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 4 6 ( 2 0 2 1 ) 2 5 3 7 6 e2 5 3 8 4

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journal homepage: www.elsevier.com/locate/he

Superior hydrogen generation from sodium

borohydride hydrolysis catalyzed by the bimetallic
CoeRu/C nanocomposite

Wenkai Huang, Fuhua Xu, Xiang Liu*

College of Materials and Chemical Engineering, The Engineering Research Center of Eco-environment in Three Gorges
Reservoir Region, Ministry of Education, Key Laboratory of Inorganic Nonmetallic Crystalline and Energy Conversion
Materials, China Three Gorges University, Yichang, Hubei, 443002, China

highlights graphical abstract

A series of bimetallic M-Ru/C

nanocomposites are synthesized
for H2 generation.

H2 generation is synergetically
improved by alloying Ru/C with Co
or Ni.

The TOF of Co-Ru/C is 117.69
mol(H2)$molRu-1$min-1.

The TOF of Co-Ru/C reaches to
436.51 mol(H2)$molRu-1$min-1 in the
presence of NaOH.

article info abstract

Article history: Sodium borohydride has been widely regarded as a promising hydrogen carrier owing to its
Received 6 April 2021 greatly hydrogen storing capability (10.8 wt%), high weight density and excellent stability
Received in revised form in alkaline solutions. Herein, we first design and synthesize a series of bimetallic M-Ru/C
9 May 2021 nanocomposites (including FeeRu/C, CoeRu/C, NieRu/C and CueRu/C), via simply alloying
Accepted 12 May 2021 of commercial Ru/C with nonprecious metal, for superior H2 evolution from the NaBH4
Available online 16 June 2021 hydrolysis. The result exhibits that H2 generation is synergetically improved by alloying Ru/
C with Co or Ni, while it is hindered by alloying Ru/C with Fe or Cu. Indeed, CoeRu/C
Keywords: presents the highest efficient catalytic activity for H2 generation, with the TOF of
Sodium borohydride 117.69 mol(H2)$mol1 1 1 1
Ru$min , whereas Ru/C is only 57.08 mol(H2)$molRu$min . In addition,

Hydrogen the TOF of CoeRu/C reaches to 436.51 mol(H2)$mol1

Ru $min
1
(96.7 L(H2)$g1 1
Ru $min ) in the

CoeRu/C presence of NaOH.

Bimetallic © 2021 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.
Hydrolysis

* Corresponding author.
E-mail address: [email protected] (X. Liu).
https://doi.org/10.1016/j.ijhydene.2021.05.083
0360-3199/© 2021 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.
 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 4 6 ( 2 0 2 1 ) 2 5 3 7 6 e2 5 3 8 4 25377

CoeRu/C reaches to 436.51 mol(H2)$mol1 Ru $min

1
(96.7 L(H2)$
Introduction g1 1
) in the presence of 0.09 M NaOH.
Ru $min

With the rapid development of economy, the exploration of

low cost, high efficient and eco-friendly renewable energy Experimental section
sources has attracted wide attention due to the increasingly
serious energy crisis and environmental problems [1e5]. Chemicals and materials
Recently, hydrogen is comprehensively considered as the one
of most highly potential alternative energy sources to hydro- Sodium borohydride (NaBH4, 97%) was obtained from Shanghai
carbon fuels from fossil sources (e.g. petroleum, coal and Lingfeng Chemical Reagent Co., Ltd. Borane-ammonia complex
natural gas) due to its eco-friendly and extremely high-energy (H3N$BH3, 97%) was received from Aladdin Reagent Co., Ltd.
density [6e9]. As a promising hydrogen carrier, sodium boro- Ruthenium on carbon (Ru/C, Ru 5% wt), Iron (III) nitrate non-
hydride (NaBH4) has attracted a wide range of interests owing ahydrate (Fe(NO3)3$9H2O, 98.5%), Nickel chloride hexahydrate
to its greatly hydrogen storing capability (10.8 wt%), high (NiCl2$6H2O, 99%) and Copper sulfate pentahydrate (CuSO4-
weight densities and excellent stability in alkaline solutions $5H2O, 99%) were supplied by Shanghai Macklin Biochemical
[10e17]. Normally, sodium borohydride hydrolysis under Co., Ltd. Cobalt (II) nitrate hexahydrate (Co(NO3)2$6H2O, 99.99%)
alkaline conditions provides 4 stoichiometries of H2 (Eq. (1)) and Carbon (AR, 200 ) were purchased from Shanghai Jiuding
without CO2 release and its by-product NaB(OH)4 could be Chemical Technology Co., Ltd. Sodium hydroxide NaOH (AR,
reconverted back to the reactant [18,19]. Hydrogen evolution 500 g) was obtained from Tianjin Komiou Chemical Reagent
upon the hydrolysis of sodium borohydride usually requires Co., Ltd. The chemicals listed above were used as provided
noble metal (such as Rh, Pt, Pd, Au and Ru) based catalysts for a without further purification.
quick H2 release [20e28]. However, the practical uses of these
noble metal have been seriously restricted by their rareness Synthesis of CoeRu/C nanocomposite
and high cost [29e32]. Therefore, a large number of efforts
have recently been made to design and develop earth- Firstly, 0.004 mmol of Ru/C (8.08 mg) and 8.0 ml of H2O were
abundant alternative catalysts [33e35]. For examples, Zhao's dispersed into a Schlenk flask. 1.0 ml aqueous solution of
group reported Co@ZIF-8 catalyzed H2 release from the hy- Co(NO3)2$6H2O (0.08 mmol) was added under stirring condi-
drolysis of sodium borohydride with the best TOF of 2.9 LH2 tion at 30  C. Then, 1.0 ml aqueous solution of borane-
min1 g1Co [36]. Liu's group also reported a cobalt based CHNA/
ammonia complex (1.0 mmol) was added quickly into the
Ti as the efficient and robust 3D catalyst for dehydrogenation above solution and stirred continuously for 1 h. Finally, the
of alkaline sodium borohydride solution for on-demand H2 precipitant was centrifuged and washed with deionized water
evolution [37]. Sun's group first reported CoP and Fe-doped CoP four times. The precipitant was named as CoeRu/C. The pre-
nanoarrays as the nonprecious metal catalysts for efficient H2 cipitant was re-dispersed in 9 ml of H2O into a Schlenk flask
generation upon sodium borohydride hydrolysis [38,39]. In form a dispersion for further use.
2020, Jiang's group first investigated the catalytic performances
of various Co-based catalysts in the hydrolysis of sodium Catalytic hydrogen generation
borohydride. And they found sulfur-containing salt plays a
positive role in the improvement of catalytic activity [40]. All the above CoeRu/C (0.004 mmol) dispersion was added
into a Schlenk flask at 30  C (water bath) with continuous
NaBH4 þ 4H2 O/NaBðOHÞ4 þ 4H2 (1)
stirring. The Schlenk flask was linked to a water-filled column
As a part of our current research interests on the explora- by the gas outlet. Then, 1.0 ml aqueous solution of NaBH4
tion of novel and efficient catalytic systems for hydrogen (1.0 mmol) was rapidly injected into the flask, time started at
generation from various H-rich chemical hydrides [41e47], the same time and recorded the volume of hydrogen and the
herein, we first design and synthesize a series of bimetallic M- corresponding time. The volume of H2 had been decided
Ru/C nanocomposites (including FeeRu/C, CoeRu/C, NieRu/C periodically by measuring the volume of variation of water in
and CueRu/C), via simply alloying of commercial Ru/C with the column. For durability tests, after the first reaction, the
nonprecious metal, for superior hydrogen generation from the precipitant was centrifuged, washed with deionized water
hydrolysis of sodium borohydride. Particularly, Ru/C, as a four times, and then re-dispersed in 9 ml of H2O into a Schlenk
heterogeneous and commercial catalyst, has been widely flask for subsequent reactions.
applied in hydrogenation reactions [48e50]. To the best of our
knowledge, it is the first available report on the compared Characterization
synergistic effects of the alloying nonprecious metal (e.g. Fe,
Co, Ni and Cu) on the commercial Ru/C for promoting H2 Transmission electron microscopy (TEM), scanning trans-
generation from sodium borohydride hydrolysis. Then we mission electron microscopy (STEM), and energy dispersive X-
found CoeRu/C exhibits the most highest TOF value of ray spectroscopy (EDX) compositional mapping of CoeRu/C
117.69 mol(H2)$ molRu1$min1, whereas commercial Ru/C were performed with a TECNAI F-20 microscope (JEOL 2100F)
is only 57.08 mol(H2)$ molRu1$min1. In addition, the TOF of operated at 200 kV. X-ray photoelectron spectrometry (XPS) of
25378 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 4 6 ( 2 0 2 1 ) 2 5 3 7 6 e2 5 3 8 4

CoeRu/C was conducted with a Thermo SCIENTIFIC ESCALAB dispersive X-ray spectrometry (EDX), X-ray photoelectron
250Xi system spectrometer with a monochromatic Cu Ka X- spectroscopy (XPS) of CoeRu/C have also been further
ray source in an ultra-high vacuum (UHV) chamber. X-ray analyzed. In Fig. S6, the nitrogen adsorption-desorption iso-
diffraction (XRD) of CoeRu/C was analyzed by a Rigaku Ultima therms of CoeRu/C show the specific surface area, pore vol-
Ⅳ. The Brunner-Emmet-Teller (BET) specific area, pore volume ume and pore size of CoeRu/C is 442.39 m2/g, 0.64 cm3/g and
and pore size of CoeRu/C was measured by a NOVAtouch fast. 5.77 nm, respectively. The HRTEM image taken from one
CoeRu/C nanocomposite (Fig. 2f) displays clear lattice fringes
with the lattice of 0.200 nm, 0.216 nm and 0.210 nm corre-
Results and discussion sponding to crystallographic planes of Co (002), Ru (002) and
alloyed CoRu [51], suggesting the co-existence of alone Co,
The micromorphologies of bimetallic M-Ru/C alone Ru and alloyed CoRu in the CoeRu/C. As shown in Fig. 4,
nanocomposites the EDX mappings of CoeRu/C nanocomposite has also been
recorded for further confirming the detailed localization of Co
In the present work, bimetallic M-Ru/C nanocomposites and Ru in the catalyst. The Fig. 4aed reveals the Co and Ru
(including FeeRu/C, CoeRu/C, NieRu/C and CueRu/C) have elements are homogenously distributed in the CoeRu/C
been obtained by using commercial Ru/C and the corre- nanocomposite. The co-existence of Co and Ru in the CoeRu/
sponding metal salt (Fe(NO3)3, Co(NO3)2, NiCl2 and CuSO4) C has been proved by the appearance of Co and Ru elements in
dissolved in water in a standard molar ratio 1 : 20 of Ru/metal the EDX sum spectrum (Fig. 4e). In addition, the chemical
ions and followed by the addition of NH3BH3 as the reductant states of each element in CoeRu/C nanocomposite have been
at 30  C (Fig. 1). Transmission electron microscopy (TEM) have further measured by XPS. The high-resolution XPS spectra of
been measured to confirm the morphology and size of the Co 2p reveals that two peaks at 783.05 eV and 799.20 eV are
bimetallic M-Ru/C nanocomposites. As shown in Fig. 2a, the ascribed to Co (II) [52], while two peaks at 780.90 and 796.92 eV
size of commercial Ru/C is only 1.03 nm (Fig. S1). The sizes of are belonged to Co (III) in Fig. 5a. The Co (0) cannot be detected
FeeRu/C (2.56 nm, Fig. 2b and S2), CoeRu/C (2.11 nm, Fig. 2c on the surface of the CoeRu/C nanocomposite. It is obvious
and S3) and CueRu/C (1.89 nm Fig. 2e and S5) only are a little that the Co (0) has been completely oxidized to Co3O4. More-
bit larger than Ru/C. over, two satellite peaks have further confirmed that Co(0) has
Whereas NieRu/C (24.86 nm) is much larger (Fig. 2d and been oxidized to the high valence cobalt. XPS of Ru 3p exhibits
S4). Then the catalytic H2 generation from sodium borohy- two peaks positions at 463.43 eV and 486.02 eV are exclusively
dride hydrolysis in water has been chosen as a model reaction assigned to the zero-valent surface atoms of Ru in CoeRu/C.
to evaluate the catalytic efficiency of bimetallic M-Ru/C
nanocomposites. As shown in Fig. 3a, the hydrolysis of so- Catalytic performances of CoeRu/C in the NaBH4 hydrolysis
dium borohydride has been carried out in the presence of
0.4 mol% bimetallic M-Ru/C nanocomposites with 1 mmol of Based on the above results, CoeRu/C nanocomposite has been
NaBH4 in water at 30  C, the result exhibits that H2 generation used for the further reaction kinetics study. We found that the
has been synergetically improved by alloying Ru/C with Co or dosages of catalyst and initial NaBH4 and reaction temperature
Ni, while hydrogen generation has been hindered by alloying could influence the hydrogen generation from the hydrolysis of
Ru/C with Fe or Cu. The Co/C does not work. Indeed, CoeRu/C sodium borohydride. Fig. 3b exhibits the catalytic activities of
is the highest efficient catalyst with the TOF of 117.69 mol(H2)$ the NaBH4 hydrolysis under the different dosages of CoeRu/C
mol1 1
Ru $min , whereas Ru/C is only 57.08 mol(H2)$ catalyst ranging from 0.2 to 0.8 mol%. The slope of H2 genera-
mol1Ru $min 1
). The order of catalytic activities of these cata- tion rate vs CoeRu/C catalyst dosage is 0.72, suggesting H2
lysts in H2 evolution is established as follow: CoeRu/ generation rate increases with the increasing CoeRu/C catalyst.
C > NieRu/C > Ru/C > FeeRu/C > Cue Ru/C > Co/C. The effect of initial NaBH4 dosage (from 0.5 mmol to 1.25 mmol)
As CoeRu/C is the most efficient catalyst, Brunner-Emmet- has been illustrated in Fig. 3c. The slope of H2 generation rate vs
Teller (BET), the high-resolution TEM (HRTEM), energy initial NaBH4 dosage is almost zero (0.14), indicating that the

Fig. 1 e The synthesis of FeeRu/C, CoeRu/C, NieRu/C and CueRu/C nanocomposites.

 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 4 6 ( 2 0 2 1 ) 2 5 3 7 6 e2 5 3 8 4 25379

Fig. 2 e TEM images of (a) Ru/C, (b) FeeRu/C, (c) CoeRu/C, (d) NieRu/C and (e) CueRu/C and (f) HRTEM of CoeRu/C.

Fig. 3 e (a) Comparison of catalytic activities of Ru/C, FeeRu/C, CoeRu/C, NieRu/C and CueRu/C in H2 evolution; (b) Plots of
the generated H2 volume vs. time for H2 evolution catalyzed by various amounts of CoeRu/C; (c) Plots of the generated H2
volume vs. time for the H2 evolution in the presence of various amounts of initial NaBH4 catalyzed by 0.4 mol% CoeRu/C; (d)
Plots of the generated H2 volume vs. time for H2 evolution catalyzed by 0.4 mol% CoeRu/C at different reaction temperatures.
25380 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 4 6 ( 2 0 2 1 ) 2 5 3 7 6 e2 5 3 8 4

293e323 K, using 1 mmol of NaBH4 in the presence of 0.4 mol%

CoeRu/C. According to Arrhenius plot, the activation energy
(Ea) for the hydrolysis is 60.09 kJ/mol, which is a little bit large
[53e57]. Then, the pH of the hydrolysis process at pH neutral
medium has been recorded in Fig. S7. The pH value increases
from 9 to 11 as the reaction proceed. The increasing of pH value
is attributed to the accumulation of product NaB(OH)4 of NaBH4
hydrolysis. In addition, the catalytic activity of the CoeRu/C
toward the hydrolysis of NaBH4 in the presence of various
concentration of NaOH (0.05e0.11 M) has been investigated in
Fig. 6. The NaBH4 hydrolysis has been provided the highest TOF
value of 436.51 molH2$mol1 Ru $min
1
in the presence of 0.09 M
NaOH. Interestingly, Ea has been decreased from 60.09 kJ/mol to
50.20 kJ/mol after the addition of NaOH (Fig. S8). To sum up, the
efficient catalytic activity of CoeRu/C is attributed to the
excellent positive bimetallic synergistic effect.

The reusability and stability of CoeRu/C on the H2 evolution

As a heterogeneous catalyst, the reusability and stability of

CoeRu/C nanocomposite has also been studied in the NaBH4
hydrolysis. So, the hydrolysis reactions have been performed
to recycle the CoeRu/C nanocomposite many times via simple
filtration at 30  C using 1 mmol NaBH4 and 10 ml of water
solution with 0.4 mol% CoeRu/C to test the durability of
catalyst. The Fig. 7a presents that the as-obtained CoeRu/C
nanocomposite has been successfully reused at least 5 times
without significantly loss in catalytic activity. In addition, the
Ru/C, fresh and separated 5th reused CoeRu/C catalyst has
been tested by XRD in Fig. 7b. We found that 5th reused
CoeRu/C catalyst basically remains the same structural as the
fresh one, indicating that as-synthesized CoeRu/C catalyst
Fig. 4 e (a) STEM image, (b) combined (Ru and Co) EDX
has acceptable stability, durability and recyclability.
compositional mapping, the corresponding (c) Ru and (d)
The catalytic performance of this CoeRu/C bimetallic
Co EDX compositional mapping, (e) sum spectrum of
nanocatalyst have been also compared with recently published
CoeRu/C.
noble metal catalysts for the hydrolysis of NaBH4. The Fig. 8
exhibits that as-synthesized CoeRu/C bimetallic nanocatalyst
are comparable and even superior to most reported catalysts
hydrogen generation rate is not affected by initial NaBH4
[58e69]. The TOF of CoeRu/C reaches to 96.7 L(H2)$g1 Ru $min
1
dosage. As shown in Fig. 3d, the reaction temperature depen- 1 1
(436.51 mol(H2)$molRu$min ) in the presence of 0.09 M NaOH.
dence of H2 generation has been investigated in the range of

Fig. 5 e Xps of CoeRu/C. (a)XPS of Co 2p and (b) Ru 3p.

 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 4 6 ( 2 0 2 1 ) 2 5 3 7 6 e2 5 3 8 4 25381

Fig. 6 e (a) Hydrolysis of NaBH4 catalyzed by 0.4 mol% CoeRu/C in the presence of 0e0.11 M NaOH in water at 30  C and (b)
Variation of the TOF obtained from various concentration of NaOH.

Fig. 7 e (a) Recycling of CoeRu/C in aqueous solution (10 mL) containing 1 mmol of NaBH4 in the presence of 0.09 M NaOH at
30  C; (b) XRD of Ru/C, fresh and 5th reused CoeRu/C.

Conclusion

In this work, a series of bimetallic M-Ru/C nanocomposites

(including FeeRu/C, CoeRu/C, NieRu/C and CueRu/C), via
simply alloying of commercial Ru/C with nonprecious metal,
have been first designed and synthesized for superior H2 gen-
eration from the hydrolysis of sodium borohydride. The result
exhibits that H2 generation was synergetically improved by
alloying Ru/C with Co or Ni, while it was hindered by alloying
Ru/C with Fe or Cu. Indeed, CoeRu/C presents the most efficient
catalytic activity for H2 generation, with the TOF of
117.69 mol(H2)$mol1 1
Ru$min , whereas Ru/C is only
1 1
57.08 mol(H2)$ molRu$min . In addition, the TOF of CoeRu/C
reaches to 436.51 mol(H2)$mol1 Ru $min
1
(96.7 L(H2)$g1 1
Ru $min )
in the presence of 0.09 M NaOH. The efficient catalytic activity
of CoeRu/C is attributed to the excellent positive bimetallic
synergistic effect. This work provides a simple and efficient
strategy to synthesize bimetallic nanocatalyst for synergisti-
Fig. 8 e The catalytic activity of CoeRu/C is compared with cally promoting hydrolysis of borohydrides in the commercial
recently published literature. scale process.
25382 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 4 6 ( 2 0 2 1 ) 2 5 3 7 6 e2 5 3 8 4

recyclable catalyst for hydrogen production from hydrazine

Declaration of competing interest in aqueous solution. J Mater Chem 2019;7:9903e11.
[12] Shi Y, Zhang B. Recent advances in transition metal
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financial interests or personal relationships that could have hydrogen evolution reaction. Chem Soc Rev 2016;45:1529e41.
[13] Duman S, Kay B, Caf F, Enez B, Fincan S. Innovative hydrogen
appeared to influence the work reported in this paper.
release from sodium borohydride hydrolysis using
biocatalyst-like Fe2O3 nanoparticles impregnated on Bacillus
simplex bacteria. Int J Hydrogen Energy 2021;46:15410e30.
Acknowledgment [14] Arzac G, Fernandez A. Advances in the implementation of
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tion of China (21805166), the 111 Project (D20015), the Engi- [15] Abdelhamid H. A review on hydrogen generation from the
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