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 Page 1 of 6 Journal of Materials Chemistry A
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Porous Ni Nanofibers with Enhanced Catalytic Effect
Cite this: DOI: 10.1039/x0xx00000x
on the Hydrogen Storage Performance of MgH2
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Jie Chen,‡a Guanglin Xia,‡a,b Zaiping Guo,b* Zhenguo Huang,b Huakun Liu,b Xuebin
Yua*
Received 00th January 2012,
Accepted 00th January 2012
DOI: 10.1039/x0xx00000x
www.rsc.org/
Porous Ni nanofibers (NFs) were synthesized via a single-
nozzle electrospinning technique with subsequent calcination
and reduction. The as-prepared continuous Ni NFs, with a
uniform diameter of ～50 nm and porous structure composed
of a myriad of nanocrystallited Ni were adopted to catalyze
MgH2. The homogeneous distribution of Ni nanoparticles
(NPs), obtained by ball milling the Ni NFs with MgH2, on the
surface of the MgH2 offered effective catalytic sites to
significantly enhance the hydrogen storage properties of
MgH2. In particular, 4% Ni NF catalyzed MgH2 (MgH2 – 4%
Ni NFs) starts to release hydrogen at only 143 oC, with a peak
temperature of 244 oC, 157 oC and 96 oC lower, respectively,
than for MgH2 catalyzed with as-milled 4% Ni powders
(MgH2 – 4% Ni powders), and it dehydrogenates completely
within only 11 min at 325 oC (7.02 wt%). Compared with
plain MgH2 and MgH2 – 4% Ni powders, the activation
energy of the as-milled MgH2 – 4% Ni NFs composite is
significantly decreased to 81.5 kJ mol-1.
Hydrogen, with the great advantages of high gravimetric energy
density (142 MJkg-1), widely available sources, light weight, and
environmental friendliness, has been considered as one of the best
alternative energy carriers to satisfy increasing demands for a
sustainable and clean energy supply.1-3 Developing a safe and
efficient hydrogen storage medium, however, is still one of the main
obstacles to the widespread application of hydrogen.4-7
Owing to its high gravimetric density (7.6 wt% H2), high
volumetric density (110 kg m-3), low cost, and abundance, as well as
its good reversibility, MgH2 has been identified as one of the most
attractive materials for solid hydrogen storage,8-14 although its
thermodynamic stability and slow kinetics limit practical application
of the MgH2 system. One of the most effective strategies to improve
the hydrogen storage performance of MgH2 is doping with additives,
such as transition metal intermetallic compounds (Nb, V, Cu, Mo,
Co, etc.).15-20 Among them, nickel has been experimentally
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DOI: 10.1039/C5TA03721B
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Journal of Materials Chemistry A Accepted Manuscript
investigated as an effective and inexpensive catalyst to reduce the
activation energy of hydrogen desorption from MgH2.21-24 Shang et
al. reported that MgH2 with the addition of microsized Ni (7 μm)
gave the most rapid desorption kinetics among several selected
additives, including Al, Fe, Nb, and Cu.25 Furthermore, recent
theoretical calculations and metal-catalysis studies have shown that
downscaling catalysts to the nanoscale leads to further enhanced
catalytic effects.26,27 For example, Hanada et al. studied the H-
storage properties of ball-milled MgH2 with a small amount of Ni
nanoparticles (NPs) as catalyst, which indicated that their 2 mol %
Ni-nanodoped MgH2 composite could desorb 6.5 wt% H2 in the
temperature range from 150 to 250 °C, whereas pure MgH2 did not
decompose.28 Afterwards, Xie et al. investigated the nanocatalyst
mechanisms systematically, confirming that the enhanced desorption
kinetics are mainly attributable to the lower decomposition barrier of
the hydride phase and the accelerated combination of hydrogen
atoms on the surface of the MgH2 because of the addition of Ni
NPs.29 In addition, reducing the particle size of the catalyst realizes
sufficient dispersion on the surface of the MgH2 and enhances the
intimate interface between the Ni particles and the hydride,
therefore, providing more active catalytic sites.16,30
Herein, we present a simple and efficient strategy for the synthesis
of Ni nanofibers (NFs) via the electrospinning technique. A sketch
of the typical electrospinning setup is illustrated in Fig. 1. Basically,
an electrospinning system consists of three major components: a
high voltage power supply, a spinneret (e.g., a pipette tip) and a
grounded collecting plate (usually a metal screen), which utilizes a
high voltage source to inject charge of a certain polarity into the
polyvinylpyrrolidone (PVP)/Ni(NO3)2 solution. When the electric
field applied reaches a critical value, the repulsive electrical forces
overcome the surface tension forces and eventually, a charged jet of
the solution is ejected from the tip of the Taylor cone and an
unstable and a rapid whipping of the jet occurs in the space between
the capillary tip and collector which leads to evaporation of the
solvent, generating PVP-coated Ni(NO3)2 fibers. Porous Ni NFs can
be prepared by the calcination of as-electrospun NFs, followed by
reduction in hydrogen atmosphere. The as-prepared Ni NFs
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composed of loosely connected Ni nanocrystallites with a uniform
diameter are easy to break up into ultrafine Ni NPs during the ball-
milling process, which results in good distribution of the Ni NPs on
the surface of the MgH2. Hence, higher surface area of the Ni NPs
with a diameter of 17 nm, enhanced intimate interfaces between Ni
and MgH2, homogeneous distribution, and more active catalytic sites
can be achieved, leading to remarkable catalytic effects on MgH2.
Favorable hydrogen desorption properties of the resultant MgH2
composite were observed and are discussed, based on these
experiments. In addition, activation energy of 81.5 kJ mol-1 for the
MgH2 – 4% Ni NFs composite has been obtained, and it
demonstrates enhanced kinetics.
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Fig.1 Schematic illustration of the electrospinning process of a Ni(NO3)2-PVP
mixture using a single-needle nozzle.
As shown in Fig. 2(a), the as-spun nitrate/PVP composite NFs are
randomly oriented with smooth surfaces and average diameter of ～
200 nm. After thermal annealing up to 500 °C, the uniform fibrous
nanostructure is well preserved during the calcination to form NiO,
as displayed in panel (b) of Fig. 2. The as-prepared NiO NFs are
homogeneous and continuous, with a significant diameter shrinkage
to ～50 nm due to the decomposition of the PVP polymer template.
The magnified transmission electron microscope (TEM) image of
the NiO NFs [Fig. 2(c)] reveals that each NiO NF is composed of a
number of NiO ultrafine nanocrystallites with a typical diameter of 5
–10 nm. These nanoscale crystallites are stacked one by one along
the direction of the nanotube axis, giving the nanofiber a rough
surface. Note that numerous holes or voids among the nanograins
can be directly observed in Fig. 2(b, c) owing to the removal of PVP
during the calcination. Fig. 1(d) and (e) show typical scanning
electron microscope (SEM) and TEM images of the Ni NFs
collected at low and high magnification, respectively, demonstrating
that the one-dimensional (1D) fibrous structures with ～ 50 nm
average diameter could be preserved during the entire thermal
reduction process. They are quite thermally stable without structural
collapse. Nonetheless, it should be noted from Fig. 2(e) that the Ni
NPs exhibit a large average grain size of 20 nm. The growth of
individual Ni nanograins required the consumption of more material
nearby, which simultaneously triggered the formation of nanograin
spacing and created greater spacings among the nanograins.31 As a
result, the continuous fibrous structure of the precursor was replaced
by a more loosely connected nanocrystalline morphology, which is
favored for the subsequent homogeneous dispersion of Ni NPs on
the MgH2 surface during the ball milling. The high-resolution TEM
(HRTEM) image of the Ni NFs [Fig. 2(f)] reveals the crystalline
character of Ni, and the distance between the lattice fringes is 0.20
nm, corresponding to the d-spacing of the (111) planes of face-
2 | J. Name., 2012, 00, 1-3
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centered-cubic (fcc) Ni, further demonstrating the successful
fabrication of porous Ni NFs.
Journal of Materials Chemistry A Accepted Manuscript
Fig.2 (a) SEM image of the as-electrospun PVP-coated Ni(NO3)2 NFs and (b, c)
TEM images of the NiO NFs; (d) SEM, (e) TEM, and (f) HRTEM images of the Ni
NFs, with the inset to (f) showing the corresponding selected area electron
diffraction pattern.
The crystal phase and structural information on the as-synthesized
NiO NFs before and after reduction were obtained by X-ray
diffraction (XRD) measurements. As shown in Fig. S1, three
prominent diffraction peaks at 37.3o, 43.3o, and 62.8o can be ascribed
to the (101), (012), and (110) planes of cubic NiO (JCPDS card no.
47-1049), respectively. The high intensity and sharp peaks indicate
the good crystallinity of NiO. After reduction, pure Ni phase could
appear, as revealed by two diffraction peaks at 44.5o (111) and 51.6o
(200) that are indexed to the Ni crystalline structure (JCPDS card no.
65-0380), corresponding to the HRTEM results in Fig. 1(f), without
the detection of NiO phase.
To explore the effects of Ni NFs on the dehydrogenation
performance of MgH2, a comparison of the thermal decomposition
performance of the as-prepared MgH2 – Ni NFs with the ball-milled
MgH2 – Ni powder composites and pure MgH2 as a control sample
was conducted by mass spectroscopy (MS). Fig. 3 illustrates the
hydrogen decomposition performance of as-milled MgH2– Ni NFs,
the MgH2 – Ni powders, and MgH2, respectively. Pure MgH2 started
to release hydrogen at ~340 oC, with a peak temperature of 385 oC.
The figure clearly shows that both the onset temperature and the
peak temperature are tremendously reduced with the addition of Ni
NFs or powders. The MgH2 – 2% Ni powders began to release H2 at
300 oC, with a peak temperature of 376 oC, about 40 oC and 9 oC
lower than for pure MgH2, respectively. This downward trend was
more obvious with an increasing amount of catalyst. For example,
the onset and peak temperatures of MgH2 – 4% Ni powders were
further reduced to 300 oC and 340 oC, respectively. Compared with
Ni powder catalyzed MgH2, the 2 wt% NF–doped MgH2 sample
exhibited much better desorption performance with the onset and
peak temperatures downshifted to 170 oC and 278 oC, respectively,
which was even about 130 oC and 62 oC lower than for the MgH2 –
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DOI: 10.1039/C5TA03721B

4% Ni powders. The significant decrease in the desorption
temperature demonstrated the outstanding catalytic performance of
the Ni NFs. Moreover, with the further addition of NFs to 4%, the
MgH2 exhibited the lowest desorption temperature among all these
mixtures. Specifically, the onset and peak temperatures of the MgH2
presented in Fig. 4. It shows that the as-milled MgH2 has the
worst desorption rate and the smallest desorption capacity
compared with all the composites: only 0.75 wt% hydrogen was
desorbed, even after 90 min. The addition of 4% Ni powders
could considerably improve the desorption performance of

Journal of Materials Chemistry A Accepted Manuscript

– 4% Ni NFs were around 143 oC and 244 oC, about 197 oC and 141
o
C lower than for the as-milled MgH2. In addition, the two-step
decomposition caused by uneven blending, observed in the
desorption process for MgH2 – 2% Ni NFs, could also be eliminated.
Detailed comparison of the operating temperatures is listed in Table
1. The significantly decreased operating temperature of MgH2
indicated that Ni NFs can significantly improve the desorption
properties of MgH2, with performance superior to that of Ni
powders.
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MgH2, which released 2.18 wt% H2 within 30 min. By
comparison, 2% Ni NF catalyzed MgH2 could release 6.16 wt%
H2 within the same time, while the amount of 7.02 wt% H2
could be desorbed in less than 15 min from the MgH2 – 4% Ni
NFs composite, approaching its theoretical releasable capacity.
These results obviously demonstrate the superior dehydriding
kinetics induced by the introduction of Ni NFs compared with
Ni powders.
Taking both the operating temperature and the desorption capacity

into consideration, presentative MgH2 – 4% Ni NFs composite was

selected for further study. Fig. 5(a) shows that the MgH2 – 4% Ni
NFs had a hydrogen release of ~5.6 wt% and ~6.9 wt% even at
temperatures as low as 250 oC and 275 oC respectively, whereas pure
MgH2 hardly decomposes, as reported in the literature.28,29 With
increasing operating temperature, the MgH2 – 4% Ni NFs composite
features faster kinetics. Upon further elevating the temperature to
300 °C, 325 oC, hydrogen capacities of 6.57%, 7.02% in 11 minutes
could be reached, respectively, after a drastic hydrogen evolution
within several minutes. In contrast, ball-milled MgH2 – 4% Ni
powders can only release 5.38 wt% H2 in the same time at the even
higher temperature of 375 oC, as shown in Fig. 5(b). From the
current experimental results, it can be concluded that the Ni NFs are
much superior compared with the traditional Ni powders towards
improving dehydrogenation of MgH2, corresponding to the previous
results from MS and isothermal experiments.

Fig.3 MS results for pure MgH2, ball-milled MgH2 – Ni powders, and MgH2 – Ni
NFs with different mole ratios(2%, 4%), with a heating rate of 5 °C min−1.

Table 1 Onset dehydrogenation temperature and the peak temperature for as-
milled samples.

Sample name Onset temperature Peak

(oC) temperature(oC)

Bulk MgH2 340 385

MgH2 – 2% Ni 300 376

powders
Fig.4 Isothermal dehydrogenation curves of the pure MgH2, ball-milled MgH2 - Ni
powders, and MgH2 – Ni NF composites with different mole ratios (2%, 4%) at
MgH2 – 2% Ni 170 278 300 oC.
NFs
For a quantitative evaluation of the enormously improved
dehydriding kinetics of the as-prepared MgH2 – 4% Ni powders, the
MgH2 – 4% Ni 300 340 apparent activation energy (Ea) was calculated by fitting the
powders isothermal dehydriding curves at different temperatures using the
Johanson–Mehl–Avrami–Kolmogorov (JMAK) equation:
MgH2 – 4% Ni 143 244 ln ln1  α ηlnt r
NFs where a is the fraction already reacted at time t, k is the rate constant,
and ƞ is the Avrami exponent, which is generally used to understand
the dimensionality of the MgH2/Mg growth process and obtain
The dehydrogenation kinetics of Ni NF catalyzed MgH2 was insight into the dehydrogenation mechanism.32-35 Plotting
evaluated via isothermal desorption patterns at 300 oC, as ln[−ln(1−α)] against ln t in the range 0.2 α0.5 yields a straight
line, where ƞ = slope and k = eintercept/slope. A hydrogen desorption

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fraction ranging from 0.2-0.5 was adopted to fit the kinetic curves.
The values of k were applied to calculate the dehydrogenation
activation energy according to the Arrhenius equation. As shown in
Fig. 5(c), it gives the activation energies of approximately 81.5 kJ
mol−1 and 141.3 kJ mol-1 for the MgH2 – 4% Ni NFs and its MgH2 –
4% Ni powder counterpart, respectively. The significant decrease in
activation energy gives direct evidence of the improvement of the
hydrogen release kinetics resulting from the Ni NF catalysts.
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Fig.5 (a) Hydrogen desorption kinetics curves of the milled MgH2 – 4% Ni NF
composite at different temperatures, (b) hydrogen desorption kinetics curves of
the milled MgH2 – 4% Ni powder composite at different temperatures, (c)
4 | J. Name., 2012, 00, 1-3
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Arrhenius plots according to the isothermal H2 desorption of the MgH2 – 4% Ni
NFs and MgH2 – 4% Ni powders.
Journal of Materials Chemistry A Accepted Manuscript
Fig.6 X-ray diffraction patterns of as-milled samples: (a) MgH2, (b) MgH2 – 4% Ni
powders, and (c) MgH2 – 4% Ni NFs; and of the samples after dehydrogenation:
(d) MgH2, (e) MgH2 – 4% Ni powders, and (f) MgH2 – 4% Ni NFs.
Fig.7 SEM image (a), TEM image (b), EDX spectrum (c), scanning TEM image (d) of
the MgH2-4% Ni NFs composite after ball-milling with the corresponding Mg map
(e) and Ni map (f).
To further understand the relevant effects of the Ni NFs on the
desorption performance of MgH2, morphology and microstructure
studies of the composites after ball milling were conducted. The
XRD patterns [Fig. 6(a-c)] indicated that the composite after milling
mainly contained the MgH2 phase, which demonstrated that MgH2
did not decompose during ball milling. A broad Ni peak could be
observed from the XRD diffraction patterns of the MgH2 – 4% Ni
NFs sample, indicating the small grain size of Ni. The average
particle size of Ni, calculated from the Debye–Scherrer equation, is
∼17.6 nm. After the decomposition, the peaks belonging to Mg
This journal is © The Royal Society of Chemistry 2012
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appeared, together with the disappearance of MgH2 [Fig. 6(d-f)],
which directly confirms the complete dehydrogenation of MgH2.
Furthermore, from Fig. 6(f), we can see that a small amount of
Mg2Ni phase was formed due to the high temperature heat treatment
upon dehydrogenation.
Additionally, the microstructure of the MgH2 – 4% Ni NFs
composite after ball milling was also investigated by TEM. From
Fig. 7(a, b), clearly, the 1D fibrous structure of Ni was broken up
during the ball-milling into numerous Ni NPs with a uniform size
distribution of ～10 – 20 nm, corresponding to the calculation results
based on previous XRD results in Fig. 6, which were distributed
homogeneously on the surfaces of the MgH2. The energy dispersive
X-ray spectroscopy (EDX) spectrum [Fig. 7(c)] further identifies the
elemental composition of Ni and Mg. As we can see from the EDX
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elemental maps for the MgH2 – 4% Ni NFs after ball milling [Fig.
7(d-f)], the element Ni is dispersed homogeneously on the MgH2
matrix, consistent with the results of Fig. 7(b). As mentioned above,
the Ni NFs exhibited a porous morphology, which was composed of
stacks of a number of loosely connected Ni NPs. This special
precursor structure not only benefits the uniform dispersion of Ni in
the system during ball milling, but also effectively prevents the
aggregation of particles and provides a more intimate reaction
between the catalyst and the MgH2. By using the as-prepared Ni NFs
with their distinctive structure, ultrafine Ni NPs were fabricated
successfully with favorable distribution on the surfaces of the MgH2.
It is well known that the reaction kinetics of MgH2 are enhanced
with decreasing particle size of the catalyst, due to the higher surface
area, shorter intimate interfaces between Ni NPs and the hydride,
and more catalytic active sites on the surface of the MgH2. Hence, Ni
NFs exert a better catalytic effect than Ni powders on the hydrogen
storage performance of MgH2.
Conclusions
In summary, we have successfully developed a facile and
simple method to synthesize porous Ni NFs by a single-nozzle
electrospinning technique. The as-synthesized Ni NFs showed
enhanced catalytic effects on the dehydrogenation performance
of MgH2, with the rapid release of 7.02 wt% hydrogen in 11
min at 325 °C. Moreover, the onset dehydrogenation
temperature of MgH2 significantly decreased with increasing
amounts of Ni catalyst, i.e., from 340 oC for pure MgH2, to 170
o
C for the MgH2 – 2% Ni NFs composite, to the lowest value of
143oC for the MgH2 – 4% Ni NFs sample. In addition,
activation energy of 81.5 kJ mol-1 for the as-milled MgH2 – 4%
Ni NFs composite has been obtained, which demonstrates the
enhanced kinetics. The novelty of the methodology lies in the
use of NFs composed of Ni nanocrystallites as the precursor,
which can realize the homogenous dispersion of Ni NPs on the
surface of the hydride. It is proposed that the well-distributed
Ni NPs could significantly enhance the intimate interface
between Ni and the hydride, thus providing more active
catalytic sites, which can give rise to excellent hydrogen
storage properties for the MgH2. Furthermore, the strategy of
utilizing the electrospinning technique for fabricating NFs as
catalysts opens up a prospective route for the synthesis of
superior catalysts for other hydrogen storage materials.
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DOI: 10.1039/C5TA03721B
Experimental Sections
Fabrication of Ni NFs
To synthesize Ni NFs, a three-step process was adopted as
described below. In the first step, 0.35 mmol nickelnitrate
Journal of Materials Chemistry A Accepted Manuscript
hexahydrate (Ni(NO3)2·6H2O, A.R., Alfa-Aesar Inc., USA) and
polyvinylpyrrolidone (PVP, Mw ≈ 1 300 000, Sigma-Aldrich
Inc.,USA) were dissolved in a mixed solution of 1.25 mL N,N-
dimethylformamide (DMF, A.R., Tianjin Chemical Corp.,
China) and 1.25 mL ethanol (A.R., Tianjin Chemical Corp.,
China), with vigorous stirring for 5 h to make a homogeneous
spinning dope. The well-prepared precursor solution was
poured into a syringe with an 18-gauge blunt-tipped needle. We
set the voltage, which was provided by a high-voltage power
supply between the needle and the collector, at 12 kV. The flow
rate of solution was approximately 250 µL h−1 controlled by a
syringe pump (Longer, TJP-3A, China), and a grounded
stainless steel plate was horizontally placed 15 cm from the
needle to collect the nanowires. Secondly, the as-collected
fibers produced by electrospinning were annealed in air at 200
°C with a heating rate of 1 °C·min−1, and then sintered at 500
°C for 3 h to obtain the nanoporous NiO fibers. Finally
successive reduction to 400 °C for 2 h was conducted under
dynamic H2 atmosphere under a pressure of 1 bar and yielded
the 1D nanoporous Ni fibers with a heating rate of 1 °C min−1.
Preparation of nanocatalyzed MgH2 composites
The composites were synthesized from commercially available
MgH2 (Alfa Aesar 98%) and the prepared Ni NFs as catalyst.
The MgH2 powder was mixed with Ni NFs by ball milling for 5
h to form a mixture for further experimental trials. The mole
ratios of Ni catalyst to MgH2 were 2% and 4%, respectively.
The ball milling was performed on a planetary ball mill (QM-
1SP2, Nanjing) with a ball-to-powder weight ratio of 50:1 and a
rotation speed of 200 rpm. For comparison, 2 mol% and 4 mol%
Ni powders (Alfa Aesar) were ball-milled with MgH2 under
identical conditions, respectively. In addition, pure MgH2
without catalyst was also ball milled in same way as a reference
sample. All the materials were handled in a glovebox filled
with purified argon (99.999%), which could keep the water
vapor and oxygen levels below 1 ppm by recycling the
purification system to protect samples from hydroxide
formation and/or oxidation.
Characterization
Mass spectrometry (MS, Netzsch STA 449C) was conducted at
room temperature at a heating rate of 5 °C min−1 under dynamic
argon with a purge rate of 80 mL min-1. The phase composite
on of the powders was analyzed by X-ray diffraction (D8
Advance, Bruker AXS) with Cu Kα radiation. Amorphous tape
was used to prevent any possible reactions between the sample
and air during the XRD measurements. The morphology of the
samples was evaluated using a field emission scanning electron
microscope (FE-SEM; JEOL7500FA, Tokyo, Japan) and a
transmission electron microscope (TEM; JEOL 2011 F, Tokyo,
Japan). Elemental analysis was performed with an Elemen Tar
Vario EL3 Elemental Analysis. The hydrogen storage
properties of the ball-milled MgH2/Ni NFs composite, the
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Journal of Materials Chemistry A Accepted Manuscript

hydrogen pressure below 0.02 atm.
Acknowledgements
This work was partially supported by the National Natural
Science Foundation of China (21271046, 51471053) and the
PhD Programs Foundation of the Ministry of Education of
China (20110071110009). Z. Guo acknowledges funding from
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