Layered Transition-Metal Ditellurides in Electrocatalytic Applications - Contrasting Properties

Article abstract of DOI:10.1021/acscatal.7b02080

The layered compounds and especially transition-metal dichalcogenides are at the forefront of current research on electrocatalytic materials. Despite the fact that electrocatalytical properties of molybdenum and tungsten disulfides are well-known, their tellurium analogues are significantly less explored. Here we show an effective method for MoTe₂ and WTe₂ chemical exfoliation based on alkali metal intercalation and subsequent reaction with water. The as-synthesized and exfoliated tellurides were characterized in detail and investigated for potential application in electrocatalysis. The inherent electrochemical activity related to both cation and anion was observed. This is dominantly related to the oxidation tendency of tellurium. The MoTe₂ and WTe₂ show significantly contrasting properties toward the hydrogen evolution reaction, where MoTe₂ shows highly increased HER activity with little dependence on electrochemical treatment, whereas WTe₂ shows slightly worse improvement and strong dependence on the electrochemical treatment. In particular, the exfoliated MoTe₂ exhibits improved electrocatalytic activity for hydrogen evolution reaction and possesses a huge application potential.

Full text of DOI:10.1021/acscatal.7b02080

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Article
Layered transition metal ditellurides in
electrocatalytic applications – contrasting properties
Jan Luxa, Pavel Vosecky, Vlastimil Mazánek, David
Sedmidubsky, Martin Pumera, Petr Lazar, and Zdenek Sofer
ACS Catal., Just Accepted Manuscript • DOI: 10.1021/acscatal.7b02080 • Publication Date (Web): 13 Jul 2017
Downloaded from http://pubs.acs.org on July 13, 2017
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Layered transition metal ditellurides in electrocatalytic applications – contrasting
properties
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J. Luxaa, P. Voseckýa, V. Mazáneka, D. Sedmidubskýa, M. Pumerab, P. Lazarc and Z. Sofera*
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a
Department of Inorganic Chemistry, University of Chemistry and Technology Prague,
Technická 5, 166 28 Prague 6, Czech Republic. Eꢀmail: zdenek.sofer@vscht.cz; Fax: +420ꢀ
22044ꢀ0422
b
Division of Chemistry and Biological Chemistry, School of Physical and Mathematical
Sciences, Nanyang Technological University Singapore 637371, Singapore
c
Department of Physical Chemistry and Regional Centre of Advanced Technologies and
Materials, Palacký University Olomouc, tř. 17. Listopadu 1192/12, 771 46 Olomouc, Czech
Republic
ABSTRACT
The layered compounds and especially transition metal dichalcogenides are at the forefront of
current research on electrocatalytic materials. Despite the fact that electrocatalytical properties
of molybdenum and tungsten disulfides are well known their tellurium analogues are
significantly less explored. Here we show an effective method for MoTe2 and WTe2 chemical
exfoliation based on alkali metal intercalation and subsequent reaction with water. The as
synthesized and exfoliated tellurides were characterized in detail and investigated for potential
application in electrocatalysis. The inherent electrochemical activity related to both cation and
anion was observed. This is dominantly related to the oxidation tendency of tellurium. The
MoTe2 and WTe2 show significantly contrasting properties towards hydrogen evolution
reaction, where MoTe2 shows highly increased HER activity with little dependence on
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electrochemical treatment whereas WTe2 shows slightly worse improvement and strong
dependence on the electrochemical treatment. In particular, the exfoliated MoTe2 exhibits
improved electrocatalytic activity for hydrogen evolution reaction and possesses a huge
application potential.
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KEYWORDS
tellurides; transition metals; hydrogen evolution; exfoliation; nanostructures
INTRODUCTION
With the demand of renewable energy sources, more and more attention is being
funneled into the research of efficient hydrogen evolution reaction (HER) catalysts. It is
highly desirable to replace highꢀcost platinum with cheaper and more available alternatives. A
large number of candidates have been recently proposed and widely explored. These include
porous metallic nanocatalysts, doped graphene, metal oxides, metal phosphides and transition
metal dichalcogenides.1ꢀ11 Over the past years, enormous amount of attention has been paid to
the last mentioned: transition metal dichalcogenides (TMDs).12, 13
TMDs are composed of stacked layers with general formula of MX2 (M= transition
metal, X= S, Se, Te). Strong covalent bonds within layers and weak Van der Waals forces
between layers make this group of materials excellent candidates for exfoliation.14ꢀ16 Several
methods have been developed for the preparation of atomically thin layers. These include
chemical vapor deposition (CVD), mechanical exfoliation and also probably the most
efficient liquid phase exfoliation and ion intercalation based exfoliation.17ꢀ20 Ion intercalation
based exfoliation is especially intriguing, as it can induce a phase transition from
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semiconducting 2H phase to metallic 1T phase.1, 21 The extent of phase transition to 1T is of
pivotal importance since this phase exhibits better HER catalytical activity than 2H phase21, 22
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Most of the research on TMDs HER catalysis has been devoted to MoS2 and WS2. A
variety of methods have been developed for the enhancement of HER performance of these
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compounds.22ꢀ28 As far as ion intercalation based exfoliation goes, nꢀbutyllithium is the most
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commonly used intercalant.14,
Aromatic based exfoliation agents such as sodium
naphtalenide have also been shown to produce single layer sheets with a high yield.31, 32 Aside
from the aforementioned 2H ꢀ> 1T phase transition, the increased catalytic activity also stems
from the increased amount of edges, which are the HER active sites.22, 23, 33 In fact, the
approach of increasing the edge site concentration via decreasing size of the catalyst is very
fashionable.34ꢀ36
Despite the promising results, many of the TMDs family members remain unexplored
in terms of HER catalysis. Most of the reports deal with MoS2 and WS2 and their composites
with conductive substrates such as graphene.37, 22, 27, 38ꢀ41 Lately, research on other TMDs
including molybdenum and tungsten diselenides has begun to proliferate.42, 43 However, very
little attention has been paid to molybdenum and tungsten ditellurides. As of now, there is
only one paper dealing with molybdenum and tungsten ditellurides.44 Since that paper deals
with liquid phase exfoliation, there is still a knowledge gap about performance of chemically
exfoliated MoTe2 and WTe2. Despite the fact that their electrochemical properties are
relatively unexplored, MoTe2 and WTe2 have been intensively studied for some of their
outstanding physical properties. For example they are both soꢀcalled typeꢀII Weyl semimetals
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which gives rise to extraordinary physical properties.45,
WTe2 can also exhibit
superconducting properties and very high magnetoresistance.47, 48
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In this work we demonstrate the influence of chemical exfoliation of MoTe2 and WTe2
on the HER catalytical properties. For this purpose we have incorporated two commonly used
exfoliation reagents – nꢀbutyllithium and sodium naphtalenide. Thorough characterization
revealed strong tendency towards oxidation after exfoliation of both MoTe2 and WTe2. The
knowledge acquired from the inherent electrochemistry investigation allowed for the
extraction of potentials used for the oxidative/reductive pretreatment aiming for further
enhancement of calatytical properties. The schematic drawing of tellurides exfoliation
procedure is shown on Scheme 1.
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Scheme 1. The schematic drawing of exfoliation procedure based on lithium intercalation and
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subsequent exfoliation by reaction with water.
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RESULTS AND DISCUSSION
In this paper we show the relations between electrocatalytic activity of layered
ditellurides and their structure as well as their degree of exfoliation. Significantly contrasting
properties are observed on the hydrogen evolution reaction (HER) catalysis of chemically
exfoliated transition metal ditellurides, namely MoTe2 and WTe2. For more detailed
comparison, bulk materials are described too. Two of the previously reported exfoliation
reagents were used to intercalate and subsequently exfoliate these materials. One of them, nꢀ
butyllithium is commonly used for the exfoliation of transition metal dichalcogenides
(TMDs). The other one, sodium naphtalenide has also been previously reported to be suitable
for high yield exfoliation of TMDs, especially in the case of layered transition metal
disulfides.
A variety of analytical techniques including scanning electron microscopy (SEM),
energy dispersive spectroscopy (EDS), Raman spectroscopy and Xꢀray photoelectron
spectroscopy were employed to carefully characterize the materials from the viewpoint of
composition and structure. The results extracted from inherent electrochemistry
measurements were used to probe the potential activation of materials via oxidation/reduction.
Samples in this work are referred to on the basis of procedure used for exfoliation (Bulk, BuLi
and Naph) and eventually the reductive/oxidative electrochemical treatment (red.; ox.).
Electron micrographs depicting the morphology of molybdenum and tungsten
ditellurides are shown in Figure 1.
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Figure 1. SEM micrographs of bulk and exfoliated MoTe2 (top) and WTe2 (bottom). Scale
bars correspond to 5 µm.
A striking transition from large regularly shaped crystals of bulk material to wrinkled small
crystallites of exfoliated materials was clearly observed. SEM micrographs documented the
successful exfoliation using nꢀbutyllithium and sodium naphtalenide reagents. However, most
of the wrinkling formed during the exfoliation was observed only on the edges of relatively
large sheets. This was especially apparent in the case of WTe2 BuLi suggesting that the yield
of single to fewꢀlayered sheets was much lower than in the case of transition metal sulfides,
where the use of same exfoliation reagents led to high yield of single to fewꢀlayered sheets.31
Composition as well as elemental distribution was measured by SEMꢀEDS. Element
distribution maps are shown in Figure S1 and the composition is summarized in Table 1. The
maps revealed homogeneous distribution for all the samples, but there was a tremendous
increase in oxygen content contrasting with the oxygen free bulk materials. Such an increase
is most likely related to an increased surface area introduced by the exfoliation. Even though
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this is quite typical for chemically exfoliated TMDs, such a high oxygen content indicated
higher susceptibility of molybdenum and tungsten tellurides toward oxidation, compared to
other TMDs.1
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Further characterization was performed with TEM and HRꢀTEM (Figure 2). The individual
exfoliated plates with single and few layer thickness exhibit lateral sizes in the range from
hundred of nanometers up to few microns. Elemental distribution map measurement
performed by EDS (Figure S2) shows homogeneous distribution of elements without any
evidence of phase separation and decomposition.
Figure 2. TEM and HRꢀTEM images of TMDs with SAED insert. The scale bar on TEM
images correspond to 1 ꢀm and 500 nm (MoTe2 Naph) and the scale bar on HRꢀTEM image
corresponds to 5 nm.
Table 1. Composition of bulk and exfoliated Molybdenum and Tungsten ditellurides obtained
by EDS.
Sample
M (at. %) Te (at. %) O (at. %)
Te/M
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MoTe2 Bulk 31.3
MoTe2 BuLi 16.9
MoTe2 Naph 21.7
WTe2 Bulk 31.7
WTe2 BuLi 23.0
WTe2 Naph 24.2
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Xꢀray diffraction (XRD) was used to verify the phase purity of both synthesized bulk
and exfoliated molybdenum and tungsten tellurides. The XRD patterns are shown in Figure
S3 together with structures of MoTe2 and WTe2. Pure 2H phases were successfully
synthesized for both bulk materials. Exfoliation by both nꢀbutyllithium and sodium
naphtalenide led to a partial decomposition into tellurium and the corresponding telluride.
However, the degree of decomposition was very low in all cases (approximate concentration
of Te lower than 5 wt. %). Despite the high concentration of oxygen (EDS and XPS), no
reflections related to the oxides were detected. This indicates the presence of amorphous
oxides only. Although the reflections of exfoliated tellurides are quite sharp and narrow, we
attribute this to restacking which is quite typical for TMDs. It was shown by SEM that
significant wrinkling and lowering of sheet size took place during the exfoliation.
Raman spectroscopy was employed for further structural characterization of MoTe2
and WTe2. Raman spectra of MoTe2 in the 160ꢀ400 cmꢀ1 region are shown in the left part of
Figure 3. Several modes were found in this region. An inꢀplane mode at ~ 235 cmꢀ1 denoted
as E12g and outꢀofꢀplane mode at ~ 174 cmꢀ1 denoted as A1g were observed in MoTe2 bulk and
MoTe2 Naph samples.49, 50 A1g mode was not observed in the MoTe2 BuLi sample. This was
caused by an overlap with an intense peak with a maximum at~130 cmꢀ1 which is not
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completely shown in the region displayed in Figure 3. Raman spectrum over a wider range of
wavenumbers is shown in the supporting information (Figure S4). Apart from the peak at 130
cmꢀ1, several additional peaks were identified in the MoTe2 BuLi Raman spectrum: an intense
peak at ~ 119 cmꢀ1 and two peaks at ~ 820 and 995 cmꢀ1 which are related to the presence of
MoO3.51 None of these peaks were detected in other MoTe2 spectra. This is also in good
agreement with the high concentration of oxygen in the MoTe2 BuLi sample (see EDS
discussed previously and XPS discussed in the following sections). Additional peak denoted
as B2g was observed in the Raman spectrum of MoTe2 Naph. This peak appears neither in
Raman spectrum of the bulk nor in the single layer MoTe2 suggesting that MoTe2 Naph
sample was composed of few layers thick sheets.52 The absence of this peak in the Raman
spectrum of MoTe2 BuLi may indicate that this material was composed of atomically thin
sheets that do not possess this phonon vibration.52
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Figure 3. Raman spectra of bulk and exfoliated MoTe2 (left) and WTe2 (right).
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Raman spectra of WTe2 are shown in the right part of Figure 3. Four peaks were
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detected in the 100 – 250 cmꢀ1wavenumber region. These peaks located at ca. 213, 164, 143
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and 124 cmꢀ1 are denoted as A1 , A1 , A1 and A1 , respectively.53 Even though the peak
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positions are in good agreement with the literature for all WTe2 samples, the peak intensity
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ratios are in good agreement only for bulk WTe2. We observed significant lowering of A1
mode intensity while the remainder of the modes exhibited an increase in intensity as well as
strong broadening, which was especially apparent for WTe2 Naph sample. We have not
observed any softening of the modes associated with the decreased number of layers below
five layers reported in the literature.53 We suggest that the strong broadening of individual
modes was related to the decrease of lateral size of individual sheets which was observed by
SEM.
In the next step, surface composition was examined by Xꢀray photoelectron
spectroscopy (XPS). Survey spectra (Figure S5) were firstly recorded. The composition
extracted from the survey spectra and the chalcogen to metal ratios are summarized in Table
S1. The carbon shown in the results originates from adventitious carbon and hydrocarbon/CO2
contamination. An increase in oxygen concentration can be seen for both exfoliated MoTe2
and WTe2 samples. This is related to the increase of surface area, which allows faster surface
oxidation. The susceptibility of MoTe2 and WTe2 towards oxidation has already been reported
previously.53, 54 The chalcogen to metal ratios also revealed that the exfoliation produces
tellurium rich surface in the case of MoTe2 and metal rich surface in the case of WTe2.
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Figure 4. Highꢀresolution XPS spectra of a) MoTe2 Mo 3d, b) WTe2 W 4f, c) MoTe2 Te 3d
and d) WTe2 Te 3d.
High resolution coreꢀlevel spectra were further recorded for Mo 3d, W 4f and Te 3d
states (Figure 4). Firstly, deconvolution of Mo 3d spectrum in Figure 4a revealed the
presence of two oxidation states in both bulk and exfoliated MoTe2. Mo34+ 3d5/2 and Mo4+
3d3/2 pair at ca. 228.7 eV and 231.8 eV, respectively, was attributed to MoTe2 whereas the
pair located at ca. 232.8 eV and 236 eV was attributed to molybdenum in Mo6+ oxidation state
(MoO3 typical for TMDs). A dramatic increase of Mo6+ peaks intensity can be clearly seen
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especially in the case of MoTe2 BuLi. This is in good agreement with EDS and Raman
spectroscopy measurements (see previous sections) and further confirms the susceptibility of
MoTe2 towards oxidation. Interestingly, intercalation and subsequent exfoliation does not
induce any phase transition from 2H to 1T. However, this has been previously reported for
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some others TMDs. The concentrations of the individual valence states are summarized in
Table S2. Figure 4b displays the high resolution coreꢀlevel spectra of W 4f state. Similarly to
Mo 3d, two pairs of peaks were detected in the W 4f spectra, namely W4+ 4f7/2 together with
W4+ 4f5/2 at ca. 31.7 and 33.9 eV, respectively, from 2H WTe2, and W6+ 4f7/2 together with
W6+ 4f5/2 at ca. 35.5 and 37.7 eV, respectively, from WO3. Additionally, a new pair of peaks,
originating from 1T WTe2, was observed at slightly lower binding energies than 2H WTe2.
This is in high contrast with MoTe2, in which no 1T phase was observed. Moreover, it can be
seen from Table S2 that most of the WTe2 is in the form of 1T phase, especially in the case of
WTe2 Naph. This suggests that the exfoliation process of WTe2 is highly favorable for the 2H
ꢀ> 1T phase transformation. On the other hand, an increase of W6+ concentration can be seen
in the case of exfoliated WTe2 as well. This was again attributed to an increased surface area
and higher degree of oxidation introduced during the exfoliation. Finally, Te 3d coreꢀlevel
spectra of MoTe2 and WTe2 are displayed in Figure 4c and Figure 4d, respectively. A very
similar trend to that observed in Mo 3d and W 4f spectra can be seen here. In contrast to a low
concentration of TeO2 in bulk materials, the exfoliated samples exhibited an increased
concentration of oxidized species. Generally, nꢀbutyllithium exfoliation route seemed to result
in more oxidized materials than sodium naphtalenide exfoliation route for both MoTe2 and
WTe2. Despite the expectations, the increased degree of oxidation does not necessarily lead to
a decrease of HER catalytic properties as will be discussed in the following sections.
In the next step, we performed inherent electrochemistry measurements. This is highly
advantageous for the extraction of electrochemical potentials used for electrochemical
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activation treatment (oxidation/reduction). Cyclic voltammetry curves for both anodic and
cathodic scans in a phosphate buffer solution are shown in Figure 5 for MoTe2 and Figure 6
for WTe2. From the CV curves, potentials used for electrochemical oxidation/reduction
pretreatment were identified. Potentials higher/lower by ca. 0.2 V than the most
positive/negative oxidation/reduction peak were used.
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Firstly for the MoTe2 Bulk, a peak at ca. 0.55 V followed by an inconspicuous
reduction peak at ca. ꢀ0.84 V emerges in the anodic scan. This oxidation peak was shifted to
about 0.37 V in the following scans. Similarly, the same oxidation and reduction peaks were
present in the cathodic scans with the exception of the reduction peak at ꢀ0.84 V which only
emerged in the following scans. This suggested that the reduction peak is related to the
reduction of moieties formed during the oxidation at 0.55 V/0.37 V. From the literature and
our previous work we can conclude that the oxidation peak can be at least partially ascribed to
an oxidation process of tellurium.55, 56 For more detailed investigation, we also performed
XPS measurements after electrochemical oxidation/reduction with the results shown in
Figure S6 and summarized in Tables S3 and S4. The increase in TeO2 concentration in
MoTe2 Bulk ox. is quite unsurprising. However, the striking TeO2 concentration increase for
MoTe2 Bulk red. was unexpected. This may be a result of a metastable intermediate formation
which is readily oxidized under exposure to ambient atmosphere. The HR XPS spectra of Mo
3d revealed changes in Mo6+ concentration. A complete reduction to Mo4+ in MoTe2 Bulk red.
and a slight increase of Mo6+ in MoTe2 Bulk ox. can be seen. This indicates that the oxidation
observed in the CV curves may be an overlap of Te and Mo oxidations.
The situation becomes much more complex in case of nꢀbutyllithium and sodium
naphtalenide exfoliated MoTe2. Obviously, exfoliation introduces new oxidizable/reducible
moieties, which is apparent from the broadening of oxidation peak at 0.55V and appearance
of new reduction peaks. The similarity of CV curves for both MoTe2 BuLi and MoTe2 Naph
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makes it apparent that both routes produce similar reducible/oxidizable moieties. However,
reduction peaks are less intensive in the case of MoTe2 Naph and the analysis of XPS spectra
(Figure S6 and Table S4) revealed, that both Te and Mo are more easily reduced in the case
of MoTe2 Naph. The smaller current indicates fewer reducible species which were shown to
be likely metastable and tend to oxidize under ambient conditions.
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Figure 5. Inherent electrochemistry measurements of bulk and exfoliated MoTe2. Conditions:
PBS (pH 7.2), scan rate 0.1 V/s.
The WTe2 Bulk behavior was very similar to that of MoTe2 Bulk and the comparison
revealed only one additional peak at ca. ꢀ1.5 V. Since the difference is in the metal element,
we expect that this signal originated from tungsten. The XPS spectra after electrochemical
oxidation/reduction (Figure S7 and Tables S6 and S7) revealed an increased concentration of
W6+ in both reduced and oxidized WTe2 Bulk. This was in contrast to MoTe2 Bulk which was
successfully reduced by cathodic potentials. As expected, this was even more pronounced for
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WTe2 Bulk ox. The analysis of Te 3d spectra also showed an increase in TeO2 concentration,
which was also very well apparent by the emergence of a new pair of peaks in the W 4f
spectra. This was not observed in the untreated materials.
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Inspection of the complex CV curves of WTe2 BuLi and WTe2 Naph revealed that the
exfoliation of WTe2 introduced new oxidizable/reducible moieties. Firstly, an increase in
current was clearly apparent for both exfoliated samples. Additionally, the reduction peak
previously observed at about ꢀ1.5 V shifted to about ꢀ1 V in both anodic and cathodic scans
suggesting either an activation of reducible moieties or a presence of new ones. Moreover, the
oxidation peak at about 0.4 V and the reduction peak are related to each other. It is obvious
from Figure 6 that the oxidation current increased significantly after sweeping to negative
potentials. This suggested a reversible oxidation of products formed by the electrochemical
reduction. The complexity of the surface chemistry was mostly pronounced in the WTe2 Naph
sample which exhibited multiple oxidation peaks (anodic scan) and multiple reduction peaks
(cathodic scan).
XPS spectra again revealed a high instability and susceptibility of the exfoliated WTe2
towards oxidation. While an increase of the oxidized species is apparent in WTe2 BuLi red.
and WTe2 Naph red., a complete oxidation is observed for samples treated with anodic
potentials.
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Figure 6. Inherent electrochemistry measurements of bulk and exfoliated WTe2. Conditions:
PBS (pH 7.2), scan rate 0.1 V/s.
Finally, the exfoliated molybdenum and tungsten ditellurides were tested for their
hydrogen evolution reaction (HER) catalytical activity. The bulk material as well as bare
glassy carbon (GC) and Pt/C catalyst measurements are included for comparison.
AOverpotential at ꢀ10 mA.cmꢀ2 was used to compare the individual samples. Results of HER
measurements are shown in Figure 7. Because of their low surface area and thus lower
amount of HER actives sites, both bulk MoTe2 and WTe2 exhibited the largest overpotentials.
Electrochemically untreated MoTe2 Bulk exhibited an overpotential of ꢀ0.75 V which
increased to ꢀ0.80 V for MoTe2 Bulk red. and ꢀ0.90 V for MoTe2 Bulk ox. becoming even
worse catalyst than the bare GC electrode. WTe2 in its untreated bulk form showed a slightly
higher catalytic activity (ꢀ0.64 V) than the bulk MoTe2, but electrochemical treatment led
again to slightly higher overpotentials. The difference between oxidized and reduced bulk
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WTe2 was negligible with overpotentials of ꢀ0.68 V and ꢀ0.69 V for WTe2 Bulk red. and
WTe2 Bulk ox., respectively.
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Exfoliation invoked a dramatic increase in HER catalytic activity, which was very well
documented by the overpotential decrease. We attribute this to an increase in surface area
introduced during the exfoliation and a presence of 1T phase in the exfoliated WTe2. BuLi
exfoliated MoTe2 and Naph exfoliated MoTe2 exhibit the respective overpotentials ꢀ0.38 V
and ꢀ0.40 V. Interestingly, both electrochemical oxidation and reduction have a minute
influence on the catalytical activity especially in the case of MoTe2 where only a slightly
higher overpotential can be observed for MoTe2 BuLi red. This effect was a bit more
pronounced in the case of MoTe2 Naph with a little higher difference between the
performance of untreated and electrochemically treated samples. The XPS analysis discussed
in the previous section revealed dramatic changes in the surface composition. The fact that
HER activity remained nearly the same suggests that even the oxidized surface of MoTe2 may
serve as a HER catalyst and that the activity is hindered only to a minimal degree. This was
strikingly different from MoS2 where the treatment with oxidative potentials led to worsening
of HER activity. The catalytic activity of molybdenum and tellurium oxides also has to be
taken into account and asks for more attention in the future.
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We performed density functional theory (DFT) calculation of hydrogen bonding onto
edges of MoTe2 and WTe2 to elucidate their activity for HER. Intrinsic activity for HER can
be assessed by the Gibbs free energy of the adsorbed H (∆GH), because a material with
(nearly) thermoneutral ∆GH (i.e. ∆GH ≈ 0 eV) is expected to be effective for HER.57 Pt/C is,
by far, the best electrocatalyst and its ∆GH has been found to be almost perfectly
thermoneutral.58 We focus on the metal edge of MoTe2 and WTe2, since the edges have been
found to be active facets for molybdenum and tungsten disulfides, whereas the (0001) basal
planes have been found to be inert.23, 42 Our calculations reveal that the bare metal edges (i.e.
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metal edge at 0% Te coverage) are unstable, because they have a very high energy and
undergo serious structural changes, which disrupt the nanostripe. The adsorption of tellurium
monomer atoms (i.e. 50% Te coverage) is necessary to stabilize the edge. It should be noted
that the specific structure (the coverage of chalcogen atoms on the edge) depends mainly on
the chemical potential of tellurium containing species under the operating conditions and can
seriously affect the calculated adsorption enthalpies.59 The resulting Gibbs free energy of
adsorbed H is 0.57 eV and 0.34 eV for the metal edge of MoTe2 and WTe2, respectively. In
comparison, molybdenum disulfide and diselenide have respective ∆GH of ꢀ0.36 eV and 0.02
eV for the equivalent adsorption at 25 % hydrogen coverage of the Moꢀedge.42, 57 Tungsten
disulfide and diselenide have ∆GH of ꢀ0.04 eV and 0.17 eV under the same circumstances,
respectively. The hydrogen atom thus binds to the tellurium monomer atoms at the metal
edge, but the bond is weaker than the HꢀS bond in analogous molybdenum and tungsten
dichalcogenides. A similar trend of an increased adsorption enthalpy as one descends through
the group of dichalcogenides has been recently calculated for platinum dichalcogenides.55
Increasing the size of chalcogen atom (in the sequence S, Se, Te), the bonding orbitals
become larger and more diffused and, consequently, the bond between the atom and the
hydrogen weakens. As a result, both MoTe2 and WTe2 should intrinsically exhibit HER
performance inferior to that of their disulfides and diselenides, which can adsorb hydrogen
more effectively (∆GH close to zero). It should be emphasized, that our calculations are of a
model character, and have therefore inherent limitations. One of limitations is the
computational model, which represents catalytic site as an ideally straight edge in vacuum, i.e.
the roles of lattice imperfections, edge curvature, and solvent effects are neglected. Moreover,
although the ∆GH has been widely considered to be a useful indicator for the catalytic activity,
it describes only equilibrium thermodynamics of the reaction and may not be directly related
to the activation barrier for HER.60
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Compared to MoTe2, the WTe2 seems to offer a lot more possibilities in terms of
possible electrochemical activation. While the exfoliated MoTe2 after electrochemical
treatment exhibited nearly the same activity, there were major differences in untreated and
electrochemically treated WTe2. WTe2 BuLi with an overpotential of ꢀ0.60 V showed only a
minor improvement over bulk WTe2 but became much more active after electrochemical
treatment. The overpotentials lowered down to ꢀ0.55 V for WTe2 BuLi red. and even more
down to ꢀ0.40 V for WTe2 BuLi ox. This was quite surprising if we consider the XPS results
which revealed that the surface of this material was fully corroded. Therefore, the catalytic
activity of surface oxides may play even more important role than in the case of MoTe2.
Finally, WTe2 Naph with an overpotential of ꢀ0.51 V showed a slightly higher intrinsic
activity than WTe2 BuLi. However, in this case, the electrochemical treatment did not lead to
an improvement of HER catalytic activity. On one hand, WTe2 Naph ox. was also revealed to
be fully corroded but still outperformed WTe2 Naph red.. This again calls for more attention
on how the presence of surface oxides influences the overall HER performance of TMDs.
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Figure 7. HER performance measured by LSV in 0.5M H2SO4 with a slow scan rate of 2
mV/s. Average overpotential values are shown in the right part of the figure. Error bars are
based on triplicate measurements.
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Finally, Tafel slopes extracted from the LSV curves are displayed and compared in
Figure 8. As a benchmark for potential application performance, Tafel slopes are of high
importance. Values of Tafel slopes around 150 mV/dec of both MoTe2 Bulk and WTe2 Bulk
showcased their small HER catalytic activity, which is not enhanced neither by
electrochemical oxidation nor reduction. The exfoliated MoTe2 samples exhibited Tafel slope
of 57 mV/dec and 47 mV/dec for MoTe2 BuLi and MoTe2 Naph, respectively, showcasing the
major improvement in comparison with the Bulk sample. Only minimal differences in Tafel
slope values can be observed for electrochemically treated samples. This is in good agreement
with LSV measurements. WTe2 BuLi and WTe2 Naph (56 mV/dec and 58 mV/dec,
respectively) Tafel slopes also follow the overall HER activity very well. The improvement of
WTe2 ox. HER activity was also confirmed by the decrease of Tafel slope to 42 mV/dec.
Figure 8. Tafel slopes extracted from LSV measurements. Average values and error bars are
based on triplicate measurements.
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In summary, we have thoroughly characterized bulk and chemically exfoliated MoTe2
and WTe2 and tested their activity towards hydrogen evolution reaction. The feasibility of
electrochemical activation via the oxidation or reduction was also inspected. Exfoliation using
both nꢀbutyllithium and sodium naphtalenide led to a dramatic increase in oxygen content.
We attributed this to an increased rate of oxidation caused by increased surface area observed
by SEM. XPS analysis revealed that both metals as well as tellurium were oxidized during the
process of exfoliation. The degree of oxidation of the individual elements was strongly
dependent on the exfoliation route.
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Presence of various reducible/oxidizable surface moieties in the exfoliated
molybdenum and tungsten ditellurides was detected by the inherent electrochemistry
measurements. A variety of different characteristic signals also clearly shows that these
moieties were dependent on used exfoliation agent. With the use of potentials inferred from
the inherent electrochemistry measurements, we have tested the materials for possible
enhancement of catalytic properties. Surface analysis after electrochemical treatment revealed
a very high susceptibility of molybdenum, tungsten as well as tellurite towards oxidation.
Finally HER catalytic activities were determined for all of the studied materials. HER
performance was significantly enhanced in the case of MoTe2 exfoliated with both nꢀ
butyllithium and sodium naphtalenide and both materials performed similarly even after both
electrochemical treatments. More pronounced enhancement was observed for WTe2
exfoliated with sodium naphtalenide. On the other hand, nꢀbutyllithium exfoliated WTe2
showed much more promising possibilities for electrochemical pretreatment activation
surpassing the sodium naphtalenide exfoliated WTe2. Interestingly, despite the very high
degree of corrosion, these materials, especially MoTe2, retain their high HER activity. This is
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of high importance, because the loss of catalytic activity due to surface corrosion is not an
issue in this case.
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EXPERIMENTAL
Materials
Molybdenum powder (99.9%) and tungsten powder (99.9%) were obtained from Alfa Aesar,
Germany. Tellurium (99.999%) was obtained from Mateck, Germany. Nꢀbutyllithium (2.5 M
in hexanes) and sodium (99.9%) were obtained from SigmaꢀAldrich, Czech Republic.
Naphthalene and tetrahydrofuran (THF) were obtained from Penta, Czech Republic.
Synthesis procedures
MoTe2 and WTe2 were prepared by synthesis from elements in evacuated quartz glass
ampoules. Stoichiometric amount of Mo (for MoTe2), W (for WTe2) and Te corresponding to
10g of ditellurides was placed in quartz glass ampoule (100x15mm; 2mm wall thickness) and
evacuated on the base pressure of 1x10ꢀ3 Pa. Subsequently, quartz ampoule was melt sealed
by oxygenꢀhydrogen welding torch. The sample was heated to 600 °C for 48 hours. Ampoule
content was mechanically mixed for 10 minutes and heated to 800 °C for 48 hours and then to
850 °C for 12 hours after the first heating procedure. All heating and cooling rates were 5
°C/min.
Prepared TMDs were then prepared by chemical exfoliation method. Glovebox with an Argon
atmosphere was used for the exfoliation process. Prior to exfoliation, powder samples were
dried at 70 °C for 24h. After cooling down to room temperature, samples were loaded into the
glovebox. Lithium intercalation was performed by stirring 1g of individual TMD with excess
(1.5x moles compared to TMD) of nꢀbutyllithium solution (hexane). Sodium naphtalenide
solution used for exfoliation of 1g of TMD powder was prepared by mixing sodium metal
with naphthalene in dried tetrahydrofuran. Glass coated magnetic stir bars were used to avoid
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fluorine contamination. Intercalated TMDs were then filtered via 0.45 ꢀm nylon membrane.
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30 mL of hexane or 30mL of tetrahydrofuran was used to wash lithium or sodium intercalated
TMDs, respectively. The exfoliated materials were then dispersed in 100 mL of water (under
inert Argon atmosphere) and ultrasonicated for 15 min. Purification was performed by
dialysis and filtration. Prior to any further use, materials were dried in vacuum oven at 50 °C
for 48h.
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Characterizations
Scanning electron microscope (SEM) equipped with FEG source (Tescan Lyra dual
beam microscope) was used for morphology measurements. Energy dispersive spectroscopy
(EDS) analyzer (XꢀMaxN) with a 20 mm2 SDD detector (Oxford instruments) was used for
the measurements of composition. Data were evaluated using AZtecEnergy software. Before
the measurement, samples were placed onto a conductive carbon tape. All measurements were
carried out with 15 kV acceleration voltage.
An inVia Raman microscope (Renishaw, England) with a CCD detector was used for
Raman spectroscopy in backscattering geometry. A NdꢀYAG laser (532 nm, 50 mW) with
50x magnification objective was used for measurements. Instrument calibration was
performed with a silicon reference which gives a peak centre at 520 cm−1 and a resolution of
less than 1 cm−1. In order to avoid radiation damage, laser power output used for this
measurement was kept at 5 mW.
Xꢀray powder diffraction data were collected at room temperature on Bruker D8
Discoverer powder diffractometer (Bruker, Germany) with parafocusing Bragg–Brentano
geometry using CuK
scanned over the angular range 5
was performed in the software package EVA.
α
radiation (
λ
= 0.15418 nm, U = 40 kV, I = 40 mA). Data were
–
90° (2 ) with a step size of 0.019° (2 ). Data evaluation
θ
θ
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ESCAProbeP (Omicron Nanotechnology Ltd, Germany) spectrometer with a
monochromatic aluminium Xꢀray radiation source (1486.7 eV) was used High resolution Xꢀ
ray photoelectron spectroscopy (XPS). Firstly, wideꢀscan survey spectra of all elements were
collected. Highꢀresolution C 1s, Mo 3d, W 4f and Te 3d core level spectra were also recorded.
Relative sensitivity factors were used to evaluate the element concentrations. Samples were
placed onto conductive carbon tape and the electron gun was used to eliminate sample
charging during measurement (1–5 V).
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The electrochemical characterization was performed by cyclic voltammetry using
potentiostat PGSTAT204 (Metrohm Autolab B.V., The Netherlands) with three electrode setꢀ
up. Glassy carbon working electrode (GC), glass carbon auxiliary electrode (GC) and
saturated Ag/AgCl reference electrode were obtained from Gamry (USA). For the inherent
electrochemistry measurements a 1 µl of 1 mg/ml of TMD suspension was dropꢀcasted onto
the surface of GC electrode and dried to obtain a homogeneous layer. CV curves were then
measured in an argon purged 50 mM phosphate buffer solution with a scan rate of 0.1 V/s. A
new portion of material was applied before every measurement. GC electrode was cleaned by
polishing (0.05 ꢀm alumina) before every measurement. Hydrogen evolution reaction (HER)
was performed in argon purged 0.5 M H2SO4 solution with a scan rate of 2 mV/s. All the
measurements were performed three times, always with a new portion of material dropꢀcasted
on the GC electrode. For the electrochemical treatment measurements, materials were
reduced/oxidized at potentials specific for each material, rinsed in distilled water, dried and
then used for individual measurements with conditions described above.
DFT calculations
DFT calculations were performed using the projectorꢀaugmented wave method
implemented in the Vienna Ab initio Simulation Package (VASP).61, 62 The energy cutoff for
the planeꢀwave expansion was set to 350 eV. We used optimized van der Waals functional
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optB86bꢀvdW functional,63 which works very well for both covalent and van der Waals bonds
in layered materials.64 We considered the adsorption of hydrogen onto the surface and edge
sites of single layered ditellurides. The surface (basal plane) was modeled by a 4x4 supercell
(16 Mo or W atoms) in connection with 3x3x1 kꢀpoint sampling. The layers were separated
by 18 Å of vacuum. The edge was modeled by a 4x4 nanostripe, i.e. it contained four atoms
along the edge and the nanostripe was four atoms wide. The nanostripe model of the asꢀ
cleaved edge of the 2H structure exposed both telluride terminated edge and metal terminated
edge. We focused on the metal terminated edge. We used 50 % Te coverage of the metal edge
for both MoTe2 and WTe2 to stabilize dangling bonds at the edge. The Brillouin zone of the
oneꢀdimensional nanostripe was sampled by 1x3x1 kꢀpoints where three kꢀpoints belonged to
the only direction in which the cell was periodically repeated. As the edge contained four
adsorption sites on tellurium atoms, possible hydrogen coverages of the edge were 25%, 50%,
75%, and 100%. The differential energy of adsorption ∆E was calculated as
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∆E= ETOT(n ETOT[(n ETOT(H2)
H*) ꢀ ꢀ1)H*] ꢀ 1/2
The Gibbs freeꢀenergy of the adsorption atomic hydrogen (∆G) was obtained as
∆G=∆E+∆EZPEꢀT∆SH
where, ∆EZPE and ∆SH was the difference in zero point energy, and entropy between the
adsorbed hydrogen and hydrogen in the gas phase. These thermal corrections were found to
be independent of particular adsorption site, and thus ∆G at standard condition was
determined by ∆E plus a thermal correction constant of 0.29 eV.57
AUTHOR INFORMATION
Corresponding Author
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*Zdeněk Sofer, Dept. of Inorganic Chemistry, University of Chemistry and Technology
Prague, Technická 5, 166 28 Prague 6, Czech Republic. Eꢀmail: zdenek.sofer@vscht.cz.
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ASSOCIATED CONTENT
Supporting information.
The EDS maps of exfoliated and nonꢀexfoliated tellurides obtained by SEM and TEM, Xꢀray
diffractograms, Raman spectra of MoTe2 BuLi, XPS survey spectra, high resolution Mo 3d,
W 4f and Te 4f spectra and composition obtained by XPS, composition of tellurides after
electrochemical pretreatment obtained by XPS.
ACKNOWLEDGMENT
Project was supported by Czech Science Foundation (GACR No. 17ꢀ11456S and GACR No.
16ꢀ05167S) and by specific university research (MSMT No. 20ꢀSVV/2017). This work was
created with the financial support of the Neuron Foundation for science support.
AUTHOR CONTRIBUTIONS
M. P. and Z. S. planned and supervised the project. J. L., P. V. and V. M. and D. S. planned
and conducted the experiments. P. L. performed DFT calculations. The manuscript was
written through contribution of all authors.
COMPETITING FINANTIAL INTERESTS
The authors declare no competing financial interests.
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