CoBP nanoparticles supported on three-dimensional nitrogen-doped graphene hydrogel and their superior catalysis for hydrogen generation from hydrolysis of ammonia borane

Article abstract of DOI:10.1016/j.jallcom.2017.11.137

P-doped noble-metal-free CoB nanoparticles (NPs) anchored on a three-dimensional nitrogen-doped graphene hydrogel (NGH) have been successfully synthesized trough a simple one-pot co-reduction method and further used as catalyst toward catalytic hydrolysis of ammonia borane (NH₃BH₃) at room temperature. Benefiting from the synergistic electronic effect between Co, B, and P, as well as the strong metal-support interaction between CoBP and 3D NGH, the as-synthesized Co_0.79B_0.15P_0.06/NGH catalyst exhibits excellent catalytic activity toward hydrolysis of ammonia borane, with the turnover (TOF) value of 32.8 min^?1, which is almost 5 times higher than that of undoped Co_0.85B_0.15/NGH NPs, and higher than most of the reported noble metal free catalysts.

Full text of DOI:10.1016/j.jallcom.2017.11.137

Journal of Alloys and Compounds 735 (2018) 1271e1276
Contents lists available at ScienceDirect
Journal of Alloys and Compounds
journal homepage: http://www.elsevier.com/locate/jalcom
CoBP nanoparticles supported on three-dimensional nitrogen-doped
graphene hydrogel and their superior catalysis for hydrogen
generation from hydrolysis of ammonia borane
Yana Men 1, Jun Su b 1, Xiaoqiong Du , Lijing Liang , Gongzhen Cheng , Wei Luo
a
,
,
a
a
a
a, *
a
College of Chemistry and Molecular Sciences, Wuhan University, Wuhan, Hubei, 430072, PR China
Wuhan National Laboratory for Optoelectronics, Huazhong University of Science and Technology, Wuhan, Hubei, 430074, PR China
b
a r t i c l e i n f o
a b s t r a c t
Article history:
Received 20 September 2017
Received in revised form
P-doped noble-metal-free CoB nanoparticles (NPs) anchored on a three-dimensional nitrogen-doped
graphene hydrogel (NGH) have been successfully synthesized trough a simple one-pot co-reduction
method and further used as catalyst toward catalytic hydrolysis of ammonia borane (NH
temperature. Benefiting from the synergistic electronic effect between Co, B, and P, as well as the strong
metal-support interaction between CoBP and 3D NGH, the as-synthesized Co0.79 0.06/NGH catalyst
exhibits excellent catalytic activity toward hydrolysis of ammonia borane, with the turnover (TOF) value
3 3
BH ) at room
1
November 2017
Accepted 10 November 2017
Available online 11 November 2017
B
0.15
P
ꢀ
1
of 32.8 min , which is almost 5 times higher than that of undoped Co0.85
B0.15/NGH NPs, and higher than
Keywords:
Nitrogen-doped graphene hydrogel
CoBP
most of the reported noble metal free catalysts.
©
2017 Elsevier B.V. All rights reserved.
Hydrogen storage
Ammonia borane
1. Introduction
sustained catalysts toward hydrolysis of AB is extremely desirable,
but still a great challenge [31,32].
Hydrogen has been considered as one of the most promising
alternative energy carrier for the future energy conversion and
storage, probably due to its high energy density and environmental
benignity [1e6]. However, safe and efficient storage of hydrogen
still remains a key issues to the forthcoming “hydrogen economy”
catalyst
NH BH þ2H Oƒƒƒ!NH BO þ3H
(1)
3
3
2
4
2
2
Hetero-atoms doping has been considered as one of the most
efficient way to increase the catalytic activity of metal catalysts.
Transition metal phosphides (TMPs), which have a slight of charge
transfer from the metal atoms to P [33e35], have been extensively
served as effective electrocatalysts in overall water splitting
36e41], on account of a strong electronic interaction between the
metal and P. Recently, Fu and coworkers first reported Ni P Nano-
catalysts prepared by reacting Ni(OH) powder with solid NaH PO
[
7e9]. To this end, a large number of hydrogen storage approaches
have been investigated, including physical absorption materials
10,11], metal hydrides [12,13], and chemical hydrides [14e16].
Among them, ammonia borane (NH BH , AB) with high stability
[
3
3
[
and high hydrogen content (19.6 wt.%) [17e20], has been consid-
ered as the most potential candidate for the chemical hydrogen
storage material [21e25]. As shown in Eq. (1), AB is able to release
hydrogen though the catalytic hydrolysis process, in which 3 mol
2
2
2
2
in argon at 543 K and their excellent catalytic performance in the
dehydrogenation of AB [42]. Subsequently, the same group re-
ported CoP nanoparticles obtained from a Co precursor using the
2
H can be obtained [26]. Currently, noble metal based materials (Rh,
Pt, or Ru) [27e30] are considered as the most effective catalysts for
catalytic hydrolysis of ammonia borane, however, their high cost
and scarcity severely hinder their large-scale applications. There-
fore, the development of noble-metal-free, highly efficient and
2 2
NaH PO -reduction method in argon at 573 K toward effectively
catalytic hydrolysis of AB [43]. One the other hand, transition metal
borides, such as CoB, NiB, and Co-Ni-B have already shown great
potential as catalysts toward catalytic hydrolysis of AB [44e46].
Despite great efforts have been made, it still remains a big challenge
to achieve desired non-noble metal based catalysts with high effi-
ciency and long-term stability. Moreover, to the best of knowledge,
doping two hetero-atoms into non-noble metal-based catalyst with
*
Corresponding author.
E-mail address: wluo@whu.edu.cn (W. Luo).
These authors contributed equally.
1
https://doi.org/10.1016/j.jallcom.2017.11.137
925-8388/© 2017 Elsevier B.V. All rights reserved.
0

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Y. Men et al. / Journal of Alloys and Compounds 735 (2018) 1271e1276
enhanced catalytic activity toward catalytic hydrolysis of AB, has
not been reported yet.
2.4. Preparation of N-doped graphene
Following this strategy, herein, for the first time, we reported a
simple one-pot synthesis of CoBP nanoparticles (NPs) supported on
three dimensional (3D) nitrogen-doped graphene hydrogel (NGH),
and their superior catalytic performance toward catalytic hydro-
lysis of AB. The 3D NGH was chosen as the supported substrate for
arching the as-synthesized CoBP NPs due to its large surface area,
porosity, electrical conductivity, and excellent stability [47e50].
Thanks to the synergistic electronic interaction between Co, B, and
P, as well as the strong metal-support interaction between CoBP
During a typical synthesis of the N-doped graphene (NGH)
process, 630 mg of GO was added into a 100 mL flakes with 70 mL of
deionized water. A GO dispersion of 9 mg/mL was obtained by
ultrasonication for 2 h, which was doped with nitrogen (N) atoms
by adding 3.0 mL of C H N gradually at room temperature. In the
2 8 2
next step, the suspension was stirred magnetically at 298 K for
30 min and subsequently transferred into a 100 mL Teflon-lined
ꢂ
autoclave which was heated at 180 C for 12 h. After being cooled
to room temperature, the as-obtained NGH hydrogel was dialyzed
against DI-water for at least 24 h to remove the impurities.
0.15
and 3D NGH, the obtained Co0.79B P0.06/NGH exhibits superior
catalytic performance toward hydrolysis of AB, with a turnover
ꢀ1
frequency value (TOF) of 32.8 min , which is higher than most of
the reported non-noble metal based catalysts, and even compara-
ble to noble metal based catalysts.
2.5. Synthesis of CoBP/NGH catalysts
In a typical experiment for CoBP/NGH NPs, 4 mg NGH was
dispersed into 1.5 mL ultrapure water in a two-necked round bot-
tom flask. The mixture was dispersed uniformly by ultrasonication.
2
. Experimental
ꢀ
1
Then, 0.4 mL cobalt chloride solution (CoCl
2
, 0.1 mol L ), and
2.1. Chemicals and materials
different amounts of NaH PO solution (0 mmol, 0.02 mmol,
2
2
ꢀ
1
0.06 mmol, 0.1 mmol, 0.1 mol L ) were added into the flask.
All chemicals were commercial and used without further puri-
Ultrasonication was required to obtain an equably dispersion. The
resulting mixture was then reduced by aqueous solution containing
1 mmol NaBH4 with vigorous stirring at 298 K. After the reaction
completely, the product was collected by centrifugation washing,
and drying by pump vacuum.
fication. Ultrapure water was used as the reaction solvent.
Cobalt chloride hexahydrate (CoCl O, Sinopharm Chemical
þ6H
Reagent Co., Ltd., ꢁ99%), Sodium hypophosphite (NaH PO , Aladdin
Co., Ltd. ꢁ99.0%), Sodium ammonia sulfate ((NH SO , Aladdin Co.,
Ltd.ꢁ99.0%) Tetraphydrofuran (THF, Sinopharm Chemical Reagent
Co., Ltd., >98%), sodium borohydride (NaBH , Sinopharm Chemical
Reagent Co., Ltd., >96%), potassium permanganate (KMnO
Shanghai Chemic Co., Ltd, ꢁ99.5%), hydrogen peroxide (H
2
2
2
2
4
)
2
4
4
2.6. Catalytic hydrolysis of AB
4
2
,
,
2
O
In a typical experiment, The hydrolysis reaction of AB by CoBP/
NGH NPs were tested at 298 K. Various CoBP/NGH NPs doping with
different phosphorus content were added into a 25 mL two-necked
round bottom flask. One neck was connected to a gas burette to
monitor the volume of the gas evolution, and the other for the
Sinopharm Chemical Reagent Co., Ltd, ꢁ30%), phosphoric acid
(
(
H
H
3
PO
SO
4
, Sinopharm Chemical Reagent Co., Ltd, AR), sulfuric acid
, Sinopharm Chemical Reagent Co., Ltd, 95e98%), ethanol
2
4
absolute (C H
2 5
OH, Sinopharm Chemical Reagent Co., Ltd., ꢁ99.7%),
, Sinopharm Chemical Reagent Co., Ltd.,
99.0%), graphite power (Sinopharm Chemical Reagent Co., Ltd,
99.85%) were used as received.
ꢀ
1
ethylenediamine (C
2
8
H N
2
introduction of AB (1 mmol, 1 mol L ). A water bath was used to
control the temperature of the reaction solution at 298 K. The value
of turnover frequency (TOF) can be calculated using Equation (2).
ꢁ
ꢁ
2.2. Preparation of ammonia borane (AB)
TOFinitial ¼ Patm
V
nCo
H
2
=RT
(2)
t
Sodium borohydride (NaBH
4
, 0.05mol) and sodium ammonia
sulfate ((NH SO , 0.1mol) were added to a 250 mL two-necked
4
)
2
4
where TOF initial is initial turnover frequency, Patm is the atmo-
spheric pressure, VH2 is the volume of the generated gas when the
conversion reached 50%, R is the universal gas constant, T is room
temperature (298 K), nCo is the mole amount of Co and t is the
reaction time. The temperatures were varied from 298 to 313 K to
obtain the activation energy (Ea), while CoBP/NGH and AB were
kept the same ratio (catalyst/AB ¼ 0.04).
round-bottom flask with one neck connected to a condenser.
Tetrahydrofuran (THF, 100 mL) was transferred into the flask, and
the contents were vigorously stirred at 313 K. The reaction was
under a nitrogen atmosphere. After 4 h, the resultant solution was
filtered by suction filtration and the filtrate was concentrated under
vacuum at room temperature. Then, the product was purified by
diethyl ether.
2.7. Cycle stability tests
2.3. Preparation of graphene oxide (GO)
For cycle stability tests, catalytic reactions were tested 5 times
(
Graphene oxide) GO was prepared by a modified Hummers
method [51]. During this process, 3.0 g carbon black was added into
a mixture of concentrated H SO /H PO (360:40 mL) in a 1 L flakes.
Then, a certain amount of KMnO (18.0 g) was gradually added to
by adding another the same molar contents of AB (1 mmol) after
the previous cycle at 298 K.
2
4
3
4
4
2.8. Physical characterizations
the flakes. The resulting mixture was then heated to 323 K and
stirred for 12 h. After cooling to room temperature, the mixture was
Powder X-ray diffraction (XRD) patterns were measured by a
added to 400 mL of water with 30% H
2
O
2
(3 mL). After adding 2 mL
Bruker D8-Advance X-ray diffractometer using Cu K
a
radiation
ꢂ
of excess H , a permanent yellow color was formed, which
2
O
2
source (
l
¼ 0.154178 nm) with a velocity of 8 /min. Inductively
indicated that the complete oxidation of the graphite was observed.
The resulting solution was centrifuged to obtain the product. Then,
the obtained product was washed with deionized water, 30%
diluted hydrochloric acid, and absolute ethyl alcohol many times
and then dried in vacuum at 298 K.
coupled plasma-atomic emission spectroscopy (ICP-AES) was per-
formed on IRIS Intrepid II XSP. X-ray photoelectron spectroscopy
(XPS) measurement was performed with a Kratos XSAM 800
spectrophotometer. The morphologies and sizes of the samples
were observed by Tecnai G20 U-Twin transmission electron

Y. Men et al. / Journal of Alloys and Compounds 735 (2018) 1271e1276
1273
microscope (TEM) equipped with an energy dispersive X-ray de-
tector (EDX) at an acceleration voltage of 200 kV. Scanning electron
microscopy (SEM) images were obtained using an electron micro-
scope (SIGMA, ZEISS).
Ea was calculated to be 39.42 kJ molꢀ1, which is quite lower than
those of most of reported Co-based catalysts and even some noble-
metal based catalysts as indicated in Table S2.
The powder X-ray diffraction (XRD) patterns of all the samples
shown in Fig. S2 indicate the as-prepared CoBP/NGH catalysts with
amorphous structure. It has been reported that amorphous struc-
ture belongs to metastable phase, which contains a lot of short-
range order of atoms and long-range disorder structure with
more active sites in comparison to the crystalline phase [53].
3
. Results and discussion
Nitrogen-doped graphene hydrogel (NGH) was first prepared at
ꢂ
1
80 C according to a reported hydrothermal method [52]. Then the
0.15
The Co0.79B P0.06 was also analyzed by X-ray photoelectron
CoBP/NGH catalysts with different phosphorus doping were suc-
cessfully prepared via a simple one-pot co-reduction approach and
studied for catalytic hydrogen generation toward hydrolysis of AB
at room temperature. During this process, the NGH was used as
support. NaBH was not only used as a boron source, but also as a
4
reductant, in which the metal precursors were reduced to form CoB
NPs. The CoBP/NGH with different phosphorus doping were ob-
spectroscopy (XPS). As shown in Fig. 3a, the signals of Co 2p3/2
peaks at binding energies of 778.5eV, 780.6eV and 786.4eV are
0
assigned to the Co , oxidized Co and satellite state, respectively.
Similarly, the signals of P 2p peaks (Fig. 3b) at binding energies of
0
1
29.1eV and133.5 eV are attributed to P and oxidized P, respec-
tively. And the signals of B1s (Fig. 3c) peaks located at binding
0
energies of 188.7eV and 191.7eV are attributed to B and BeO,
tained by changing the amounts of NaH
detected by inductively coupled plasma-atomic emission spec-
troscopy (ICP-AES) as shown in Table S1. Initially, Co0.85
2 2
PO , which were further
respectively. The formation of oxidized metals may be result from
being exposure to oxygen during the catalysts preparation process
B
0.15/NGH
[54]. Obviously, after doping P, the peak of Co 2p3/2 located at the
were prepared to test the catalytic activity toward the hydrolysis of
AB. As expected, it needs more than 10 min to release only 2.5
binding energies of 778.5eV has a positive shift of 0.4 eV in
Co0.79B0.15P0.06/NGH when comparing to Co0.85B0.15/NGH, probably
due to the decrease of electron density and increase of d-band
vacancies in the metal active sites [55], which might result in
boosting the catalytic activity. On the other hand, comparing with
the binding energy of pure P (129.7eV) [56], the peaks of P 2p
located at the binding energy of the 129.1eV for Co0.79B P /
0.15 0.06
NGH is negative shifted to about 0.6 eV, which indicates that there
is low charge transfer from the Co to P. In addition, the peaks of B 1s
ꢀ
1
equivalent of gas (Fig. 1a), with the TOF value of 6.2 min , which
exhibits relatively low catalytic activity and hydrogen selectivity.
However, after doping with the phosphorus, the resulted CoBP/
NGH catalysts exhibit much enhanced catalytic activities with 100%
0.15
hydrogen selectivity. Specifically, the Co0.79B P0.06/NGH exhibited
the highest catalytic activity among all the catalysts tested, with the
ꢀ1
TOF value of 32.8 min , which is almost 5 times higher than that of
0.15/NGH without P doping, and higher than those of most of
Co0.85
B
0.15 0.06
located at the binding energy of the 188.7 eV for Co0.79B P /
the previous reported non-noble metal based catalysts as shown in
Table S2. These results highlight the synergistic effect between CoB
and P in facilitating hydrolysis of AB. Furthermore, for comparison,
NGH has a positive shifted of 0.3 eV comparing with the binding
energy of pure B (188.4eV) [57]. All results indicate that there is
strong electronic interaction between Co, P and B, which can
further influence the bonding configuration of the metal active
center, resulting in an enhancement of catalytic activity. Further-
0.15
the Co0.79B P0.06/NGH NPs without supported material or sup-
ported on graphene oxide (GO) were also prepared, and their cat-
alytic activities toward hydrolysis of AB were studied. As shown in
Fig. S1, their catalytic activities are both inferior to that of
0.15
more, as shown in Fig. S3, for the C1s of Co0.79B P0.06/NGH, it can
be seen clearly that the oxygen containing functional groups eCeO,
and eC]O disappeared, and the eCOO decreased significantly,
comparing with the C1s of GO (Fig. S2a) [58], which suggest that
the abundant of oxygen groups have been reduced. At the same
time, a new peak at 285.2eV can be observed, which is due to the
doping of nitrogen atoms. Meanwhile, as shown in Fig. S4, three
types of nitrogen doped species can be observed clearly for N1s of
Co0.79
B
0.15
P
0.06/NGH, suggesting the three dimensional nitrogen-
doped graphene hydrogel is beneficial for the hydrolysis of AB
(vide infra).
0.15
The durability of Co0.79B P0.06/NGH was also tested in cycle
experiment by adding the same molar amount of AB after the
previous completion at room temperature. As shown in Fig. 1b,
even after five cycles, the catalytic activity and hydrogen selectivity
were still maintained well. To obtain the activation energy (Ea) of
0.15
Co0.79B P0.06/NGH NPs. The binding energies of 399.6 eV, 398.1 eV
and 400.8 eV are corresponding to pyrrolic N and pyridinic N,
graphitic N, respectively [59]. In general, it can be suggested that
nitrogen atom has been doped into the carbon bonds of graphene
catalytic hydrolysis of AB by Co0.79
decomposition reaction temperatures were varied from 298 K to
13 K as shown in Fig. 2a. According to the Arrhenius equation, the
0.15
B P0.06/NGH, the catalytic
3
Fig. 1. (a) Catalytic performance tests of Co0.79
Co0.80 0.04/NGH, Co0.79 0.06/NGH, Co0.80
B
0.15
P
0.06/NGH with different molar of P content. (catalyst/NH
3
BH
3
¼ 0.04) (a, b, c, and d, represent the Co0.85
B0.15/NGH,
BH at room temperature.
B
0.16
P
B
0.15
P
B
0.13
P
0.07/NGH) (b) durability tests of Co0.79 0.06/NGH toward the dehydrogenation hydrolysis of NH
0.15
B P
3
3

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Y. Men et al. / Journal of Alloys and Compounds 735 (2018) 1271e1276
Fig. 2. (a) Time plots for hydrogen generation toward the dehydrogenation hydrolysis of NH
catalyst/NH BH BH
¼ 0.04) (b) Arrhenius plot of lnk versus 1/T during the hydrolysis of NH
3
BH
3
catalyzed by Co0.79
0.15
B P0.06/NGH at temperatures ranging from 298 to 313 K.
(
3
3
3
3
over Co0.79B P
0.15
0.06/NGH.
0.15
Fig. 3. (a) The XPS spectra of (a) Co 2p 3/2 and (b) P 2p and (c) B 1s for the Co0.79B P0.06/NGH NPs.
successfully from the C 1s and N 1s of Co0.79
which may significantly enhance the interaction between metal
and support to facilitate the hydrolysis of AB [60].
Furthermore, as shown in Fig. S5, the N-doped graphene
hydrogel is cylindrical elastic hydrogel solid, with the diameter of
B
0.15
P
0.06/NGH NPs,
pore-size distribution of the NGH (Fig. S7(b)), it can be seen clearly
that most of the pores possessing a volume of 0.288 cm /g, with a
peak pore diameter of 3.697 nm. It is reported that these pores
could greatly increase the contact with AB and facilitate the facile
release or evolved hydrogen bubbles during the catalysis [61].
3
2
.1 nm and height of 3.7 nm. It can be seen clearly from the scan-
The microstructure of the obtained Co0.79
were analyzed by transmission electron microscopy (TEM). As
shown in Fig. 4a and b, Co0.79 0.06 nanoparticles are well
dispersed on the 3D NGH. For comparison, Co0.85 0.15/NGH NPs
0.15
B P0.06/NGH NPs
ning electron microscope (SEM) (Fig. S6), the structure of NGH is
three-dimensional poriferous reticulate, which has varieties of
porous sizes. Furthermore, the porosity of the NGH was measured
B
0.15
P
B
by N
2
adsorption/desorption at 77 K. As shown in Fig. S7(a), the BET
were also characterized by TEM (Fig. S8), however, severely ag-
gregation is observed, which might impede the mutual effect
2
specific surface area of the NGH sample is 190.42 m /g. From the

Y. Men et al. / Journal of Alloys and Compounds 735 (2018) 1271e1276
1275
0.15
Fig. 4. TEM images of with different magnifications (a, b) of Co0.79B P0.06/NGH.
between the NH
3
BH
3
molecule and metal active centers, resulting
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in the decrease of the catalytic activity. Furthermore, the energy-
dispersive X-ray (EDX), as shown in Fig. S9, confirms the co-
presence of Co, B and P. In addition, the CoBP/NGH catalysts after
stability test were further characterized by XRD and TEM. As shown
in Fig. S10, the XRD indicates CoBP/NGH after stability test still
possess amorphous structure. However, slight aggregation of CoBP
NPs were observed from the TEM images as shown in Fig. S11,
which might be the reason for the decrease of the catalytic per-
formance. Further study about increasing the stability of the cata-
lysts is still in process in our lab.
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[
[
4
. Conclusions
[
In summary, the three-dimensional nitrogen doped graphene
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B
0.15
P
0.06/NGH catalyst exhibits superior catalytic
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Supplementary data related to this article can be found at
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