure
stabilization, and the projector augmented wave (PAW)
scheme is used to study the atomic and electronic structure
of CNT network structures.20 The basis set was expanded with
a kinetic energy cutoff of 600 eV. First, a self-consistent
calculation was done to obtain converged charge density, and
then DOS and band-structures are calculated using that charge
density. A 1 × 1 × 12 grid within the Monkhrost-Pack scheme
was used to sample the Brillouin zone for self-consistent
calculation.21 Gaussian smearing is approached with smearing
width 0.2 eV. A higher k-point mesh of 1 × 1 × 24 was used for
calculation of DOS. The dipole correction is included for a
Coulomb interaction because of the presence of H+ ion. All the
calculations are done using Vienna Ab initio Simulation
Package (VASP).22,23
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3. RESULTS AND DISCUSSION
3.1. Structure and Chemical Composition of the 3D
CNTs. The Fourier transform-infrared (FT-IR) spectra of each
sample are shown the Supporting Information Figure S2, and
the functional groups are identified. This shows the
functionalization of the samples after each step of the chemical
treatments, as predicted. It should be noted that the 3D
MWCNT produced from both the Cheap Tubes and Sigma-
Aldrich are characterized and subjected to HER studies,
whereas the data from Cheap Tubes are given in the main
manuscript (that of Sigma-Aldrich are shown in the Supporting
Information). Additionally, transmission electron microscopic
(TEM) images in the main manuscript are those from Sigma-
Aldrich, and that of Cheap Tubes are provided in the
Supporting Information. It has also to be noted that all the
data from different CNTs (also different batches of synthesis)
have given similar results.
The coupling reaction is schematized in Figure 1A. The
coupled structure is theoretically verified in the later section.
The TEM image of bare MWCNTs is given in Figure 1B (also
Figure S1A,B). It is evident from the image that one tube is
tying over the other one while there is no chemical coupling
between them. Figure S1B shows the lattice plane discontinuity
and phase contrast difference in the uncoupled and crossed
CNTs. However, Figure 1C shows a CNT junction after Suzuki
coupling. The small nanoparticles decorated are that of Pd, and
an extensive washing using diluted HNO3 can remove these
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Figure 3. (A,B) Linear sweep voltamograms (LSVs, in three electrode system, Pt as counter electrode, and Ag/AgCl (sat. KCl) as reference
electrode) of different SWCNTs and MWCNTs, respectively. LSVs are performed in 0.5 M H2SO4 with a scan rate of 10 mV/s. The onset and over
potentials (@ current density 10 mAcm−2) are marked. The standard samples such as Pd/C and Pt/C are also compared in the panels (the LSVs of
the same samples before/after “poisoning” are shown in the Supporting Information). (C,D) Represent electrochemical impedance spectra (EIS) of
SWCNTs and MWCNTs, respectively. The EIS are conducted in 0.5 M H2SO4 using graphite as counter electrode.

nanoparticles (Figure 1C inset, shows such a washed junction
which is devoid of all the nanoparticles). Various parts of these
washed and unwashed samples of 3D MWCNT developed
using both the types of MWCNTs are shown in Figure S3.
These results indicate that interconnected CNTs can be formed
after the Suzuki cross-coupling reaction, and the Pd nano-
particles used can be largely removed from the scaffold using
extensive washing. Furthermore, a high-resolution (HR) TEM
image of the washed junction is shown in Figure 1D. It can be
inferred from this image (also from Figure S3I,J) that the lattice
planes are continuous in the junction, unlike that found in
uncoupled CNTs, indicating the formation of a C−C coupling.
The effect of functionalization of CNTs via the coupling
reaction makes it dispersible in the water/IPA mixture, and a
stable ink of 3D MWCNT after a week’s aging is shown in
Figure 1F. The MWCNTs (−COOH functionalized) shown in
Figure 1E indicate that bare CNTs are not dispersible in this
mixture. Photographs of the CNT dispersions of the
intermediate steps functionalization are provided in Supporting
Information Figure S4, and it indicates the high stability of 3D
MWCNT in water/IPA mixture. This is an added advantage of
this coupling reaction which leads to highly stable inks; those
are otherwise technically challenging for the practical use of
CNTs in electrode development. The residual metals present in
the washed samples are analyzed using inductively coupled
plasma-atomic emission spectroscopy (ICP-AES), high-reso-
lution transmission electron microscopy (HRTEM), selected
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area electron diffraction (SAED, using TEM), and energy-
dispersive spectrum (EDS) analysis using a EDS (EDAX)
detector attached to scanning electron microscope (SEM).
ICP-AES analysis data is given in Table S1, and it shows that
though there is negligible variation in the metal contents from
batch to batch and also CNTs obtained from different vendors,
all the amounts are limited to <50 ppm. The EDS of purified
3D SWCNT is shown in the Supporting Information Figure S5.
The spectrum shows the absence of any metallic impurities
(presence of carbon and oxygen are shown) including Pd in the
sample, and the corresponding SEM image of the sample is
shown in the inset of EDS spectrum. The TEM images of 3D
SWCNT are shown in Figure 1G, H (TEM, HR-TEM,
respectively). The interconnectivity among nanotubes is
ensured in 3D SWCNT too. The black spots in the HRTEM
images are identified as trace Pd metals, as shown in the
Supporting Information Figure S6.
Micro-Raman spectroscopy is conducted on various samples
to know about the coupling induced changes in the vibration
modes. Figure 2A summarizes the Raman spectra of various
samples taken at 24 °C (297 K) using a 633 nm laser excitation
(all the measurements are carried out with same spot size
(N.A.), intensity, and acquisition time, and all the samples are
prepared in the same solution drop casting and drying method
to reduce the bundling effects24).
The important vibration bands are marked in Figure 2A.25
3D SWCNT shows an enhanced and broadened D band,
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indicating the enhancement in the out-of-plane bending mode
induced D-band phonon.26 The MWCNTs have considerable
D-band in the pristine form itself, and the 3D MWCNT did not
show a considerable change in the D band phonon; however, a
drastic change in the 2D band is observed, indicating the roles
of induced defects upon functionalization and coupling. The in-
plane anisotropic stretching modes (G+ and G−) of SWCNTs
are found to be not affected after coupling. This is in agreement
with the theoretical and experimental reports that the inter- or
intratubular interactions will not affect the frequencies of C−C
vibration,27 but the radial breathing mode (RBM) of SWCNTs
can be affected by bond softening or bundling.28 Though no
theoretical study is available on the effect of covalent
interactions on the RBM modes of SWCNTs, a considerable
shift in the resonance peak can be expected from inter/
intratubular interactions, which are due to the changes in their
electronic transitions.27 The (7,6) SWCNTs have the RBM
expected to be originated at ∼261 cm−1, and this RBM is
observable in Figure 2B with the excitation of 532 nm (2.33
eV). However, a drastic drop in the intensity is observed after
coupling, and this can be due to the considerable shift in the
resonance of those coupled SWCNTs. The Raman studies are
also conducted at 633 nm excitation (1.96 eV), where the (7,6)
nanotubes show a resonance energy transfer due to E22
electronic transition.29 The Raman spectrum of SWCNTs
show two distinct peaks, and this may be due to the resonance
Raman scattering of two different chirality nanotubes, (7,6) and
(7,5), where both of them have similar E22 transitions.27,30
Furthermore, a drastic drop in the intensities of both chiralities
are observed after coupling. This can be again due to the
changes in the resonance frequency of a large fraction of
nanotubes after coupling. To further verify that the existing
resonant peaks in Raman spectra are due to uncoupled/barely
coupled SWCNTs, temperature-dependent Raman studies and
their reversibility are tested in the range of 297−723 K. The
results are shown in Figure 2D. The RBM modes are highly
temperature-dependent, and the softening of the C−C bond
upon heating can reversibly change the line shape along with
the intensity. The heating of 3D SWCNT shows a reversible
change in both the line shape and intensity of 261 cm−1 RBM
band, indicating the softening of the C−C bond predicted and
observed for individual/bundles of SWCNTs.31 Hence, Raman
studies on SWCNTs and 3D SWCNT show a similar variation
in RBM line shape and intensity upon heating, though the
coupling drastically reduced the integrated RBM intensities. In
MWCNTs, the RBM mode associated with a smaller diameter
inner tube can be observed only if a good resonance condition
is established. In general, the RBM signal from large diameter
tubes is too weak to be observable, and hence, the ensemble
average of inner tube diameter broadens the signal in
MWCNTs. Thus, RBM is not observable in the case of
MWCNT Raman spectrum.
3.2. Electrochemical HER Studies. Figure 3A shows the
HER LSVs of various bare SWCNTs. It has been reported that
SWCNTs are catalytically active toward HER in acidic
medium.32 The onset potential for the reaction is found to
be ∼ −0.6 V (Figure 3A), and it matches well with earlier
reports.26 The acid treatment reduced the onset potential to
−0.45 V, in tune with the earlier reports that acidic treatment
(−COOH functionalization) can cut the SWCNTs to
introduce more nanographitic catalytically active sites.33 This
is further established by the fact that chlorination could not
alter the onset potential of the carboxylated SWCNTs,
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indicating that simple halogenation did not improve the
activity. The 3D SWCNT has HER onset potential of ∼
−0.23 V (∼233 mV less than that of functionalized SWCNTs)
and an overpotential at 10 mAcm−2 current density −0.49 V
(this is ∼ −111 mV less than that of functionalized SWCNTs).
A comparison with the benchmarked palladium-supported
carbon (Pd/C, 20 wt %, Sigma-Aldrich) is also shown in the
figure, where the reaction starts at ∼0 V with a sluggish kinetics
as inferred from the slow increase in the current density over
the potential sweep. The role of unwashed Pd or any other
trace metals (though if there is any, it will be present in other
functionalized samples and bare CNTs too) can be studied by
blocking the metal sites by KSCN (−SCN group can block the
catalytically active sites of metals),6 and this is termed as
“poisoning”. In order to show the effectiveness of poisoning,
the Pd/C modified working electrode is poisoned with KSCN
by dipping the electrode in 3 M KSCN. The electrode activity
before and after poisoning is shown in the Supporting
Information Figure S7. The CVs are taken with the Pd/C
modified electrodes before and after −SCN poisoning. It can be
seen that the poisoning completely blocks the activities due to
Pd. Further, the activities of the SWCNTs before and after
poisoning is carried out in a similar way, and the results are
shown in the Supporting Information Figure S8. It is clear from
this experiment that the poisoning of the CNTs did not affect
the activity of nanotubes toward HER. It is also found that the
raw palladium catalyst (Tetrakis) is not at all HER active, and
hence, residual Tetrakis will not contribute to any HER
performance (Figure S9).
The HER activities of various MWCNT samples are shown
in Figure 3B. MWCNTs are electrochemically inactive,34 and
the presented data also reveals the inactiveness of MWCNTs
toward HER catalysis. The acid treatment or chlorination also
could not bring the HER activity to MWCNTs. This further
shows that the acidic treatment cannot break/cut MWCNTs as
it happened for SWCNTs, and the activity of SWCNTs after
acid treatment is mainly due to the exposed nanographitic
surfaces. However, the intermediate residue of Suzuki coupling,
where the chlorinated CNTs are partially converted to boronic-
functionalized ones, named MWCNT-PhB(OH)2, shows the
HER activity with an onset potential of ∼ −0.3 V. This
activeness is due to the partial coupling of MWCNTs during
the transmetalation. The 3D MWCNT has an augmented HER
activity with an onset potential of ∼ −0.15 V and an
overpotential at 10 mAcm−2 current density of −0.3 V. The
performance of benchmarked HER catalyst Pt/C is also shown
for comparison, and its characteristic features (onset and over
potentials) match well with the reports.35
The inherent activity of an electrocatalysts can be obtained
from the exchange current density (j0). Exchange current
density is an important kinetic parameter in electrocatalysis
which is related to the rate of electron transfer under
equilibrium conditions (i.e., at zero overpotential). The
magnitude of the exchange current density can influence the
rate of the electrochemical reaction at other potentials.29 The
Tafel equation which depicts the dependence of steady-state
current densities on a variety of overpotentials can be used to
calculate the exchange current density. The linear portion of the
Tafel plot is fit to the Tafel equation: μ = a + b log j; where b is
the Tafel slope, μ is the over potential, and j is the current
density. An efficient catalyst will have high exchange current
density.36 In our study, the exchange current density for
3DSWCNT and 3DMWCNT are found to be 151 and 0.52
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Figure 4. (A) Schematic structures of (top) side view of carbon nanotubes interconnected with benzene molecule, (bottom) top view of carbon
nanotubes interconnected with benzene molecule. The hydrogen ion (H+) ion is attached to the CNT on the top position. The hydrogen ion (H+) is
attached to the surface of CNT (yellow: carbon atom; green: hydrogen atom). (B) Band structure (left) and density of states (dos) of benzene
molecule. (C) Band structure (left) and density of states (dos) of a metallic CNT. (D) Band structure and density of states of benzene chemically
connected by two metallic CNTs. (E) Band-structure and density of states (dos) of single-CNT with H+ ion. (F) Band structure and density of states
of chemically connected two CNTs with benzene in the presence of H+ on the CNT surface.

which are ∼50 and 8 times higher than that of the their bare
counterparts in both the cases, respectively. This indicates that
the coupling effectively enhances the kinetics of charge transfer
in both the cases.
To further probe the feasibility of 3D SWCNT/MWCNT
toward HER, EIS studies are conducted in HER conditions at a
potential −203 mV (vs RHE), and the results are shown in
Figure 3C,D (see also Supporting Information Figure S10).
The Rct values observed after fitting Randles plot for
3DSWCNT, SWCNT, 3DMWCNT, and MWCNT are found
to be 420 Ω, 16.85 kΩ, 70 Ω, and 1.69 kΩ, respectively. The
lower Rct values after coupling indicate the augmented electron
transfer kinetics of 3D SWCNT and 3D MWCNT in
comparison to their respective individual CNTs toward HER.
Further, comparison of LSVs having current density calculated
using geometrical area and electrochemical surface area
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(calculated using Randles-Sevcik equation), catalyst loading
dependent LSVs and EIS at −203 mV (vs RHE) are carried out
to confirm that the observed augmented HER activity is due to
the coupling rather than high loading or nonfaradic capacitance
contributions. The details are shown in Supporting Information
Figure S11, and these studies confirm the role of 3D CNTs in
HER performance in comparison to their uncoupled ones. The
stability of the electrocatalysts toward the catalytic reaction is
another concern in many catalysts when they are used in real-
world applications. In order to study the long-term perform-
ance of 3D CNTs, chronoamperometric studies are conducted
at −0.4 V, and results are shown in Figure S12. Both
3DSWCNT and 3DMWCNT show stable HER current density
for more than 20 h, indicating stability of these junctions.
3.3. Theoretical Investigations. In order to provide the
roles of linkage molecule as well as addition of hydrogen ion to
DOI: 10.1021/acscatal.7b00032
ACS Catal. 2017, 7, 2676−2684
ACS Catalysis
the CNT network structure, a first-principles computational
scheme using density functional method is conducted.37,38
Here, CNTs having chirality (5,5)-metallic are used to make
the stable bonded structure through the benzene molecule, in
order to mimic the experimentally explained connected CNT
structures. It is to be noted that CNTs with different chirality
provided similar results. Then the hydrogen ion (H+) is added
subsequently to the covalently bonded CNT structures. A
schematic of the structure is shown in Figure 4A.
On the basis of relaxed geometry of the CNT coupled system
described above, the adsorption energy between coupled CNTs
and benzene molecule is calculated as 12.5 eV, suggesting
strong chemical bonding between CNTs and benzene molecule
(this is found to be the most stable configuration compared to a
single CNT-functionalized benzene system). The equilibrium
distance between the extreme end C atom of benzene and
nearest C atoms of CNT was calculated as approximately 1.8 Å
after optimization. Further, the H+ ion on the top of C atom of
CNT was found to be the most stable configuration at a
distance of 1.16 Å.
In order to understand the atomic level picture of the role of
covalently connected CNTs in an augmented HER reaction,
electronic structures of individual CNTs and the intercon-
nected CNTs with and without hydrogen are studied. The band
structures and density of states (DOS) of different systems are
analyzed in detail. The insulating and metallic properties of
benzene and CNTs (5 × 5) are shown in Figure 4B and C,
respectively. Figure 4D shows the band structure CNTs
interconnected with benzene molecule. The following things
are noticed from these calculations: in the case of coupled
CNTs, a reduced number of states appeared near the Fermi
energy as compared to pure CNT. In addition, the band near
the Fermi energy has a lower dispersion, and the orbital analysis
suggests that the band has a much stronger component derived
from the benzene molecule. Here the attached benzene
molecule acts as a charge donor, and charge transfer occurs
from the molecule to the nanotubes. This will result in bands
due to CNTs being pushed away from the Fermi energy.
However, when the H+ ion is added to pure CNT (5,5) (Figure
4E), the charge transfer occurs from coupled CNTs to the H+
ion. In this case, Fermi energy is shifted toward the valence
band, indicating that H+ ions works as a charge acceptor.
When H+ ion is added to the chemically cross-linked CNTs
through benzene, the above-mentioned effect is more
pronounced, as shown in Figure 4F. Indeed, one notices here
that the band dispersion becomes similar to that of pristine
metallic CNTs as it appears near the Fermi energy in this
coupled system in the presence of H+ ion. In addition, a higher
density of states near the Fermi energy is clearly observed for
this structure. Both these outcomes make the system better for
the HER reaction in terms of providing a greater number of
density states for electron transport for the HER reaction while
providing an excellent surface for hydrogen ion adsorption.
Furthermore, calculation is conducted to find the total
energy with linker parallel and perpendicular with CNT axis
because various types of CNT junctions are reported in the
previous work.5 The total energy in the case of parallel linker is
found to be −789.04 eV, whereas in the case of perpendicular
linker, it is −793.93 eV. Hence, the configuration with the
perpendicular linker is energetically more stable than the
system with a parallel linker. This study has also extended to
the possibilities of more than one linker molecule in the
coupling reaction (see Supporting Information Figure S13). A
2683
Research Article
second linker is placed at a distance of 2.5 Å and parallel to
another linker (linkers are covalently coupled among the
nanotubes), as it is viewed in Figure S13 in Supporting
Information. It is found that additional linkages increase the
number of bands and hence DOS, and a linear dispersion
occurs at Fermi energy due to Pz orbital as shown in Figure
S13B,C. Hence multiple linkers can also augment the HER
kinetics.
4. CONCLUSIONS
SWCNTs and MWCNTs are subjected to Suzuki coupling
reactions resulting in the formation of 3DSWCNT and
3DMWCNT sponges. Detailed electron microscopy studies
are conducted to prove the formation of CNT junctions, and an
extensive washing technique rendered removed the residual
metallic impurities and Pd nanoparticles from the CNT
network (or limited their amount to <50 ppm). HER reaction
studies in acidic medium showed that coupled 3D CNTs have
enormous HER activities (3DSWCNT has reaction onset
potential of ∼ −0.23 V, which is ∼233 mV less than that of
functionalized SWCNTs, and 3DMWCNT has the same value
of ∼ −0.15 V, where MWCNTs do not show any activity)
compared to their uncoupled ones. The DFT studies show that
the benzene coupled CNTs are forming stable structures with a
resulting chirality in the relaxed structures. This C−C coupling
results in the band engineering of CNTs where a metal to
insulator like transition is observed. The coupling bring H+ ions
close to the CNT sites, and a further transition from insulator
to metal-like is observed in the presence of H+ ion in the
coupled CNTs, giving an augmented charge transfer process
from CNTs to H+ ion, in tune with the experimental
observations where enhanced HER properties in acidic medium
are observed in Suzuki-coupled CNTs. This study not only
opens the possibilities for the design of CNTs-based new
catalysts for electrochemical reactions but also brings a unique
opportunity for the engineering of CNT band structures by
selective functionalization and cross-coupling reactions.
■
ASSOCIATED CONTENT
*
S Supporting Information
The Supporting Information is available free of charge on the
ACS Publications website at DOI: 10.1021/acscatal.7b00032.
Photographs and TEM images of Suzuki coupled CNTs,
FTIR data of functionalized CNTs, CVs and LSVs of
various samples toward HER reaction, and stability of 3D
CNTs in HER reaction (PDF)
■
AUTHOR INFORMATION
Corresponding Authors
*E-mails for T.N.N.: tnn@tifrh.res.in, tn_narayanan@yahoo.
com.
*E-mail for S.K.N.: nayaks@iitbbs.ac.in.
ORCID
Kiran K. Tadi: 0000-0002-8647-9379
Ravi K. Biroju: 0000-0002-4152-7509
Tharangattu N. Narayanan: 0000-0002-5201-7539
Notes
The authors declare no competing financial interest.
DOI: 10.1021/acscatal.7b00032
ACS Catal. 2017, 7, 2676−2684
ACS Catalysis Research Article

■ ACKNOWLEDGMENTS
The authors thank the TIFR-Centre for Interdisciplinary
Sciences (TCIS), Tata Institute of Fundamental Research for
the financial support. S.K.N. and M.S. would like to thank
Centre of Excellence on Novel Energy Materials supported by
Ministry of Human Resources, India.
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2684 DOI: 10.1021/acscatal.7b00032

ACS Catal. 2017, 7, 2676−2684