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Porous and single-crystalline-like molybdenum


nitride nanobelts as a non-noble electrocatalyst for
alkaline fuel cells and electrode materials for
supercapacitors

J. Liu a,b,**, K. Huang c, H.L. Tang d, M. Lei c,*


a
Institute for Superconducting and Electronic Materials, University of Wollongong, NSW, 2522, Australia
b
School of Materials Science and Engineering, Central South University, Changsha, Hunan, 410083, China
c
State Key Laboratory of Information Photonics and Optical Communications & School of Science, Beijing University
of Posts and Telecommunications, Beijing, 100876, China
d
State Key Laboratory of Advanced Technology for Materials Synthesis and Processing, Wuhan University of
Technology, Wuhan, 430070, China

article info abstract

Article history: Replacing precious and nondurable Pt catalysts with cheap materials is a key issue for
Received 13 August 2015 commercialization of fuel cells. Intriguing transition metal nitrides (TMNs) have attracted
Received in revised form great attentions as promising economic alternatives to Pt catalysts due to their noble
26 October 2015 metal-like properties. However, most of as-synthesized TMNs are nanoparticles until now.
Accepted 17 November 2015 Clearly, the practical catalytic activities of such materials have hitherto been intrinsically
Available online xxx restricted by the relatively small surface area and poor crystallinity of nanoparticles. Here,
highly porous and “single-crystal-like” Mo2N nanobelts with high density of nanopores
Keywords: have been synthesized on gram-scale. These novel Mo2N nanobelts exhibited high elec-
Porous Mo2N nanobelts trocatalytic activity in alkaline electrolyte even better than that of other non-Pt materials
Oxygen reduction reactions and appear to be promising Pt-free cathodic electrocatalysts in alkaline fuel cells.
AFCs This discovery reveals a new type of metal nitride ORR catalyst and appear to be promising
Supercapacitors Pt-free cathodic electrocatalysts in alkaline fuel cells.
Copyright © 2015, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights
reserved.

high efficiency, low cost and environmental benignity. Fuel


Introduction cells and supercapacitors as promising energy conversion and
storage units have been widely studied for applications in
Increasing energy demands have stimulated intense research stationary power sources and battery powered electric vehi-
on alternative energy conversion and storage systems with cles [1]. However, the fact that their performance requires

* Corresponding author. Tel./fax: þ86 10 62282050.


** Corresponding author. Institute for Superconducting and Electronic Materials, University of Wollongong, NSW, 2522, Australia. Tel./
fax: þ86 10 62282050.
E-mail addresses: liujun4982004@csu.edu.cn (J. Liu), minglei@bupt.edu.cn (M. Lei).
http://dx.doi.org/10.1016/j.ijhydene.2015.11.086
0360-3199/Copyright © 2015, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.

Please cite this article in press as: Liu J, et al., Porous and single-crystalline-like molybdenum nitride nanobelts as a non-noble elec-
trocatalyst for alkaline fuel cells and electrode materials for supercapacitors, International Journal of Hydrogen Energy (2015), http://
dx.doi.org/10.1016/j.ijhydene.2015.11.086
2 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y x x x ( 2 0 1 5 ) 1 e6

continuous improvement, has encouraged ever greater sci- electrodes because of their high conductivity, low cost and
entific efforts toward the search for new materials that could high chemical resistance [8].
replace the current state-of-the-art materials. As well known, material surfaces play an important role in
Catalysts for oxygen reduction reactions (ORR) are at the the catalytic activity and capacitance. The effective integra-
heart of key renewable-energy technologies for fuel cells [2,3]. tion of high surface areas and good crystallinity is expected to
Pt and its alloys remain the most efficient ORR catalysts, but be very effective in promoting their catalytic activity and
the high cost and scarcity of Pt hamper further development capacitance. However, unlike metal oxides and main group
of fuel cell technologies based on these materials. Although a metal nitrides with rich nanostructure morphologies, most of
broad range of alternative catalysts based on nonprecious as-synthesized TMNs are nanoparticles until now [8]. Clearly,
metals (Fe, Co, etc.), metal oxides (Fe2O3, Fe3O4, Co3O4, IrO2, the practical catalytic activity and capacitance of such mate-
etc.), nitrogen-coordinated metal on carbon, and metal-free rials have hitherto been intrinsically restricted by the rela-
doped carbon materials have been actively pursued [4], the tively small surface area and poor crystallinity of
development of novel non-noble catalysts which can substi- nanoparticles. Therefore, it is highly desirable to accomplish
tute platinum-based catalysts are strongly required. TMN nanostructures with high surface area and good crys-
The most widely used active supercapacitor electrode tallinity to enhance their catalytic activities and improve their
materials are carbon, conducting polymers or transition metal capacitances for supercapacitors.
oxides (TMOs) [5]. TMOs characterized by their low-cost Herein, we successfully synthesize gram-scale, highly
and high specific capacitance (such as, MnO2 generally with porous and “single-crystal-like” [11] Mo2N nanobelts with high
the capacitance of 100e160 F/g [6], MoO2 with a capacitance of density of ultra-fine nanopores by topotactic chemical trans-
140 F/g [7]), have attracted significant interest as active elec- formation from single crystal MoO3 nanobelts. Although
trode materials for supercapacitors instead of carbon. How- traditional solid-state nitriding reaction using micrometer- or
ever, their poor electrical conductivity and mechanical issues larger-sized powders is known to be a brute-force technique
such as low structural stability exist for TMO electrodes [6], for the synthesis of many porous metal nitride materials [12],
often resulting in degraded long-term electrochemical cycla- it has disadvantages: it requires diffusion over long distance;
bility and limited rate capability. large strain nucleation barriers must be overcome; the pore
Intriguing transition metal nitrides (TMNs) have been sizes are large; and the microstructure of the final materials is
widely studied due to their scientific and technological difficult to control. However, these disadvantages might be
importance [8]. The band structure of TMNs is qualitatively ameliorated or eliminated by using nanocrystalline materials
similar to those of fcc transition metals in the shape and as starting reactants. For example, ZnO NWs have been con-
relative ordering of the bands. For the transition metals, the verted into single-crystalline ZnAl2O4 spinel nanotubes via
d-band begins to fill from Ru and Os to Pd and Pt. This solid-state reaction [13]. In our work, single crystal MoO3
coincidence of the band structure seems responsible for the nanobelts have been converted into highly porous and single-
observed similarity in catalytic properties between Group 4e6 crystalline-like Mo2N nanobelts via a slowly nitrided solid-
TMNs and the Group 8e10 transition metals [8]. The elec- state reaction. Such single-crystal-like Mo2N nanobelts are
tronic structure strongly related with properties of TMNs here reported as promising Pt-free cathodic electrocatalysts in
studied by various spectroscopic techniques. Thus, the filled alkaline fuel cells for the first time, exhibiting high electro-
states of d-band were narrowed after formation of nitrides, catalytic activity toward oxygen reduction. Highly porous
resulting in the similar electronic structure of noble metals Mo2N nanobelts also exhibited high rate capability, high spe-
up to the Fermi level. On the other hand, at energies above cific capacitance of 160 F/g (higher than those of MnO2
the Fermi level, the width of the unfilled states of the metal generally with the capacitance of 100e160 F/g [6], or MoO2
was found to be broadened because of the TMNs formation, with a capacitance of 140 F/g [7]), and good cycling stability,
giving rise to a greater density of empty levels for TMNs than even at the high scanning rate of 100 mV s1, as super-
those of the parent metal. Due to the deficiency in the d-band capacitor electrode materials. The high catalytic activity and
occupation near the Fermi level, nitride surfaces could have a capacitance may result from its novel nanostructures with the
reduced ability to donate d-electrons to adsorbates. There- effective integration of their high surface area and good
fore, high reactivities of early transition metals are explained crystallinity. This discovery reveals a new type of metal
by the formation of nitrides for reactions involving the nitride ORR catalyst and appear to be promising Pt-free
donation of electrons from the metal catalysts to absorbate. cathodic electrocatalysts in alkaline fuel cells.
The broadened unfilled portion of the d-band should make
these nitrides better electronic acceptors than both the
parent metals and the Pt Group metals. Thus for reactions Experimental
that involve the donation of bonding electrons to the unfilled
orbitals of the metal substrate, nitride catalysts might be Single-crystal-like Mo2N nanobelts with high density of ultra-
more efficient than both parent metals and Pt Group metals, fine nanopores were easily obtained by a two-step route. The
such as, Cu3N nanocubes as promising Pt-free cathodic first step is gram-scale synthesis of single-crystalline and
electrocatalysts for alkaline fuel cells (AFCs) [9], and Mo2N/C uniform MoO3 nanobelts. In a typical synthesis, MoO3 powder
as Pt-free cathodic electrocatalysts for proton exchange (2 g, 99.99%, Sigma Aldrich) and 20 mL of 30% H2O2 (Sigma
membrane fuel cells (PEMFCs) [10]. Some TMNs (such as, VN, Aldrich) were mixed under vigorous magnetic stirring over-
MoNx TiN, and WN) have been also attracted great attentions night until the solution was clear yellow, and then 20 mL H2O
as replacements for MnO2 and RuO2 in supercapacitor was added to the solution before transferring to a 120 mL

Please cite this article in press as: Liu J, et al., Porous and single-crystalline-like molybdenum nitride nanobelts as a non-noble elec-
trocatalyst for alkaline fuel cells and electrode materials for supercapacitors, International Journal of Hydrogen Energy (2015), http://
dx.doi.org/10.1016/j.ijhydene.2015.11.086
i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y x x x ( 2 0 1 5 ) 1 e6 3

Teflon™ liner. The liner with its contents was then assembled relatively low at 600  C, synthesized product is pure stable
into an autoclave and kept in an oven at 190  C for 12 h. The phase Mo2N and no metastable phase MoN in it. If the syn-
product was washed with anhydrous ethanol and distilled thesis temperature is lower than 600  C, we found that the
water several times. Finally, it was dried at 80  C in vacuum for synthesized product consisted stable phase Mo2N and meta-
12 h. The second step is the synthesis of highly porous single- stable phase MoN. The synthesized Mo2N nanobelt is not a
crystalline Mo2N nanobelts transformed from single- polycrystalline nanobelt, but a single-crystal-like nanobelt
crystalline MoO3 nanobelts. In a typical run, single- [11]. Gram-scale synthesis of uniform and monodisperse
crystalline MoO3 nanobelts were slowly nitrided at 600  C for MoO3 nanobelts was achieved by a solvothermal method,
2 h under the mixed gas (10% NH3 and 90% N2) flow at 500 which is shown in the experimental section.
standard cubic centimeters per minute (sccm) and normal Fig. SI-1(a) (shown in the Supporting Information) shows x-
pressure. The heating rate of MoO3 nanobelts are 20  C per ray diffraction patterns (XRD) of the products in the first step
minute from room temperature to 600  C. (a) and the second step (b). The XRD pattern of the products in
For the supercapacitance tests, the Mo2N nanobelts were the first step can be well indexed to an orthorhombic cell with
mixed with acetylene black and poly (vinylidene fluoride) in a ¼ 3.9418  A, b ¼ 13.8137 
A and c ¼ 3.6842 
A, in good agreement
an 8:1:1 ratio. N-methyl-2-pyrrolidone was used as a solvent to with the standard data (ICDD-PDF 05-0508), confirming
form homogeneous slurry, which was then pasted on a 1 cm2 that the products obtained in the first step are MoO3 with an
piece of steel mesh and dried under vacuum at 60  C for 24 h. orthorhombic structure. As shown in Fig. SI-1(b), the XRD
Capacitance tests were run in an open beaker with a 3 elec- pattern of the products obtained in the second step can be
trode setup. The reference electrode used was Ag/AgCl (satu- well indexed to a cubic cell with a ¼ b ¼ c ¼ 4.163  A, in good
rated KCl), the counter electrode was platinum foil agreement with the standard data (ICDD-PDF 25-1366),
(1.5 cm  1.5 cm), and the electrolyte was 1 M H2SO4. All the Moreover, Energy dispersive spectroscopy (EDS) reveals that
tests were performed on a CHI660C workstation. the products consist of the elements Mo and N, and the atom
ratio is 2:1, showing in Fig. SI-2. These results can confirm that
these products are pure Mo2N with a cubic structure. The full
Results and discussion width at half maximum (FWHM) of each peak of Mo2N is larger
than that of MoO3.
Synthesis of porous Mo2N nanobelts is based on slowly The scanning electron microscope (SEM) images in Fig. SI-
nitriding MoO3 nanobelts, and is schematically displayed in 3(a), (b), (c), and (d) show that the products synthesized by the
Fig. 1. Such a solid-state nitriding reaction has been reported solvothermal method consist of a large amount of MoO3
to synthesize porous Mo2N micropowders and microfibers nanobelts with a uniform thickness of about 40 nm. The
[14,15]. Compared to these previous works, our products, the transmission electron microscope (TEM) images in Fig. SI-4
Mo2N nanobelts, have a high density of ultra-fine nanopores indicate that these MoO3 nanobelts are single crystals with
due to the short diffusion distance and the low synthesis excellent crystallinity and grow along the [001] direction. The
temperature in the reaction using nanomaterials as starting SEM images in Fig. 2(a) and Fig. SI-5 show that the nitrided
reactants. Since the atom diffusion distance is short and small samples retain the size and shape of the precursor. The
strain nucleation barriers should be overcome in the reaction disordered mesoporous structure is clearly shown by the TEM
using nanomaterials as starting reactants, the synthesis images in Fig. 2(b) and Fig. SI-6; nevertheless, a selected-area
temperature will be relatively low and the morphology can electron diffraction (SAED) pattern recorded on the crystal
be well controlled. Although the synthesis temperature is (inset) shows a diffraction pattern of single-crystal cubic Mo2N

Fig. 1 e Schematic diagram of the procedure used to fabricate single-crystalline-like Mo2N nanobelts with high density of
ultra-fine nanopores.

Please cite this article in press as: Liu J, et al., Porous and single-crystalline-like molybdenum nitride nanobelts as a non-noble elec-
trocatalyst for alkaline fuel cells and electrode materials for supercapacitors, International Journal of Hydrogen Energy (2015), http://
dx.doi.org/10.1016/j.ijhydene.2015.11.086
4 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y x x x ( 2 0 1 5 ) 1 e6

Fig. 2 e (a) SEM image, and (b) TEM image and corresponding SAED pattern (inset) of as-synthesized porous Mo2N nanobelts.

along the [001] zone axis. HRTEM image (Fig. SI-6d) further potential range (0.5eþ0.5 V vs. Hg/HgO). These results differ
shows the single-crystal lattices with embedded 2e5 nm from other reports on non-noble ORR catalysts such as FeeN/
mesopores. Nevertheless, to distinguish such crystals from C containing instable metal ions that present redox couples in
the traditional single crystals, we termed these crystals the electrochemical range [20]. The CV curve recorded from O2
“single-crystal-like” crystals [10]. Compared to the specific saturated solution exhibited a pronounced electrocatalytic
surface areas of some reported metal nitride nanoparticles, activity associated with an ORR onset potential at about
such as Mo2N nanoparticles with a specific surface area below 0.03 V vs Hg/HgO. The cathodic current density achieved a
12 m2 g1 [16,17], TaN nanoparticles with a specific surface high value of 2.96 mA cm2 at 0.17 V vs Hg/HgO, better than
area up to 61 m2 g1 [18], and AlN nanoparticles with a specific that of other non-Pt materials, such as three-dimensional N-
surface area up to 36.4 m2 g1 [19], BrunauereEmmetteTeller doped graphene aerogel-supported Fe3O4 nanoparticles [21],
(BET) analysis of the porous Mo2N nanobelts yields a specific TiN nanoparticles supported on the CNTegraphene hybrid
surface area up to 197.4 m2 g1. The pore size distribution of [22] and cubic Cu3N nanocrystals [9].
the porous Mo2N nanobelt sample ranged from 1.8 nm to Subsequently, to examine the ORR kinetics and the corre-
10 nm, and from 100 nm to 250 nm, with a maximum at sponding kinetic parameters for the novel Mo2N nanobelts,
3.4 nm, as shown in the inset of Fig. SI-7. The pores ranging linear sweep voltammograms (LSVs) were recorded at various
from 1.8 nm to 10 nm correspond to the small pores formed in electrode rotation rates from 400 to 2000 rpm, in an O2 satu-
Mo2N nanobelts, but the pores ranging from 100 nm to 250 nm rated solution with a rotating disk electrode (RDE) (Fig. 3(b)).
correspond to the holes between the different Mo2N The current shows the typical increase with rotation rate due
nanobelts. to the shortened diffusion layer. At the potential range of
Oxygen reduction reaction (ORR) activity of porous Mo2N 0.03 to 0.08 V vs. Hg/HgO, the disk current density (id) dis-
nanobelts is performed using cyclic voltammetry (CVs) in N2 played purely electrochemical kinetic current densities inde-
and O2 saturated 0.1 M aqueous KOH electrolyte solutions pendent on the electrode rotation rate. The exchange current
with scan rate of 100 mV s1 (Fig. 3(a)). No significant peak density (io) calculated through a Tafel equation is about
oxidation or reduction current peak is observed in the CV 8.2  107 A/cm2. The number of electrons transferred (n) is
curve recorded from N2 saturated solution, indicating that the calculated to be ~2.35 at 0.2 to 0.5 V vs. Hg/HgO from the
novel catalyst is electrochemically stable over the entire slopes of the Koutecky-Levichplots [23], suggesting that the

Fig. 3 e (a) Cyclic voltammetry of porous Mo2N nanobelts as ORR catalysts in N2-saturated 0.1 M KOH. Scan rate: 100 mV s¡1;
(b) Linear sweep voltammograms of porous Mo2N nanobelts as ORR catalysts in O2-saturated 0.1 M KOH at different rotating
disk electrode rotation rates. Scan rate: 10 mV s¡1.

Please cite this article in press as: Liu J, et al., Porous and single-crystalline-like molybdenum nitride nanobelts as a non-noble elec-
trocatalyst for alkaline fuel cells and electrode materials for supercapacitors, International Journal of Hydrogen Energy (2015), http://
dx.doi.org/10.1016/j.ijhydene.2015.11.086
i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y x x x ( 2 0 1 5 ) 1 e6 5

ORR catalyzed by the porous Mo2N nanobelts is a mixed pro- possibly because of their high conductivity and highly porous
cess of 2- and 4-electron transfer. framework structure, which facilitate the electrolyte pene-
The cycling stability of the porous Mo2N nanobelts as tration and provide very efficient pathways for ion and elec-
supercapacitor electrode material is demonstrated in Fig. 4(a). tron transportation. The porous framework with high surface
It is interesting that the decay in specific capacitance based on area and good crystallinity could also help to maintain the
this maximum value (160 Fg1) after a 1000-cycle test is only integrity of the material structure during charge/discharge
9%, even at the high scan rate of 100 mV1. Although the cycling and therefore, contribute to the excellent cycling
capacitance of porous Mo2N nanobelts for supercapacitors is performance of the Mo2N electrode.
lower than those of NiO with a capacitance of 585 F/g [24] and
Co3O4 with a capacitance of 599 F/g [25], it is still higher than
those of MnO2 generally with the capacitance of 100e160 F/g Conclusions
[6], or MoO2 with a capacitance of 140 F/g [7]. Most impor-
tantly, such porous Mo2N nanobelts exhibit extremely high As a summary, we report that gram-scale synthesis of highly
rate capability as supercapacitor electrodes, which is exhibi- porous and single-crystal-like Mo2N nanobelts with high
ted in the CV curves at scanning rates from 5 to 100 mV1 density of nanopores. This strategy only involves a slowly
(Fig. 4(b)). Generally, the specific capacitance will decrease nitrided reaction using MoO3 nanobelts as starting reactants.
with increasing scan rate in metal oxide electrodes, showing a These novel Mo2N nanobelts exhibited high electrocatalytic
logarithmic trend [26]. However, there is no decrease for Mo2N activity toward ORR and appear to be promising Pt-free
electrodes. The rectangular shape of the CV curves for Mo2N at cathodic electrocatalysts in alkaline fuel cells. Such Mo2N
high scanning rates is similar to that of carbon nanotubes nanostructures also exhibited high specific capacitance
(CNTs), and this rectangular shape results from the excellent (160 Fg1), high rate capability and high cycling stability as
conductivity and porous structure of CNTs [27]. Hence, such supercapacitor electrode materials. The high catalytic activity
Mo2N nanobelts exhibit extremely high rate capability, and capacitance may result from its novel nanostructures
with the effective integration of their high surface area and
good crystallinity. This discovery reveals a new type of metal
nitride ORR catalyst and appear to be promising Pt-free
cathodic electrocatalysts in alkaline fuel cells. We believe
that this involved strategy may be also extended to the prep-
aration of other TMNs with highly porous and single-crystal-
like nanobelts, such as Cu3N, TiN, WN and VN, to enhance
their catalytic activities and capacitances.

Acknowledgements

This work is supported by the Australian Research Council


through a Discovery Project (DP1094261), the National Natural
Science Foundation of China (grant No. 51202297, 51472271
and 61376018), and Program for New Century Excellent Tal-
ents in University (NCET-12-0554, NCET-13-0684). We thank
Dr. Tania Silver for the English editing of this paper.

Appendix A. Supplementary data

Supplementary data related to this article can be found at


http://dx.doi.org/10.1016/j.ijhydene.2015.11.086.

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trocatalyst for alkaline fuel cells and electrode materials for supercapacitors, International Journal of Hydrogen Energy (2015), http://
dx.doi.org/10.1016/j.ijhydene.2015.11.086
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Please cite this article in press as: Liu J, et al., Porous and single-crystalline-like molybdenum nitride nanobelts as a non-noble elec-
trocatalyst for alkaline fuel cells and electrode materials for supercapacitors, International Journal of Hydrogen Energy (2015), http://
dx.doi.org/10.1016/j.ijhydene.2015.11.086