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Highly Active, Durable Ultrathin MoTe 2 Layers for the Electroreduction of CO

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Highly Active, Durable Ultrathin MoTe2 Layers

for the Electroreduction of CO2 to CH4
Xijun Liu,* Hui Yang, Jia He, Haoxuan Liu, Lida Song, Lan Li, and Jun Luo*

planes with covalently bonded atoms are ver-

The electroreduction of CO2 to CH4 is a highly desirable, challenging research tically stacked via only weak van der Waals
topic. In this study, an electrocatalytic system comprising ultrathin MoTe2 layers interactions, which can be easily mechani-
and an ionic liquid electrolyte for the reduction of CO2 to methane is reported, cally exfoliated to form a few layers.[20] Their
efficiently affording methane with a faradaic efficiency of 83 ± 3% (similar to unique properties, including a large-specific
surface area, abundant low-coordinated sur-
the best Cu-based catalysts reported thus far) and a durable activity of greater
face atoms, and good mechanical stability,
than 45 h at a relatively high current density of 25.6 mA cm−2 (−1.0 VRHE). The make them promising for catalysis.[21–24]
results obtained can facilitate research on the design of other transition-metal Molybdenum ditellurium (MoTe2) is a weyl
dichalcogenide electrocatalysts for the reduction of CO2 to valuable fuels. semimetal, which belongs to the VI A group
of TMDs, with alternately stacked layers of
Mo and Te (TeMoTe).[25–28] Few-layer
1. Introduction MoTe2 exhibits a small indirect band gap of 1.0 eV and a theo-
retical mobility of greater than 200 cm2 V−1 s−1 at room tempera-
CO2 not only is a major contributor to global warming but ture, which has opened new applications in electronics and opto-
also is an abundant C1 feedstock. CO2 electroreduction, which electronics.[29–31] Such structural and electrical features render it
is powered by renewable energy, has attracted considerable promising for the realization of rapid electron transport during
attention for the simultaneous reduction of CO2 emissions electroreduction, which in turn may ensure long-term durability.
and reduction of environmental concerns.[1–3] In particular, C1 Hence, it demonstrates promise as a CO2 electroreduction cata-
compounds with a high-energy density, such as methane (CH4) lyst. However, the application of few-layer MoTe2 nanosheets for
and formic acid (HCCOH), are compatible with existing infra- the electroreduction of CO2 has not been reported to the best of
structures and can be substituted for fossil fuels.[4–7] Among our knowledge. Besides, ionic liquids (ILs), which are molten
the currently available materials, Cu-based catalysts have dem- salts with low volatility and high ionic conductivity, have attracted
onstrated promise for the catalysis of CO2 to CH4.[8–18] How- considerable attention for the electroreduction of CO2 as electro-
ever, high CH bond strength (434 kJ mol−1) and eight-electron lytes.[7,32,33] Catalysts and electrolytes are crucial for electroreduc-
transfer typically induce poor selectivity and a high applied tion and significantly affect the electroreduction products.
potential for these catalysts, making it unrealistic to use these Inspired by the above advantages, an ultrathin MoTe2 elec-
catalysts for practical applications.[13–16] trode/IL electrolyte system was innovatively established for the
Recently, transition-metal dichalcogenides (TMDs) have been electroreduction of CO2. To the best of our knowledge, this mate-
attracting increasing attention for the electroreduction of CO2 rial is a new electrocatalyst for the selective reduction of CO2 to
because of their unique layered structures.[19–21] In particular, their produce methane. The as-prepared catalyst exhibited a faradaic
efficiency (FE) of 83 ± 3% at a moderate applied potential of
−1.0 VRHE for methane production in an electrolyte consisting of
Dr. X. J. Liu, Dr. J. He, H. X. Liu, L. D. Song, Prof. J. Luo 1-butyl-3-methylimidazolium tetrafluoroborate ([Bmim]BF4) and
Center for Electron Microscopy water. This value corresponded to ≈137% increment as compared
Tianjin Key Lab of Advanced Functional Porous Materials
Institute for New Energy Materials and Low-Carbon Technologies with that of its bulk counterpart; this value is also comparable to
School of Materials Science and Engineering that for the best Cu electrodes reported previously under similar
Tianjin University of Technology test conditions.[9,11] Notably, this electrode can continuously pro-
Tianjin 300384, China duce methane for greater than 45 h with an FE of greater than
E-mail: xjliu@tjut.edu.cn; jluo@tjut.edu.cn
80%, indicative of their extremely favorable stability. Hence, the
Dr. H. Yang, Prof. L. Li
Tianjin Key Laboratory for Optoelectronic Materials and Devices
study reported herein can open new avenues for the develop-
Key Laboratory of Display Materials and Photoelectric Devices ment of highly efficient, robust TMD-based electrocatalysts.
Ministry of Education
School of Materials Science and Engineering
Tianjin University of Technology
Tianjin 300384, China 2. Results and Discussion
The ORCID identification number(s) for the author(s) of this article
can be found under https://doi.org/10.1002/smll.201704049.
First, ultrathin MoTe2 layers were synthesized by chemical
vapor deposition, followed by ultrasonic exfoliation (Figure 1,
DOI: 10.1002/smll.201704049 for more details see Supporting Information).[34,35]

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Figure 1. Schematic representation for the synthesis of ultrathin MoTe2 layers.
Transmission electron microscopy (TEM) images were recorded
to examine the morphology of the mechanically exfoliated
MoTe2 layers and Figure 2a shows a typical TEM image: Several
aggregated ultrathin flakes were observed. Figure 2b shows the
high-resolution TEM (HRTEM) image: Clear lattice fringes with
an interplanar distance of 0.3 nm were observed, which were
indexed to the d-spacing of the (100) plane of 2H-MoTe2. Atomic
force microscopy (AFM) images were recorded to confirm the
thickness of the ultrathin flakes. Clearly, the typical thickness of
a single MoTe2 flake was ≈2.1 nm, with a size of several square
micrometers (Figure 2c). From the cross-sectional HRTEM
image in Figure S1 (Supporting Information), the interlayer
spacing was measured to be 0.69 nm, very close to the reported
value (0.7 nm),[35] indicating that ultrathin MoTe2 flakes have
three layers. By contrast, the typical thickness of bulk MoTe2 was
greater than 300 nm (Figure S2, Supporting Information). High-
angle annular dark-field scanning TEM (HAADF-STEM) and
the corresponding energy-dispersive X-ray spectroscopy (EDX)
mapping images were recorded to confirm the composition of
the MoTe2 flakes (Figure 2d): A homogeneous spatial distribu-
tion of Mo and Te was observed over a single flake. Interestingly,
it seemed in some regions that Te is significantly concentrated,
implying the presence of excess Te in the MoTe2 flakes.
To further confirm the formation of 2H-MoTe2, X-ray dif-
fraction (XRD) and X-ray photoelectron spectroscopy (XPS)
were utilized to examine the crystal phase and chemical struc-
ture of as-prepared MoTe2. The diffraction peaks observed in
the XRD pattern (Figure 3a) corresponded to hexagonal-phase
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MoTe2 (JCPDS card no. 73–1650); this result
is in good agreement with those observed
by HRTEM. Dominant diffraction peaks
were observed at 35.2°, 29.3°, and 25.5°,
corresponding to the (103), (100), and (004)
planes of 2H-MoTe2, respectively. In addi-
tion, a tiny diffraction peak at 27.6° could
be attributed to Te phase (JCPDS card no.
36–1452), which fairly agrees well with the
EDX results (Figure 2d). XPS was utilized
to further confirm the electronic states and
bonding types of molybdenum and tellurium
in the ultrathin MoTe2 layers. In the high-
resolution Mo 3d and Te 3d spectra, Mo3d5/2
and Mo 3d3/2 peaks were observed at 228.8
and 231.8 eV, respectively, corresponding
to the MoTe bonds in 2H-MoTe2[36,37]
(Figure 3b). Weak peaks were observed
at 232.9 and 236.0 eV, corresponding to
MoO bonds. Te 3d5/2 and Te 3d3/2 peaks
were observed at 573.5 and 583.8 eV, respec-
tively, corresponding to the MoTe bonds
in 2H-MoTe2[36,37] (Figure 3c). Small peaks
were observed at 576.6 and 587.0 eV, corre-
sponding to the TeO impurity. These two
shoulder peaks of MoO and TeO corre-
sponded to the oxidation products of MoTe2
because of the facile oxidation of MoTe2 in
air.[36,37]
Further, ultrathin MoTe2 layers were used
as the cathodic catalyst and their electrocata-
lytic performance for CO2 reduction was measured in a typical
three-electrode setup using BmimBF4-H2O (with a mass ratio
of 96: 4) as the electrolyte. In addition, the catalytic activity of
bulk MoTe2 was measured for comparison. All potentials were
reported with respect to the reversible hydrogen electrode
(RHE), and each current density was normalized by the geo-
metric area of the electrode. From linear sweep voltammetry
(LSV) curves (Figure 4a), the two electrodes showed higher
current densities under CO2 atmosphere than Ar atmosphere,
demonstrating that both of them have electrocatalytic activity
toward CO2 reduction. The ultrathin MoTe2 electrode exhibited
a reduction current density of 25.6 mA cm−2 at −1.0 VRHE; this
value is 2.5 times greater than that of the bulk one, indicative
of higher electrocatalytic activity for CO2 reduction over the
ultrathin MoTe2 layers as compared to the bulk counterpart.
Gas chromatography was employed for the qualitative anal-
ysis of the gaseous products after 2 h of electrolysis at regular
time intervals. Figure 4b shows the dependence of FE for
methane selectivity on the applied potential for both electrodes.
At a low applied potential of −0.8 VRHE, an FE of 34 ± 4% for
methane production was observed over the ultrathin MoTe2
electrode, while CO (41 ± 3%) and H2 (22 ± 5%) were the
dominant products (Figure S3, Supporting Information).
With the further increase in the negative potential, the max-
imum FE (FEmax) of 83 ± 3% at −1.0 VRHE was achieved with
≈15% of CO and ≈5% of H2. This change in activity can be
attributed to the following reasons: (i) at different applied
potentials, the deviation with respect to the equilibrium
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Figure 2. Morphological characterization of ultrathin MoTe2 layers. a) TEM image, b) high-magnification TEM image, c) AFM image, and d) HAADF
STEM image and the corresponding EDX elemental mapping images of Mo and Te.

potential of the target product will impact the reaction pathway
of CO2 electroreduction and thereby led to the variation of the
reduction products, which in turn results in a change of the
FE for the target product[38,39]; (ii) the hydrogen evolution reac-
tion (HER) as the competing reaction also induces the change
in efficiency. The total FEs consistently reached 90%–103% at
all potentials where methane was selectively produced, indi-
cating that the electroreduction of CO2 is more favorable com-
pared to the HER. By contrast, for the bulk counterpart, the
FEmax of the methane was 35 ± 3%; this value is considerably
less than that of the ultrathin MoTe2 electrode. Meanwhile,
H2 was the dominant product over CO at all of the tested poten-
tials (Figure S4, Supporting Information), with the total FEs
maintained at 60%–70%. The monolithic contrast between
the two electrodes was clearly revealed in the column graph
(Figure S5, Supporting Information), indicating that ultrathin
MoTe2 layers serve as an efficient catalyst for the electroreduc-
tion of CO2 to methane with considerably suppressed H2 evo-
lution, corresponding to the fact that ultrathin layers benefit
mass transport and provide a high number of catalytically active
site, thereby improving the CO2 electroreduction performance.
Furthermore, Figure 4c and Table S1 (Supporting Information)
show the comparison of FEmax values versus CH4 between those
reported previously and our study.[7,9,11,40,41] As seen, to the best
of our knowledge, in aqueous solution, the best FEmax value for
Cu-based catalysts is 85%;[9] while for non-Cu-based catalysts,
this value is ≈22%.[40] In IL-based systems, the N-doped carbon
electrode gives a FEmax of 93% for CH4 production, which is
the best reported value thus far.[7] Clearly, the resulting FEmax
value of the ultrathin MoTe2 electrode is comparable to the best
results reported in the literature.
Stability under long-term electrolysis is another crucial factor
for evaluating the CO2 reduction performance (Figure 4d).
The reduction current density was relatively stable (high up to
25.6 mA cm−2 at −1.0 VRHE) even after 45 h. Notably, the cor-
responding FE for methane production was consistently main-
tained to be greater than 80% during electrocatalysis. These
values for the ultrathin MoTe2 electrode are comparable to
those observed for the previously reported electrocatalysts both
in ILs and aqueous solution (Table S1, Supporting Informa-
tion).[7,9,11,40,41] Therefore, ultrathin MoTe2 layers demonstrate
immense potential for practical applications.
In addition, based on the above EDX and XRD results, it can
be found that there is excess Te in the ultrathin MoTe2 sample.
To determine the effect of Te on CO2 electroreduction, FE for
CO2 reduction on Te powder was determined to evaluate its

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Figure 3. Chemical analysis of the ultrathin MoTe2 layers. a) XRD patterns and XPS spectra of b) Mo 3d and c) Te 3d.

performance (Figure S6, Supporting Information). Notably, the ultrathin MoTe2 electrode (83 ± 3% at −1.0 V). Therefore,
H2 was the main product over all the applied potentials. Mean- we can reasonably infer that this excess Te has a little impact
while, the maximum FE for CH4 production over the Te powder on the CH4 production. Moreover, we also investigated the
electrode was 5.3 ± 0.2% at −1.05 V, much smaller than that of electrochemical performance using the ultrathin MoTe2

Figure 4. CO2 electroreduction performance in a CO2-saturated BmimBF4-H2O electrolyte. a) LSV curves at a scan rate of 10 mV s−1, b) FEs for methane
at various applied potentials, c) comparison between the FEs versus CH4 obtained with MoTe2 and those reported electrocatalysts, d) chronoamper-
ometry curve at a potential of −1.0 VRHE and the corresponding FE of methane.

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Figure 5. CO2 electroreduction mechanism. a) CO2 adsorption isotherms, b) charging current density differences plotted against scan rates, c) Tafel
plots, and d) schematic representation for the electroreduction of CO2 into methane on the ultrathin MoTe2 layers.
electrode in 0.1 m KHCO3 solution (Figure S7, Supporting
Information). As a control, the ultrathin MoTe2 electrode
showed an inferior activity for CO2 electroreduction but pre-
dominantly HER. This result further confirmed that the ionic
liquids played an important role in the electroreduction of CO2
to methane over the ultrathin MoTe2 electrode.
Notably, the clearly enhanced catalytic activity and faradaic
efficiency are partially related to the ultrathin structure and
increased active sites. To confirm this viewpoint, volumetric
CO2 adsorption measurement was first carried out to explore
the reason for the enhanced electrocatalytic activity (Figure 5a).
Ultrathin MoTe2 layers exhibited a CO2 adsorption capacity
of 23.3 cm3 g−1 at 298 K and 1 atm; this value is ≈1.9 times
greater than that of the bulk counterpart, indicative of a larger
surface area for CO2 adsorption. This is beneficial for the
initial step before the reduction of CO2 to the CO2•− intermedi-
ates and subsequent reduction. In addition, the electrochemi-
cally active surface areas of the electrodes were determined by
the measurement of the double-layer capacitance (Cdl).[42] The
measured Cdl of the ultrathin MoTe2 layers was 67 mF cm−2
(Figure 5b); this value is greater than that of the bulk counter-
part (47 mF cm−2), confirming the exposure of an increased
number of catalytically active sites, and hence, enhanced elec-
trocatalytic activity. Moreover, using ionic liquids with fluorine
as the electrolyte ensures high ionic conductivity and rapid
electron transport; in addition, fluorine exhibits a stronger
interaction with CO2, facilitating the transformation of CO2
to CO2•− intermediates[7,43,44] and eventually improving the
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electrochemical process effectively. Overall, by integrating the
above-mentioned advantages, ultrathin MoTe2 layers exhibited
excellent electrochemical activity for the electroreduction of
CO2 into methane.
To further disclose the kinetic mechanism of CO2 reduction
on both catalysts, Tafel analysis was carried out (Figure 5c). In
the linear Tafel region, bulk MoTe2 exhibited a Tafel slope of
112 mV dec−1, indicating that the initial transfer of one elec-
tron from CO2 to CO2•− species is the rate-determining step
for this electroreduction.[45] In contrast, ultrathin MoTe2 layers
exhibited a low Tafel slope (68 mV dec−1); this value is similar
to the theoretical value (59 mV dec−1).[11] On the basis of the
Tafel results and the previously reported works,[7,11] a possible
mechanism for CO2 electroreduction to CH4 on the ultrathin
MoTe2 electrode was proposed (Figure 5d). Initially, a CO2
mole­cule is adsorbed on the surface of MoTe2 and then reduced
to generate CO2•−. After that, the adsorbed CO2•− couples with
a Lewis acid CO2 molecule from the electrolyte to form a
CO2CO2•− adduct, and this step is identified as the rate-lim-
iting step (RLS). Finally, the CO2CO2•− adduct undergoes the
subsequent proton–electron transfer reactions to produce CH4.
The theoretical Tafel slope[11] for this proposed mechanism is
59 mV dec−1. Meanwhile, it should be noted that the obtained
Tafel slope of the ultrathin MoTe2 electrode is 68 mV dec−1, very
close to the theoretical one. Moreover, previous work[42,45,46]
on the transition-metal dichalcogenides (such as CuS, MoSeS,
and SnS2) has confirmed the CO2 electroreduction takes place
on metal atoms. Therefore, we can consider that the CO2
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Figure 6. Calculated TDOS for MoTe2 monolayer and bulk MoTe2. The
blue-dotted line represents the Fermi level (EF).
electroreduction to CH4 on MoTe2 also involves the above steps
including the RLS.
To further gain mechanistic insights of the promoted elec-
trocatalytic performances, density functional theory calcu-
lations were performed to obtain the total density of states
(TDOSs) of MoTe2 monolayer and bulk counterpart.[47–49] As
shown in Figure 6, the TDOSs calculated for MoTe2 monolayer
and bulk counterpart are continuous near the Fermi level
(EF), indicating that the two samples possess a good electrical
conductivity.[50,51] Generally, a good electrical conductivity will
impart MoTe2 with fast electron transfer and ion diffusion
rates, and thus a catalytic improvement for CO2 electroreduc-
tion. Moreover, the highest peak of TDOSs for MoTe2 mon-
olayer (Ep = −1.48 eV) approach much closer to EF as com-
pared to the bulk counterpart (Ep = −1.57 eV). This result
demonstrates that MoTe2 monolayer possibly has a stronger
interaction with the generated intermediates during CO2
electroreduction.[51,52]
3. Conclusion
In conclusion, an ultrathin MoTe2 electrode/IL electrolyte
system was developed for CO2 reduction. This system exhibited
a relatively high reduction current density of 25.6 mA cm−2 at a
moderate applied potential (−1.0 VRHE) for the electroreduction
of CO2 to methane, with an FEmax (83 ± 3%) and good dura-
bility (45 h). These results were related to the ultrathin struc-
ture, increased abundance of the exposed active sites, and the
use of the IL electrolyte. The results obtained from this study
will encourage the research on the design of other transition-
metal dichalcogenide electrocatalysts for the reduction of CO2
to energy-rich products.
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Supporting Information
Supporting Information is available from the Wiley Online Library or
from the author.
Acknowledgements
X.J.L. and H.Y. contributed equally to this work. This work was
financially supported by the National Natural Science Foundation of
China (21601136), Tianjin Municipal Education Commission (Grant
No. 20140301), National Program for Thousand Young Talents of
China, the Tianjin Municipal Science and Technology Commission
(15JCYBJC52600), and the Fundamental Research Funds of Tianjin
University of Technology.
Conflict of Interest
The authors declare no conflict of interest.
Keywords
CO2 reduction, ionic liquids, methane, MoTe2
Received: November 19, 2017
Revised: January 27, 2018
Published online:
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