2021 IEEE 2nd KhPI Week on Advanced Technology (KhPIWeek)
Hydrogen Interaction with Tungsten Disulfide
Nanostructures
Alex Laikhtman*, Alla Zak
Physics Department, the Faculty of Sciences
Holon Institute of Technology (HIT)
Holon, Israel
alexl@hit.ac.il
Julio A. Alonso
Department of Theoretical, Atomic and Optical Physics
University of Valladolid
Valladolid, Spain
2021 IEEE 2nd KhPI Week on Advanced Technology (KhPIWeek) | 978-1-6654-1205-6/21/$31.00 ©2021 IEEE | DOI: 10.1109/KHPIWEEK53812.2021.9570070
Abstract—We report here on hydrogenation of inorganic
nanostructures of WS2 by various hydrogenation methods. Our
methodology of hydrogen activation by cold plasma, either
microwave or radiofrequency, resulted in substantial increase of
the hydrogen adsorption rate. We elucidate the chemical state of
so adsorbed/absorbed hydrogen by both experimental methods
and using theoretical modelling with density functional theory
(DFT). The experimental results revealed that hydrogen is mostly
physisorbed it also confirmed its stability at the room temperature
conditions along with relative simplicity of controlled release by
moderate heating. The DFT calculations were in excellent
agreement with the experiment showing the physisorbed state is
energetically favorable in the case of surface adsorption in one or
several layers. The DFT predicted some increase of the interlayer
distance with no adverse influence on the energy balance. This
phenomenon opens a new gate to implant foreign species inside the
nanoparticles. The preliminary experimental results of Ga
implantation following hydrogenation are excellent agreement
with these DFT predictions.
Keywords—inorganic nanoparticles; hydrogen storage; density
functional theory
Substantial progress has been made in the field of hydrogen
storage in solid state inorganic materials, and in particular
nanostructures and nanoparticles since the first reports on this
subject [1,2]. Some of us (AZ) largely contributed to the
development of the scaled-up synthetic process for production
of high purity inorganic nanotubes (INT)-WS2 phase and
inorganic fullerene-like (IF) nanostructures [3,4], which
enables to obtain up tens of kg of these materials per day. So
available large quantities of INT and IF of WS2 led to a recent
research bustle of these novel nanomaterials in both academia
and industry, suggesting numerous applications in various
fields ranging from tribology to photoelectronics and nano-
optics. [5-8]. One of the possible applications of WS2
nanoparticles is to consider them as hydrogen-storage media
owing to their layered and packed structure and high thermal
stability.
In this work we review our recent achievements in using
various methods to hydrogenate nanostructures of WS2 and to
978-1-6654-1205-6/21/$31.00 ©2021 IEEE 714
Jose Ignacio Martinez
Department of Surfaces, Coatings and Molecular
Astrophysics,
Institute of Materials Science of Madrid (ICMM-CSIC)
Madrid, Spain
study physical and chemical configuration of adsorbed
hydrogen [9,10]. The hydrogenation methods range from high
pressure molecular unactivated hydrogen, both at higher and
lower than room temperature conditions, to plasma-activated
hydrogen gas. The main objectives of this work is to determine
the mechanism of hydrogen absorption, to realize its chemical
structure and to calculate the energy states. Nanoparticles of
WS2 may serve as a model for such a research due to the
simplicity of their structure, high stability toward heating and
chemical environment, possibility to simulate how hydrogen
molecules, ions and free atoms interact with these substrate
materials. These goals may be achieved using both
experimental measurements and theoretical tools. Transmission
electron microscopy (TEM) and electron diffraction
measurements of nanostructures following various treatments
were applied to examine the effect of these treatments on
surface topography even pristine changes in the interlayer
distances. While micro-Raman spectroscopy is a method of
choice to determine bonding in hydrogenated nano- and
microstructures [11,12]. Micro-Raman spectra for numerous
WS2-based materials were reported and their data were
elaborated in very detail [13]. The weight percent and thermal
stability of the adsorbed hydrogen were determined by carrying
out the thermogravimetric analysis (TGA).
Theoretical modelling of hydrogen interaction was
performed using a density function theory (DFT). The DFT-
based structures were developed for specific WS2-
nanostructured materials to evaluate which configuration states
are favorable and stable based on energy and interatomic
distance calculations [15].
Finally, we applied the results of these DFT calculations to
experimentally observe the increase of Ga atom implantation
concentrations following plasma hydrogenation. This is
because the implantation of metal atoms like Ga, Re, etc. into
the crystal structure can change their electronic (semiconductor
to metal transfer), magnetic (diamagnetic to paramagnetic
transfer), and optical properties, surface characteristics, and
chemical behavior.
 2021 IEEE 2nd KhPI Week on Advanced Technology (KhPIWeek)
I. EXPERIMENT
The combined reduction-sulfidization process was applied in
the HIT labs to synthesize the fullerene-like nanostructures and
multilayer nanotubes of WS2. The details of the synthesis
procedure were previously described in very detail [16]. The so
obtained nanotubes have the width of 50-150 nm being >20 µm
long; the diameter of the fullerene-like WS2 nanostructures of
was in the range of 100-200 nm. Various hydrogenation
methods used by us will be described in details in the
appropriate parts of this paper.
Micro-Raman measurements were performed using the
Renishaw Invia microspectrometer with *500 magnification.
The laser spot size was in in the range of ~ 2µm and the laser
power was reduced to ~ 0.3 mW to minimize the laser-induced
heating. The advantage of this micro-Raman instrument is its
capability to measure spectral features in a range of up to 5200
cm-1 where hydrogen molecules are active.
Hydrogen weight percent and its thermal stability were
evaluated using TGA in an inert gas environment. The TGA
curves were measured in the temperature range of 25-550 °C
using the SDT Q600 TGA/DSC machine.
To compare the morphological quality of the WS2
nanostructures before and after their exposure to plasma of
hydrogen and deuterium gases, TEM micrographs were
measured in a JEOL ARM 200F TEM/STEM system. Electron
diffraction pattern served to show the modification of the inter-
planar spacing in the WS2 nanostructures as a result of
hydrogen and deuterium adsorption or intercalation processes.
To investigate the DFT-predicted effect of hydrogen
physisorption the plasma hydrogenated WS2 nanostructures
were exposed to focused ion beam (FIB) of 30 keV Ga+ ions,
for different doses. Following ion bombardments, the samples
were analyzed by electron dispersion spectroscopy (EDS), and
micro-Raman.
II. RESULTS AND DISCUSSION
A. Hydrogenation by High Pressure Molecular Hydrogen
As-prepared nanostructures of WS2 were exposed to
molecular hydrogen gas at high pressures (HP) in the pressure
interval of 1-80 bar. This type of hydrogenation was carried out
in the PCTPro-E&E volumetric system. Two sets of
experiments were performed. In the first one the hydrogenation
was carried out at room and high temperatures [9] while in the
second set lower than room temperatures were used. The
pressure-composition-temperature (PCT) hydrogen absorption
isotherms taken at 25 °C, 200 °C, and 350 °C showed that the
weight percent of absorbed hydrogen at three temperature
regimes is 0.11-0.13 % for INT-WS2 [10] and up to 0.19 % for
IF-WS2. In our previous work we assumed that exposure to
molecular H2 results in its physisorption only [9], which
explains why raising the temperatures was of no advantage.
Since physisorption processes are generally more efficient
at low temperatures, in the second set of high pressure
hydrogenations the WS2 nanostructures were hold at
temperatures between -196 °C and -60 °C. The so obtained
isotherms revealed a noticeable increase in hydrogen
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concentration to 0.16 wt. % for WS2 nanotubes and to 0.28 wt.
% for the fullerene-like nanostructures of WS2 [15]. The major
effect was measured however, at -78 °C: 0.29 wt. % for the
fullerene-like particles and 0.36 wt. % for the nanotubes. This
important increase in the hydrogen concentration at low
substrate temperatures is in general agreement with our
assumption that physisorption is the major mechanism of
hydrogen interaction also meaning that the diffusion process
generally favored by high temperatures, may be a significant
factor. This diffusion may result in penetration of hydrogen
molecules through the defects or through the open ends of the
nanotubes to their inner space.
B. Microwave and Radiofrequency Plasma Enhanced
Hydrogenations
As molecular hydrogen exposure showed to be not
sufficiently effective, we used plasma activation in an attempt
to improve the adsorption rates. Microwave (MW) plasma is
well-known to contain active species in high concentration
even at a moderate power; in addition, ~10 % of hydrogen gas
dissociates to free atoms [17]. Indeed hydrogen concentration
of >1 wt. % was measured by TGA in the MW-plasma
hydrogenated WS2 nanostructures [9]. However, the MW
plasma showed to be too aggressive with less consistent results
and even some decomposition of the substrate WS2 materials.
To avoid these drawbacks radiofrequency (RF) plasma was
used using a reactor in HIT [10]. To ensure that RF plasma
activated hydrogen indeed adsorbs or intercalates in the
nanoparticles and to elucidate the best plasma parameters,
several sets of the hydrogenated/deuterated samples were in
situ annealed and pressure increase curves were recorded as a
function of the annealing temperature. Fig. 1 depicts the results
obtained for both MW and RF-hydrogenated WS2 fullerene-
like nanoparticles and nanotubes.
Fig. 1. Pressure change following controlled heating of the WS2 nanostructures
hydrogenated by MW and RF plasma.
As observed from Fig. 1 the increase in pressure is recorded
following normalization procedure (line 1) [10]. In such a way,
we may absolutely attribute the measured pressure increase to
hydrogen release from the plasma-exposed WS2
nanostructures. Lines 2, 3, and 7 have two peaks: at 38 °C and
at ~80 °C. The peak at 38 °C is caused by some weakly bonded
H2 molecules, and the peak at ~80 °C is due to release of deeper
lying and/or strongly bound hydrogen. It can be observed from
curves integration that the most substantial hydrogen release
was obtained for the MW-hydrogenated sample (line 2) and
 2021 IEEE 2nd KhPI Week on Advanced Technology (KhPIWeek)
then by deuterated and hydrogenated fullerene-like WS2 (lines that no peaks related to H-S bonding were detected in their
3 and 5). The curves for all the RF -treated samples showed the characteristic 2000-3000 cm-1 region [19]. This failure to
maximum in the hydrogen release pressure at ~38-40 °C, while measure H-S bonds indicates that no chemisorbed hydrogen is
the release of deuterium took place somewhat slower. For all present in the WS2 nanostructures.
materials, the pressure started to grow at ~35 °C, but the
complete hydrogen desorption was achieved at the
temperatures above 300 °C. Line 4 was recorded at the delay of
5 h after completing the RF-deuteration. It serves as an
indication of hydrogen and deuterium stability even in vacuum
conditions.
TGA is a method to precisely measure the adsorbed species.
As shown on the previous paragraph, only hydrogen or
deuterium desorb. The detailed TGA results for untreated,
hydrogenated, and deuterated WS2 nanostructures were
reported previously [10]. The peak in the weight loss for the
hydrogenated sample was measured at ~80 °C so being at the
same temperature as the second peak in the pressure
measurements in Fig. 1. It is interesting to note that according Fig. 3. Micro-Raman spectra of WS2. Right part: (1) reference sample, (2) RF-
to TGA curves, hydrogenated WS2 nanostructures became hydrogenated sample, (3) RF- hydrogenated and vacuum annealed to 450 °C.
hydrophobic in contrast to hydrophilic pure WS2 [10]. Left part: the typical micro-Raman spectrum of WS2 nanoparticles.
0.7

0.6 D-D
(1)
0.5
Intensity (A.U.)

0.4

0.3
(2)

0.2
Fig. 2. Summary of hydrogen concentrations in WS2 nanoparticles
produced by different treatment methods. 0.1 (1) deuterated
o
(2) annealed to 400 C
Fig. 2 summarizes the hydrogen weight % estimated using
0.0
the TGA curves, as measured for RF-hydrogenated samples 2700 3000 3300 3600 3900
(not shown), were in the range of 0.4-0.55 wt. %. These values Fig. 4. Micro-Raman spectra of: (1) RF-deuterated; (2) 400 °C vacuum-
are higher than those measured for the WS2 nanoparticles annealed WS2 nanostructures.
exposed to unactivated, even low temperature/high pressure
hydrogen gas.
Micro-Raman scattering was performed to obtain the
information concerning the chemical configuration of absorbed
hydrogen species. The spectra were measured in the range of
100-4300 cm-1. Before hydrogenation the micro-Raman spectra
of all WS2 samples were typical of previously reported [13]
showing the E2g mode precisely at 356 cm-1 and the A1g mode
at 419 cm-1, as shown in the left part of Fig. 3. RF-
hydrogenation did not result in any change in the region of 100-
1200 cm-1. However, the curves measured in the region of
3400-4300 cm-1 and shown in the right part of Fig. 3 contain a
small feature at ~4150 cm-1 appearing only for RF-
hydrogenated nanostructures (line 2) and not present either
before hydrogenation (line 1) or after annealing of the
hydrogenated samples to 450 ºC (line 3). This spectral element
was previously related to the stretching mode in the H–H bond
so being a characteristic of the H2 molecule [12,18]. This is why
its appearance in our measured spectra proves that hydrogen
absorption took place and the absorbed hydrogen is in the
molecular form. The gradual disappearance of this peak after Fig. 5. TEM micrograph of the hydrogenated fullerene-like WS2. The location
heating is due to hydrogen desorption. We have to admit that of the interlayer spacing expansion is shown by the arrows.

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 2021 IEEE 2nd KhPI Week on Advanced Technology (KhPIWeek)
Nevertheless, to unambiguously prove that micro-Raman energies (but different adsorption distances). That is, the
spectroscopy is indeed capable to reveal molecular hydrogen in preferred adsorption configurations are on top of W atoms,
WS2, the deuterium gas in the RF plasma was used instead of where three S atoms form a triangular hollow and so allow the
hydrogen. To determine the chemical configuration of the better accommodation of physisorbed hydrogen molecules.
adsorbed deuterium, micro-Raman measurements were
performed in the spectral range of 2500-4000 cm-1, and the The H2 distances and adsorption energies were monitored
results are shown in Fig. 4. Indeed, a small peak, now centered as a function of increasing degree of the H2 coverage. We
at ~2970 cm-1 was observed (line 1). This feature was considered a variety of coverage values for H2 molecules
previously attributed to the D–D stretching mode in deuterium adsorbed on a single WS2 layer, on a WS2 surface and on the
(D2) [18,20], and, therefore, its appearance in our spectra top layer of a trilayer, varying between 0.0625 monolayer (ML)
proves that deuterium is present in the molecular form as was (one H2 molecule per unit cell) and up to the full one ML (16
in the case of hydrogen. No features related to D-S bonds were H2 molecules per unit cell). The calculated adsorption energies
observed here too [21]. Furthermore, RF plasma deuterated per H2 molecule, and the adsorption distances (between the
WS2 samples (IF and INT) were heated in vacuum to 450 ºC center of mass of the H2 molecule and the plane of S atoms) for
for up to 120 min, as for the hydrogenated samples. As seen the single layer, trilayer, and surface, and for 0.0625 ML, 0.25
ML, 0.5 ML and 1 ML coverages are in the ranges +0.05-0.06
from Fig. 4 (line 2), the intensity of the ~2970 cm-1 peak
decreased to nearly zero, supporting our assumptions that the eV and 2.83-2.86 Å, respectively, for adsorption configuration
observed mode corresponds to adsorbed D2 gas. I, and 0.06-0.07 eV and 2.95-2.98 Å, respectively, for
adsorption configuration II. The so calculated adsorption
Deuterium RF plasma exposure was performed to clearly energies have positive layers, meaning that molecular
show that the micro-Raman spectra identifies the absorbed adsorption is energetically preferential. An important outcome
molecular hydrogen in WS2 nanostructures. Bearing in mind of these DFT calculations is that the H2 adsorption on the
the atomic mass difference between hydrogen and deuterium topmost layer of the WS2 multilayered nanoparticle results in a
isotopes, the micro-Raman measurements were performed in small but measurable increase of the distance between the
the interval of 2500-4000 cm-1 and shown in Fig. 4. As in the topmost and the next, lower lying WS2 layer, and that this
case of hydrogenated samples, the spectra of all deuterated WS2 decoupling is enhanced when the H2 coverage concentration
nanostructures contain an additional feature at 2970 cm-1. It was increases: the interlayer distances of 6.13 Å for the clean WS2
attributed to the D-D stretching in a D2 molecule [18,20]. In trilayer grows up to 6.21 Å, for the full coverage. This
addition, no D-S modes [21] were measured. These observation phenomenon is in outstanding agreement with the increase of
show that similar to hydrogen, deuterium also physisorb as a the interlayer distance observed in the electron diffraction
molecule. Moreover, these results unambiguously prove the pattern measurements.
success of the RF-plasma hydrogenation process.
The TEM image of the RF-hydrogenated WS2 fullerene-
like nanoparticle presented in Fig. 5 clearly shows the isolated
locations where the interlayer distance increases to ~0.85 nm,
as shown by arrows. This is in comparison interlayer distance
of 0.62 nm in the pure WS2 nanoparticle. Such an expansion
has never been observed in pristine WS2 nanostructures but
occurs in WS2 intercalated by foreign species. The electron
diffraction revealed the expansion from 0.62 nm for the pure Fig. 6. Calculated structures for the intercalation of H2 between the 1st and the
2d layers of the WS2 trilayer: (left panel) 0.0625 ML, (right panel) 0.25 ML.
nanoparticles to 0.65 nm for the hydrogenated one. We will
later refer to this phenomenon.
C. DFT Modeling of the Hydrogen Configuration and
Adsorption Sites
Density functional theory (DFT) was used perform
atomistic simulations for planar and nanotube, layered WS2
nanostructures. The objective of these simulation is to model
hydrogen absorption These calculations greatly contribute to
the interpretation of the experimental results. The details of
these calculations were explained previously [10,15,22-25].
First, we studied the adsorption of H2 on the planar-like
WS2 nanostructures: I) H2 molecules on top of a tungsten (W)
atom arranging in parallel to the surface; II) H2 molecules on
top of a tungsten (W) atom arranging in perpendicular to the
Fig. 7. Modelled two layers adsorption of H2 on top of WS2.
surface; III) H2 molecules on top of a S (sulfur) atom arranging
in parallel to the surface; IV) H2 molecules on top of a sulfur The above calculations proved that molecular hydrogen can
(S) atom arranging perpendicular to the surface. The adsorb on the WS2 nanoparticle surface or in the outermost or
calculations reveal two preferential adsorption sites. innermost walls of the nanotubes, but not in between layers. For
configurations I and II, yielding very similar adsorption

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 2021 IEEE 2nd KhPI Week on Advanced Technology (KhPIWeek)
this purpose, simulations were performed by intercalating the
trilayer with increasing amounts of H2 positioned in between
the first and second layers. Fig. 6 illustrates the results for
0.0625 ML and 0.25 ML intercalation. The calculations showed
that the interlayer distances should increase as the hydrogen
content growths. So it is quite obvious that the calculated
intercalation energy for all cases is now negative; that is,
intercalation is less probable. The layer-layer expansion energy
is very large at first. It amounts to 1.50 eV for a tiny expansion
of 6.21-6.13 = 0.07 Å, with a rate of 1.50/0.07 = 21.4 eV/Å.
Next, in the expansion from 6.21 to 7.51 Å, the rate decreases
drastically to the value 2.26/1.3 = 1.74 eV/Å. On the other hand,
a large interlayer expansion of up to 8.5 Å in some locations
was observed by TEM (Fig. 5). We may assume, therefore, that
some H2 molecules do intercalate in the nanostructures under
the RF plasma conditions which provide the energy required for
the H2 molecules to intercalate. The mechanism of this process
may be as follows: by the potential drop of ~3Te accelerates the
plasma ions (Te is the electron temperature, ~2 eV in our
conditions [26]). These accelerated ions collide with neutrals
and form an energetic mixture of ions-neutrals flowing toward
the nanoparticles surface. The calculations of various
parameters for these plasma-related species are still underway.
In addition to plasma-induced surface modification, there is
another pass way which may be responsible for the increase in
hydrogen concentration as compared to DFT predictions. As a
test, we performed simulations for the covering of a single WS2
layer with several monolayers of H2. The starting configuration
was formed by hydrogen molecules on top of all W and S atoms
(this corresponds to 2 ML coverage in the notation used above
in this paper). The molecules were originally on the same plane.
Structural relaxation of the system allowed the hydrogen
molecules to optimize their positions forming two layers, as
shown in Fig. 7. The calculated adsorption energy, 0.058 eV
per molecule, is about the same as the adsorption energy per
molecule for a single adsorbed H2 monolayer and it indicates
that the multilayer molecular hydrogen adsorption is favorable
as well.
D. Ga implantation into hydrogenated WS2
The DFT and our experimental results predict expansion of
the interlayer distance in WS2 nanoparticles following RF
plasma hydrogenation. This expansion may enable
intercalation and implantation of other species, which are
otherwise difficult to incorporate in WS2 nanostructures.
Implantation of metal atoms like Ga, Nb, Re into the crystal
structure can change their electronic (semiconductor to metal
transfer), magnetic (diamagnetic to paramagnetic transfer), and
optical properties, surface characteristics, mechanical and
chemical behavior [27]. These parameters are of extreme
interest during the last few decades as could be useful in many
nanotechnology applications, like photovoltaics and
optoelectronics, catalysts and sensors preparation, and even
tribology and lubrication. However, such implantation
processes are complicated and frequently result in destructive
changes. When attempting to implant the pure WS2
nanoparticles with Ga+ ions using FIB, no Ga atoms were
measured for the intermediate ion doses still keeping the
pristine structure of the nanoparticles. However, when
performing the same FIB process for the RF-hydrogenated WS2
718
nanotubes, the result was different and a promising one. Table
1 illustrates Ga concentration as measured by EDS for 2
different ion doses:
TABLE 1
Ga atomic concentration following FIB of hydrogenated
WS2
Ion Dose (cm-2) Weight % of Ga
1.5×1015 0.25
3.0×1015 0.30
The micro-Raman spectra of the ion-bombarded WS2
shown in Fig. 8 indicate that no damage was caused to the
nanoparticles and they maintain their perfect structure with
only some minor oxidation.
Fig. 8. Micro-Raman spectra of pristine and FIB Ga+= bombarded WS2
nanotubes.
III. CONCLUSIONS
Nanoparticles of WS2 absorb some molecular hydrogen
when exposed to it at high pressure. Exposure to high pressure
hydrogen at low temperatures, down to -196 °C, makes the
adsorption process more efficient but suppresses the diffusion
process, which is essential for penetration of hydrogen to inner
layers. The intermediate temperature of -78 °C was found to be
optimal for adsorption and diffusion process of molecular non-
activated hydrogen as it results in the highest adsorption
concentration for this type of the hydrogenation process.
Using MW and RF plasma as the hydrogen activation
method leads to the substantial increase of hydrogen absorption
rate in both all types of WS2 nanostructures: up to 0.55 wt. %
for the RF plasma and up to 1.1 wt. %, after the MW plasma
hydrogenation.
The chemical structure and energy states of hydrogen
species absorbed in the WS2 nanoparticles were determined by
both experimental analytical techniques and a DFT theoretical
model. The micro-Raman scattering spectroscopy was capable
to detect the stretching modes of H-H and D-D at 4150 cm-1 and
2970 cm-1, respectively, so suggesting that RF-hydrogenation
produces physisorption of molecular hydrogen. This hydrogen
is found to be stable at ambient and vacuum conditions. The
DFT predicts that the physisorbed hydrogen is adsorbed in
several layers. However the intercalation energies calculated by
 2021 IEEE 2nd KhPI Week on Advanced Technology (KhPIWeek)
DFT are negative so making an intercalation less favorable.
Nevertheless, we found that molecular hydrogen intercalation
could take place under the RF-plasma.
The effect of interlayer expansion due to surface
hydrogenation predicted by the DFT calculations has been
successfully applied to show that Ga atoms can be implanted
into hydrogenated WS2 nanoparticles using the FIB technique
while such an implantation was not effective for the pure, non-
hydrogenated nanoparticles. In such a way, our findings open a
gate to introduce other species with the objective to
functionalize WS2 and similar nanomaterials by modifying
their original properties.
ACKNOWLEDGMENT
We acknowledge the support of different parts of this work
by COST actions MP1103 and MP1302. We would like to
thank A. Fruchtman and G. Makrinich (Plasma Lab., HIT) and
M. Sezen (Sabanci University, Istanbul) for their assistance
with RF plasma and TEM/FIB, respectively.
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