Highly Dispersed Bimetallic Nanoparticles Supported on Titanium Carbides for Remarkable Hydrogen Release from Hydrous Hydrazine

Article abstract of DOI:10.1002/cctc.201701633

The catalytic decomposition of hydrous hydrazine (N₂H₄?H₂O) is considered a promising candidate for the fuel-cell field, but sluggish reaction kinetics dramatically impede its practical application. In this study, bimetallic RhNi nanoparticles were successfully anchored on titanium carbides (MXene) by a one-step wet-chemical method to build superior catalysts for the decomposition of hydrous hydrazine (N₂H₄?H₂O), a compound that can be used for chemical hydrogen storage. The synthesized RhNi/MXene catalysts were characterized by X-ray photoelectron spectroscopy, transmission electron microscopy, high-angle annular dark-field scanning transmission electron microscopy, and inductively coupled plasma atomic emission spectroscopy. As a result of the particles size and a synergistic effect, the Rh_0.8Ni_0.2/MXene nanocatalyst demonstrated 100 % selectivity to H₂, excellent stability, and high reaction kinetics with a turnover frequency of 857 h^?1 for the decomposition of N₂H₄?H₂O in alkaline solution.

Full text of DOI:10.1002/cctc.201701633

Accepted Article
Title: Highly dispersed bimetallic nanoparticles supported on titanium
carbides for remarkable hydrogen release from hydrous
hydrazine
Authors: Tong Liu, Qingtao Wang, Jingzhi Yuan, Xue Zhao, and
Guanhui Gao
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ChemCatChem
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COMMUNICATION
Highly dispersed bimetallic nanoparticles supported on titanium
carbides for remarkable hydrogen release from hydrous
hydrazine
Tong Liu, [a],* Qingtao Wang, Jingzhi Yuan, Xue Zhao, and Guanhui Gao
[a]
[a]
[a]
[b]
Abstract: Catalytic decomposition of hydrous hydrazine (N
2
H
4
·H
2
O)
on MXene surface, such as Ti-OH and Ti-F bonds, not only
stabilize the nanoparticles during reduction, but also improve the
hydrophilicity of the resultant catalysts.[26-31] However, there were
a few literatures reported on MXene anchoring nanocatalysts only
the typical study on MXene supported Ru-based nanocatalysts
were prepared and applied as excellent nanocatalysts for sodium
borohydride and ammonia borane decompositions.[32,33] Here, we
creatively synthesize the RhNi bimetallic nanoparticles supported
on MXene via one-step wet-chemical approach. Unexpectedly,
are considered as one of the promising candidate for fuel cell field,
but the sluggish reaction kinetics dramatically impede their practical
application. In this study, bimetallic RhNi nanoparticles are
successfully anchored on titanium carbides (MXene) by one-step wet-
chemical method, building a block for superior catalysts toward
2 4 2
hydrous hydrazine (N H ·H O) decomposition applying for chemical
hydrogen storage. The synthesized RhNi/MXene catalysts are
characterized by XPS, TEM, STEM-HAADF and ICP-AES. Due to the
particles size and synergistic effect, the Rh0.8Ni0.2/MXene
the resultant RhNi/MXene nano-catalysts with 100% of H
selectivity indicate an extremely high catalytic activity and
excellent durability toward decomposition of N ·H O.
2
nanocatalysts demonstrate 100% H
and high reaction kinetics with turnover frequency value of 857 h
toward N ·H O decomposition in alkaline solution.
2
selectivity, excellent durability,
-
1
2
H
4
2
H
2 4
2
Figure. S1 shows the preparation of the RhNi/MXene
nanocatalyst. In a typical experiment, 100 mg MXene is dissolved
in 2 mL water in a two-neck round-bottom flask (30 mL), with
sonicating for 30 min to obtain a uniform dispersion. Then, 100 μL
rhodium chloride solution (0.8 mmol/mL) and 100 μL nickel
chloride (0.2 mmol/mL) are both added into above MXene solution
gently, with electromagnetic stirring (speed of 220 rpm) for 20 min.
Very recently, the worldwide concerns on energy crisis and
environmental pollution have stimulated intensive attention, which
is essential to pursue sustainable and renewable energy.[1-7]
Catalytic hydrogen generation from hydrogen storage materials is
regarded as a promising way to address the energy and
environmental crisis, due to its advantages of light weight, high
abundance and chemical energy per mass.[8-14] Among numerous
-1
4
Then, 24 mg of sodium borohydride (NaBH ) (1.3 mol L )
dissolved in 0.5 mL of 2.0 M NaOH solution is quickly added into
above resulted mixture under vigorous stirring for 3 h at 0 °C using
an ice bath to maintain the temperature for prevention of RhNi
NPs aggregation. The RhNi/MXene nanocatalysts are obtained
by washing with deionized water and centrifugation. The
corresponding macroscopic photos are shown in Figure S2.
The powder X-ray diffraction (PXRD) patterns of the as-
synthesized RhNi/MXene are measured (Figure. S3). The pattern
peaks at 29.8°, 35.3°, and 36.9° are assigned to MXene. In
addition, the peaks of RhNi are very small and broad, indicating
that the ultrafine RhNi NPs are successfully supported on MXene.
Additionally, for the six samples with different compositions, it can
be found that the corresponding XRD diffraction peaks gradually
shift to higher 2θ as the Ni composition increases. These results
clearly demonstrate that our obtained particles are RhNi alloys.
Figure. S4 exhibits the measured XPS spectra of RhNi/MXene in
the Rh 3d, Ni 2p, Ti 2p, O 1s, F 1s and C 1s regions, respectively.
The peaks at 284.5 eV and 281.6 eV are attributed to the binding
energy of C 1s. Additionally, the peaks corresponding to F and O
indicate the introduction of functional groups such as OH and F.
The two peaks located at 307.3 eV and 311.8 eV could be
2 4 2
hydrogen storage materials, hydrous hydrazine (N H ·H O) has
attracted much attention due to its high hydrogen density of 8.0
wt%, low molecular weight of 50.1 g/mol and excellent stability
under ambient conditions.[15-21] Therefore, it is considered as one
of the most leading candidate in promising chemical hydrogen-
storage materials. The two molar CO-free H
release from one molar hydrous hydrazine according to the
following reaction NNH → N +2H (Eqn (1)), while the
undesired reaction pathway (3H NNH →N +4NH , eqn 2) must
2
is able to efficiently
H
2
2
2
2
2
2
2
3
be avoided, because the generated NH3 is poisonous to the fuel-
cell catalysts.[22-25] In order to achieve the high efficiency of
dehydrogenation from hydrous hydrazine, it is essential to
develop catalysts with high selectivity only the catalytic
hydrogenation (Eqn (1)) occuring. Although much effort has been
engaged to improve the reaction rate and obtain high efficiency
with 100 % H
decomposition is not acceptable.
Recently, graphene-like transition metal carbide (MXene,
(OH ) has been widely investigated as a promising
support for new nano-catalysts. The abundant functional groups
2 2 4 2
selectivity, the kinetics of catalytic N H ·H O
Ti
3
C
2
x 1-x 2
F )
0
0
assigned to elemental Rh 3d5/2 and Rh 3d3/2, respectively. While
0
0
the Ni peaks corresponding to Ni 2p1/2 and Ni 2p3/2 are observed
at 851.9 and 870.3 eV.[32,33] These results clearly demonstrate
that the RhNi particles have been successfully anchored on
MXene surface. Additionally, compared to Rh/MXene, the binding
energies of Rh 3d in RhNi/MXene are negatively shifted (Figure.
S5a). In contrast, the binding energies of Ni 2p in RhNi/MXene
are positively shifted relative to that of Ni/MXene (Figure. S5b).
These shifts of the binding energies indicate the formation of RhNi
alloy and electron transferring from Ni to Rh, which benefits to
[
[
a]
b]
Dr. T. Liu, Q.-T. Wang, J.-Z. Yuan, X. Zhao
College of Materials Science and Engineering
Qingdao University of Science and Technology
53 Zhengzhou Rd, Qingdao, 266000, PR China
E-mail: liutong@qust.edu.cn
Dr. G.-H. Gao
Paul-Drude-Institut für Festkörperelektronik
Hausvogteiplatz 5–7, 10117 Berlin, Germany
1
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ChemCatChem
10.1002/cctc.201701633
COMMUNICATION
enhancing the synergistic effect in metallic catalyst, resulting in
improvement for catalytic property.
achieve 857 h-1 at 50 °C, which is rather higher than those of
reported values in Table 1.
Furthermore, the d-spacing of RhNi NPs is approximately 0.212
nm, which is between 0.219 nm of Rh (111) and 0.203 nm of Ni
(
011) (Figure. 1c), indicating that the obtained nanoparticles are
RhNi alloys. In addition, the metal loading for the Rh0.8Ni0.2/MXene
is determined by inductively coupled plasma-atomic emission
spectroscopy (ICP-AES) to be 9.8 wt%, and the the relative
compositions of the RhNi NPs yield the following compositions:
8
2 at% Rh, and 17 at% Ni, in the Rh0.8Ni0.2/MXene. Figure. S6
demonstrates the adsorption–desorption isotherms of
Rh0.8Ni0.2/MXene. The measured Brunauer–Emmett–Teller (BET)
N
2
2
-1
surface area of the RhNi/MXene is calculated to 77.83 m g due
to graphene oxide partially avoided. Moreover, the Barrett–
Joyner–Halenda (BJH) analysis shows that the average pore
-
-1
diameter is 3.6 nm with the pore volume of 0.016 cm 3 g .
Figure 2. The STEM-HAADF images of the Rh0.8Ni0.2/MXene (a) and the
corresponding elemental mapping images for Rh (b), Ni (c), C (d), O (e) and Ti
(f).
Table 1. T Catalytic activities of different catalysts for the
dehydrogenation of hydrous hydrazine
Catalyst
Solvent/medium
Temp.
°C)
Selectivity
for
100 %)
TOF
Ea
Ref.
-
1
(
H
2
(h
)
(kJ
mol
-
(
1
)
Rh0.8Ni0.2/MXene
Rh55Ni45/Ce(OH)
Rh4.4Ni/graphene
Rh34Ni66@ZIF-8
Pt0.6Ni0.4/PDA-rGO
Aqueous
NaOH
Aqueous
NaOH
Aqueous
NaOH
Aqueous
NaOH
50
50
30
50
50
100
100
100
100
100
857
395
28
38.2
This
work
34
38.8
18
35
36
140
2056
58.1
Aqueous
NaOH
33.39
(
Ni
3
Pt
7
)
0.5-(MnO
x
)
0.5
Aqueous
NaOH
5
0
100
100
100
706
471
676
50.15
40.4
53.2
/
NPC-900
3
7
Ni88Pt12/MIL-101
Aqueous
NaOH
Aqueous
NaOH
50
50
38
Ni0.8Pt0.2/MIL-101-
NH
11
2
Figure 1. TEM (a, b) and HRTEM images of the Rh0.8Ni0.2/MXene (c).
3
Ni Pt
7
/BNG-1000
Aqueous
NaOH
30
100
199.4
28.4
39
Ni0.9Pt0.05Rh0.05/La
Ni0.9Pt0.1/Ce
Ni Pt -SF
Pt60Ni40-CNDs
Ni0.58Pt0.42/graphene
Ni0.9 t0.1/MIL-101
Rh0.8Ni0.2@CeO /rGO
2
O
3
Aqueous
NaOH
Aqueous
NaOH
Aqueous
NaOH
Aqueous
NaOH
Aqueous
NaOH
Aqueous
NaOH
Aqueous
NaOH
25
25
25
50
30
30
30
100
100
100
100
100
100
100
45.9
28.1
150
170
434
140
36.4
40
19
41
42
43
44
45
2
O
3
42.3
TEM and high resolution TEM (HRTEM) are carried out to
further investigate the morphologies of RhNi NPs. The TEM and
HRTEM (Figure. 1) images of RhNi/MXene indicate that the
discrete RhNi NPs homogeneously disperse on MXene surface
with an average size of 2.8 nm (Figure. 1b inside). The elemental
mappings of Ni, Rh, C, O and Ti (Figure. 2) reveal that metal and
non-metal elements uniformly disperse throughout the whole
MXene. The formation of mono-despersed RhNi NPs benefits to
6
4
43.9
23.9
48.4
58
P
x
Mass spectrometry (MS) results further confirm the formation of
and N and the absence of NH in the released gas (Figure.
enhancing catalytic property for N
The catalytic performances of Rh
generation from N ·H O are investigated at 50 °C with a
constant molar ratio of catalyst/N ·H O = 0.067 (Figure. 3). It
can be seen that the catalytic activity and H selectivity are
2
H
4
2
·H O decomposition.
H
2
2
3
x
Ni1-x/MXene (0≤x≤1) for H
2
S7). Remarkably, the high catalytic activity is attributed to the
formation of small monodispersed RhNi NPs. As shown in Figure.
b-c, small RhNi NPs with size of 2.8 nm uniformly dispersed on
MXene surface without aggregation is observed, which could
provide more active sites for reaction, efficiently improving
performance for
2
H
4
2
2
H
4
2
1
2
strongly dependent on the metallic Rh/Ni molar ratio. Neither Ni
nor Rh shows high catalytic property, however, by alloying small
amount of Ni to Rh, both of H selectivity and kinetics rate of the
2
catalysts obviously is dramatically enhanced. Reasonably, the
remarkable catalytic activity is attributed to the molecular-scale
synergetic effect in RhNi alloy, which could enhance the electronic
effects of nanocatalysts. For all the bimetallic Rh Ni1-x/MXene (0≤
x
x ≤ 1) catalysts investigated, the Rh0.8Ni0.2/MXene exhibits
excellent catalytic activity, the corresponding TOF value can
2 4 2
N H ·H O decomposition. Additionally, the
synergetic effect between Rh and Ni could promote the catalytic
activity. The synergistic effect between bimetallic nanoparticles
can efficiently tune surface electronic states of bimetallic
nanoparticles, particularly related to local strain and effective
atomic coordination number at the surface, leading an apparent
2 4 2
improvement for N H ·H
O decomposition.[46]
2
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Furthermore, the support material plays an important role on
possible reason for the effects of the NaOH additive may be
determining the catalytic performance for
N
2
H
4
·H
2
O
explained as below: the addition of NaOH will decrease the
decomposition.[47,48] In order to evaluate the effect of the
supported materials on the catalytic performances toward the
undesired
N
H
5
+
concentration in the aqueous solution.
2
Additionally, in view of the chemical equilibrium, a strong alkaline
environment will inhibit the generation of the basic byproduct NH
which raises the H
selectivity.[53-56]
N
2
H
4
·H
2
O decomposition, catalysts are synthesized by loading
3
,
RhNi NPs on different carriers such as GO (Rh0.8Ni0.2/GO), XC-72
2
(
(
Rh0.8Ni0.2/XC-72),
Rh0.8Ni0.2/Al ), and support-free (Rh0.8Ni0.2). As shown in
·H
MCNTs
(Rh0.8Ni0.2/MCNTs),
Al
2
O
3
For the practical application of catalysts, the durability/stability
of catalysts is the key point. Therefore, the durability of the
2
O
3
Figure. S8, their catalytic performance toward
N
2
H
4
2
O
Rh0.8Ni0.2/MXene nanocatalyst up to sixth run for N
decomposition is characterized by adding additional aliquots (1.5
mmol) of N ·H O to the catalyst after the reaction completion
2 4 2
H ·H O
decomposition are inferior to that of Rh0.8Ni0.2/MXene, which is
attributed to the strong synergistic effect between nanocatalyst
and MXene support. To demonstrate the effect of MXene support
on improving catalytic activity, we measured the binding energies
of Rh 3d and Ni 2p in RhNi/MXene and support free RhNi. As
shown in Figure. S9, the binding energies of Rh 3d and Ni 2p in
RhNi/MXene are both negatively shifted compared to those of
support free RhNi, suggesting that MXene promote electron
transfer to RhNi, and benefit the cleavage of N-H bonds.[22,42]
These above results clearly illustrate that MXene, as a superior
support, would improve cooperative effect toward RhNi NPs and
2
H
4
2
for the last run. It is evident from Figure. 4a, we can find that the
catalytic activity of the as-prepared Rh0.8Ni0.2/MXene nanocatalyst
has no obvious decrease after a six-time recycle test, indicating
the as-prepared Rh0.8Ni0.2/MXene possesses a high durability in
2 4 2
N H ·H O decomposition. Furthermore, the in situ synthesized
NPs are magnetic and thus can be separated from the reaction
solution by an external magnet (Figure. 4b), which prove the
practical recycling application of the NPs more convenient. The
2 4 2
stable durability of N H ·H O is mainly attributed to dispersive
facilitates dehydrogenation of aqueous solution of N
our system.
In order to obtain the activation energy (Ea) of the N
decomposition catalysed by Rh0.8Ni0.2/MXene catalysts, the
reactions at different temperatures (25-60 °C) are carried out and
the corresponding results are shown in Figure. S10a. From the
results, the hydrogen generation rate over the Rh0.8Ni0.2/MXene
catalyst greatly depends on the reaction temperatures, which is
agreed to the previous works.[49-52] The catalytic reactions at 25,
2
H
4
·H
2
O in
metallic RhNi NPs without any aggregation of, which is proved by
TEM measurement. As clearly seen from the TEM images (Figure.
4c-d), there is no obvious aggregation of the RhNi NPs on MXene,
further confirming the advantage of the confinement effect of
MXene.
2
H
4
·H
2
O
3
5, 40, 50, and 60 °C demonstrate the corresponding TOF values
-1
of 245, 443, 507, 857, and 1204 h . The Arrhenius plot of ln TOF
vs. 1/T for this catalyst is plotted in Figure. S10b, which Ea is
calculated as 38.2 kJ·mol .
-1
2 2 4 2
Figure 4. Time course plots for H generation from N H ·H O decomposition
catalyzed by Rh0.8Ni0.2/MXene from 1st to 6th cycles (a); photographs of the
Rh0.8Ni0.2/MXene before (left) and after (right) the magnetic separation (b); and
TEM image of the Rh0.8Ni0.2/MXene NPs after the sixth cycle (c, d).
2 2 4 2
Figure 3. Time course plots for H generation from N H ·H O decomposition
In summary, monodispersed RhNi NPs are successfully
anchored on MXene surfaces via a facile one-step wet-chemical
strategy. By optimizing the fraction of Rh component in Rh-Ni
system, the synthesized Rh0.8Ni0.2/MXene catalysts demonstrate
with different Rh/Ni molar ratios (0≤x≤1) at 50 °C. The molar ratio of metal/N
O = 0.067.
2 4
H
·H
2
the most reactive function to N
of H selectivity and excellent catalytic performance of 857 h at
0 °C. Additionally, the synthesized Rh0.8Ni0.2/MXene shows
superior catalytic performance to that of Rh0.8Ni0.2/GO,
Rh0.8Ni0.2/XC-72, Rh0.8Ni0.2/MCNTs, and
Rh0.8Ni0.2. Kinetic studies on N O decomposition catalyzed
over Rh0.8Ni0.2/Mxene demonstrate that the factors of metallic
2 4 2
H ·H O decomposition with 100 %
It is found that the N
by controlling the concentration of NaOH in reaction system. The
hydrogen generation from N ·H O with/without adding NaOH is
2 4 2
H ·H O decomposition can be promoted
-1
2
5
2
H
4
2
investigated comparatively. As shown in Figure. S11, the reaction
kinetics is sluggish without NaOH. After addition of NaOH, the
reaction rate obviously increases, reaching a maximum TOF
2 3
Rh0.8Ni0.2/Al O ,
2
4 2
H ·H
-1
value of 857 h and 100 % at the NaOH concentration of 2 M. The
3
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ChemCatChem
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COMMUNICATION
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ChemCatChem
10.1002/cctc.201701633
COMMUNICATION
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COMMUNICATION
Tong Liu, ,* Qingtao Wang, Jingzhi
Yuan, Xue Zhao, and Guanhui Gao ,*
Page 1. – Page 5.
Highly dispersed bimetallic
nanoparticles supported on titanium
carbides for remarkable hydrogen
release from hydrous hydrazine
Bimetallic RhNi nanoparticles are successfully anchored on titanium carbides (MXene), building a block for superior catalysts toward hydrous
hydrazine decomposition applying for chemical hydrogen storage. Due to the particles size and synergistic effect, the Rh0.8Ni0.2/MXene
-1
nanocatalysts demonstrate high selectivity, excellent durability, and high reaction kinetics with turnover frequency value of 857 h in alkaline
solution.
5
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