Dehydrogenation of sodium borohydride using cobalt embedded zeolitic imidazolate frameworks

Article abstract of DOI:10.1016/j.jssc.2021.122034

In the last decades were witnesses that hydrogen is in the limelight as an environmentally benign and alternative energy source to fossil fuels. The hydrolysis of sodium borohydride (NaBH₄) is promising for the synthesis of materials/chemical compounds and on-demand hydrogen generation-based applications. Herein, cobalt embedded zeolitic imidazolate frameworks (Co@ZIF-8) were synthesized at ambient temperature via a one-pot method (within 60 ?min). X-ray diffraction (XRD) pattern ensures the successful synthesis of a pure phase of Co@ZIF-8 crystals. Transmission electron microscope (TEM) and nitrogen (N₂) adsorption-desorption isotherm reveal that Co@ZIF-8 has a hierarchical porous structure. Co@ZIF-8 exhibited high catalytic activity for the hydrolysis of NaBH₄ with a hydrogen generation rate (HGR) of 7230 ?mL?g_cat^?1?min^?1 (18 ?× ?10⁶ ?mL?g_Co^?1?min^?1). The high catalytic performance and the simple synthesis procedure of Co@ZIF-8 endow the material's high potential to be a catalyst for hydrogen generation via the hydrolysis of hydrides such as NaBH₄.

Full text of DOI:10.1016/j.jssc.2021.122034

Journal of Solid State Chemistry 297 (2021) 122034
Contents lists available at ScienceDirect
Journal of Solid State Chemistry
journal homepage: www.elsevier.com/locate/jssc
Dehydrogenation of sodium borohydride using cobalt embedded zeolitic
imidazolate frameworks
Hani Nasser Abdelhamid
Advanced Multifunctional Materials Laboratory, Department of Chemistry, Assiut University, 71516, Assiut, Egypt
A R T I C L E I N F O
A B S T R A C T
Keywords:
In the last decades were witnesses that hydrogen is in the limelight as an environmentally benign and alternative
Metal-organic frameworks
Zeolitic imidazolate frameworks
Hierarchical porous materials
Hydrogen
4
energy source to fossil fuels. The hydrolysis of sodium borohydride (NaBH ) is promising for the synthesis of
materials/chemical compounds and on-demand hydrogen generation-based applications. Herein, cobalt
embedded zeolitic imidazolate frameworks (Co@ZIF-8) were synthesized at ambient temperature via a one-pot
method (within 60 min). X-ray diffraction (XRD) pattern ensures the successful synthesis of a pure phase of
Co@ZIF-8 crystals. Transmission electron microscope (TEM) and nitrogen (N
2
) adsorption-desorption isotherm
reveal that Co@ZIF-8 has a hierarchical porous structure. Co@ZIF-8 exhibited high catalytic activity for the
ꢁ1
ꢁ1
6
ꢁ1
ꢁ1
hydrolysis of NaBH
The high catalytic performance and the simple synthesis procedure of Co@ZIF-8 endow the material’s high po-
tential to be a catalyst for hydrogen generation via the hydrolysis of hydrides such as NaBH
4
with a hydrogen generation rate (HGR) of 7230 mLꢀgcatꢀmin (18 ꢂ 10 mLꢀgCo ꢀmin ).
4
.
1
. Introduction
has lightweight/volume and produces hydrogen with high purity. The
process can be controllable and produces hydrogen for on-demand uses.
However, the process is kinetically slow and requires a catalyst to pro-
mote the process [48–51]. Thus, several materials were investigated as
Zeolitic imidazolate frameworks (ZIFs) [1–3] are a subclass of
metal-organic frameworks (MOFs) [4–13] with high thermal and
chemical stability [14]. Among several ZIFs, ZIF-8 (zinc imidazolate) has
been used as a substrate to encapsulate and support several species such
as enzyme horseradish peroxidase and magnetic nanoparticles [15],
catalysts for hydrogen generation via the hydrolysis of NaBH
high cost of precious metal catalysts, e.g., Ru, Pt, and Pd, limit their
applications as catalysts for the hydrolysis of NaBH [53]. On the other
4
[52]. The
4
achiral Cu
x
S [16], cobalt [17], dye [18,19], polysaccharides [20], and
side, transition metals are cheap and offer comparable efficiency [54].
The use of transition metals requires support to enhance the performance
and prevent aggregation of the active catalytic species. ZIFs are adequate
supports for transition metals than other supports such as MXene, MoS ,
2
and carbon nanotubes (CNTs) [55–57]. However, further explorations
are highly required to improve their efficiency.
Herein, the synthesis of cobalt encapsulated hierarchical porous ZIF-8
(Co@ZIF-8) has been reported. The synthesis procedure is simple using a
one-pot at ambient temperature. The reaction takes place in water
without the need for any organic solvent. The application of the syn-
thesized materials for the generation of hydrogen via the hydrolysis of
aggregation-induced emission molecule [21]. It can also proceed into
film/carbon cloth [22], membrane [23,24], and three-dimension (3D)
product [25]. It has been applied for several applications, including
catalysis, biomedicine, energy, and environmental-related fields [19,
2
5–33].
Hydrogen (H
fossil fuel with high energy content and environmental byproducts (e.g.,
O) after combustion [34]. It can be used for portable electronic devices
2
) gas is promising as an alternative energy source to
H
2
and proton exchange membrane fuel cell (PEMFC). Several companies
such as Toyota, Hyundai, and Honda have recently marketed small
H
2
-powered vehicles [34]. It can also be used for environmental appli-
4
NaBH was reported. Co@ZIF-8 material exhibited high catalytic activity
cations such as dye degradation [35] and reducing nitrophenol com-
compared to other previously reported materials.
pounds [36–38]. There are several methods for hydrogen production
[
39–47]. Among these methods, hydrides’ hydrolysis (1 mol NaBH
4
2. Materials and methods
produces 4 mol H ) offers several advantages. NaBH has high hydrogen
2
4
storage (gravimetric weight 10.6%) compared to other materials. NaBH
4
3 2 2
2-methylimidazole (Hmim), Zn(NO ) ⋅6H O, sodium hydroxide,
E-mail address: hany.abdelhamid@aun.edu.eg.
https://doi.org/10.1016/j.jssc.2021.122034
Received 3 January 2021; Received in revised form 27 January 2021; Accepted 31 January 2021
Available online 5 February 2021
0022-4596/© 2021 Elsevier Inc. All rights reserved.

H.N. Abdelhamid
Journal of Solid State Chemistry 297 (2021) 122034
Fig. 1. Schematic representation for the synthesis of Co@ZIF-8.
Fig. 2. a) XRD patterns Co@ZIF-8 and simulated XRD for ZIF-8, and b) Co@ZIF-8 before and after catalysis.
2
cobalt chloride (CoCl ), were purchased from Sigma Aldrich (Germany).
2.2. Characterizations instruments
4
NaBH was purchased from Alfa Aeser (UK).
The crystal phase purity of Co@ZIF-8 was approved using X-ray
diffraction (XRD, Philips1700 diffractometer) with wavelength, current,
and accelerating voltage (Vac) of 1.54 Å, 40 mA, and 40 V, respectively.
Imaging was performed using transmission electron microscopy (TEM,
JEM-2100, JEOL, Japan, Vac 200 kV). X-ray photoelectron spectroscopy
2
.1. Synthesis of Co@ZIF-8
A solution of NaOH (0.4 mL, 0.1 M) was added to a Zn(NO
3.2 mL, 0.84 M) at ambient conditions. A white gel was observed. Then,
a CoCl solution (0.64 g) was added. The solution was subjected to
stirring for 10 min before the addition of Hmim (32 mL, 3 M). The re-
action solution was continuously stirred for 30 min. A solution of NaBH
10 mmol) was added for the reduction of Co2þ to Co. The product was
3 2
) solution
(
(
K
XPS) was measured using Thermo Fischer (K-alpha, monochromated, Al
radiation, 1486.6 eV). The content of cobalt in Co@ZIF-8 was
2
α
measured using the atomic absorption flame (AAF, Buck scientific 210
VGC). For this measurement, Co@ZIF-8 was dissolved in a strong nitric
acid using ultrasonication. Surface areas (Brunauer–Emmett–Teller
4
(
separated using filtration and washed several times with water and
ethanol to remove unreacted species.
(SBET), and Langmuir specific surface areas (SLang)) and pore volumes of
2

H.N. Abdelhamid
Journal of Solid State Chemistry 297 (2021) 122034
Fig. 3. XPS analysis of Co@ZIF-8, a) survey, b) C1s, c) N1s, d) O1s, e) Zn2p, and f) Co2p.
Fig. 4. a) TEM and b) HR-TEM of Co@ZIF-8.
3

Fig. 5. a) Nitrogen adsorption-desorption isotherm, b) BET surface area fitting, pore size distribution using c) BJH model, and d) DFT model.

H.N. Abdelhamid
Journal of Solid State Chemistry 297 (2021) 122034
Co@ZIF-8 were carried using a nitrogen adsorption-desorption analyzer
(
Quantachrome Instrument Corporation, USA, at 77 K). Co@ZIF-8 was
ꢃ
degassed at 100 C for 3 h under vacuum before measurements. The
external surface area (SExt) was determined using the t-plot method. BJH
method (Barrett, Joyner, and Halenda) and Density functional theory
(
DFT) models were used to evaluate the pore size distribution.
2.3. Hydrolysis of NaBH
4
The hydrolysis of NaBH
4
solution (0.19 g in 100 mL H
2
O) was tested
ꢃ
at 30 C. The water displacement method was used to measure the
hydrogen generated volume during the reaction [58]. Hydrogen was
exhausted through a Tygon tube to an inverted graduated cylinder
.Co@ZIF-8 (100 mg) was added to a NaBH
4
solution (0.19 g in 100 mL
of water) following the same setup.
The effect of Co@ZIF-8 catalyst loading was investigated using
catalyst loading of 100 mg, 10 mg, and 5 mg following the same exper-
iment setups. Investigation of the impact of NaBH
tested for 0.19 g, 1 g, 2 g, and 3 g using 10 mg, and 5 mg of Co@ZIF-8.
After a specific time, the reaction flask was recharged with NaBH
4
amount was also
4
Fig. 6. The hydrolysis of NaBH without and with Co@ZIF-8.
4
without catalyst separation. The hydrogen generation rate (HGR) was
calculated by the active cobalt catalyst’s per unit weight and was defined
-
1
-1
as mLꢀmin ꢀgcatalyst
.
3
. Results and discussion
3.1. Materials characterization
The synthesis of Co@ZIF-8 was achieved at room temperature in an
aqueous solution (Fig. 1). NaOH converts zinc nitrate to a white pre-
cipitate of zinc hydroxide nitrate [59]. A violet precipitate was formed
after the addition of the Hmim solution. XRD pattern of the formed violet
color precipitate is reported, as shown in Fig. 2. The XRD patterns of the
synthesized materials and the simulated pattern of ZIF-8 are overlapped
very well, indicating the formation of a pure phase of ZIF-8 after the
addition of Hmim (Fig. 2). The XRD peak broadening of the formed
crystal is due to the small particle size of the formed crystals. According
to Scherer’s equation (Eq. (1)), Co@ZIF-8 has a crystallite size of 50–100
nm.
0
:9λ
Fig. 7. The effect of Co@ZIF-8 loading on hydrogen generation via
NaBH hydrolysis.
τ
¼
1
βcosθ
4
Where:
τ
is the size of the crystallite; λ is the wavelength of X-ray radi-
ation; β is the line broadening at half the maximum intensity in radians,
and θ is the Bragg angle.
The XPS analysis of Co@ZIF-8 is shown in Fig. 3. The elemental XPS
survey shows elements of C, N, O, Zn, and Co (Fig. 3a). XPS analysis of
2
C1s show speaks corresponding to sp (284.9 eV), –C–N (286.2 eV), and
–
–
–C N (287.8 eV, Fig. 3b). The analysis of N1s shows two peaks at 398.8
–
–
N– and C–N–, respectively
eV and 399.4 eV, which can be assigned to C
Fig. 3c). The oxygen species are due to the adsorbed water and car-
(
bonate (531.8 eV) into ZIF-8 (Fig. 3d). The XPS analysis of the Zn 2p
region shows two peaks at 1021.9 and 1044.9 eV (Fig. 3e). The Co2p
spectrum can be fitted to 8 peaks: 781.4 eV, 783.6 eV, 786.3 eV, 789.5
eV, 797.0 eV, 799.4 eV, 802.3 eV, and 805.3 eV (Fig. 3f). The two peaks
at 781.4 eV and 797.0 eV (separated by 15 eV) can be assigned to Co
2
p3/2 and Co 2p1/2, respectively (Fig. 3f). The other peaks are satellite
peaks for Co 2p3/2 and Co 2p1/2. The observable satellite features at
86.3 eV refer to Co (II). These observations indicate that the reduction
of Co (II) using NaBH was incomplete or due to coordination of Co to
7
4
mim. There was no peak corresponding to B (suppose to be at 187.7 eV),
indicating no Co–B formation [70]. Cobalt loading in Co@ZIF-8 is 524
ppm, according to AAF analysis.
Fig. 8. The effect of NaBH
drolysis using Co@ZIF-8 of 5 and 10 mg.
4 4
amount on hydrogen generation via NaBH hy-
The morphology and particle size of Co@ZIF-8 were evaluated using
TEM and high-resolution TEM (Fig. 4). TEM image (Fig. 4a) shows
5

H.N. Abdelhamid
Journal of Solid State Chemistry 297 (2021) 122034
Fig. 9. Mechanism of NaBH
4
hydrolysis using Co@ZIF-8.
Co@ZIF-8 with a particle size of 50–200 nm, which agrees with the size
calculated from Scherer’s equation using XRD data (Fig. 2a). The formed
crystals exhibited a truncated cubic crystal morphology without any
observation of the aggregation of cobalt nanoparticles (Fig. 4a). The
crystal contains a mesopore inside the crystal particle with a size of 5–20
nm (Fig. 4a). It is essential to mention that conventional ZIF-8 is
microporous material with a pore size of fewer than 2 nm [1]. The small
pore volume of microporous ZIF-8 prevents the diffusion of large mole-
cules. On the other side, Co@ZIF-8 contains a mesopore structure as well
as the micropores of conventional ZIF-8. In other words, Co@ZIF-8 is a
hierarchical porous material.
Table 1
4
Summary of catalysts used for hydrogen generation via NaBH hydrolysis.
Catalyst
Synthesis Procedure
Catalysis
Conditions
Ratea
Ref.
Co–B
CoCl
NaBH
2
solution þ
solution
0.04 M CoCl
solution, 15 wt%
2
26000
[70]
4
NaBH
4
, 5 wt%
ꢃ
NaOH, 30
Cat. 6 mol%,
C
Co@ZIF-8
1. Deposition-
precipitation
2935
19400
[55]
b
NaBH
4
, 0.75 mmol,
ꢃ
2
. In-situ reduction
30
C
using NaBH
4
2
Nitrogen (N ) adsorption-desorption isotherm of Co@ZIF-8 is shown
Co@ZIF-9
CoB/ZIF-8
Solvothermal
Cat. 25 mg, NaBH
4
,
3642
454
[63]
[56]
in Fig. 5a. It shows type-IV indicating the presence of micropore to
mesopore regime. The analysis reveals BET surface area, Langmuir sur-
ꢃ
0
.5 wt%, 30
C
1. Solvothermal
Cat. 10 mg, NaBH
4
1.67 wt%, NaOH 5
wt%
Cat. 20 mg, NaBH
10 wt%, NaOH 6
2
-1
2
-1
face area, and external surface area of 200 m ꢀg , 250 m ꢀg , and 197
2
. NaBH
4
reduction
2
-1
m ꢀg , respectively (Fig. 5b). The pore size distribution was evaluated
using BJH (Fig. 5c) and DFT (Fig. 5d) model. Data analysis confirms the
presence of a pore size of 3.5–25 nm with a maximum pore size 10 nm
that agrees with the TEM image (Fig. 4a).
Co@C
1. Co-MOF-71 (24 h
4
4
1680
1746
[71]
[62]
ꢃ
at 110 C in an oven),
ꢃ
2
. Calcination at 700
wt%, 30
C
ꢃ
C for 8 h under N
2
atmosphere
Fe
3
O
4
@C–Co
1. Solvothermal (200
Cat. 30 mg, NaBH
0.26 M
ꢃ
C, 10 h)
4
3.2. Hydrogen generation via NaBH hydrolysis
2
. Hydrothermal
ꢃ
(180 C, 4 h),
Hydrogen generation via the hydrolysis of NaBH
a catalyst has been reported. The self-hydrolysis of NaBH
process (Fig. 6a). The production of hydrogen via NaBH hydrolysis is
4
using Co@ZIF-8 as
annealing under
nitrogen,
4
is a slow
3
. Reduction with
NaBH
Carbonization of ZIF-
4
4
kinetically limited under ambient conditions in the absence of a catalyst.
Co@ZIF-8 has a large pore size and may render the diffusion of reactions
feasible. Furthermore, water molecules can be dissociated into the
external surface of ZIF-8 crystal, leading to acidic and basic sites [60].
Thus, Co@ZIF-8 has been investigated as a catalyst for the hydrolysis of
Co
3
O
4
@C
Cat. 500 mg Lꢁ1,
4900
1807
10290
[68]
[72]
[67]
6
7
4
NaBH 4730
ꢁ
1
mgꢀL ; NaOH, 1
ꢃ
M, T ¼ 30
C
ꢃ
Zn1Co1Co@NC
Co@C
1. Synthesis at 120
for 4 h,
C
Cat. 10 mg,
NaBH
4
100 mg,
NaBH
NaBH
. The generated volume of hydrogen via the self-hydrolysis of
or in the presence of ZIF-8 is low compared to the generated
4
2
. Calcination at 900
NaOH 0.8 g
4
ꢃ
C for 3 h
volume in the presence of Co@ZIF-8 materials (Fig. 6). Co@ZIF-8 can
serve as an effective catalyst for the hydrolysis of NaBH (Fig. 6).
1. Impregnation-
chemical
Cat. 20 mg, NaBH
1 wt%; 1 wt%
4
4
2
. Reduction of
cobalt salt using
NaBH in DMF
NaOH1 wt.%, 27
C
The effect of the catalyst loading (5 mg, 10 mg, and 100 mg) was
investigated, as shown in Fig. 7. There is no dramatic change in the
generated volume of hydrogen for different catalyst loadings. This
observation indicates that even low catalyst loading, e.g., 5 mg, can
efficiently catalyze the reaction. Data reveal that Co@ZIF-8 is an effective
ꢃ
4
Co@ZIF-8
One-Pot synthesis,
Room temperature,
Cat. 5 mg, NaBH
3 wt%
4
7230
Here
(18 ꢂ
6
b
1
0 )
Notes: a, mLꢀ minꢁ1ꢀgꢁ1; b, mLꢀminꢁ1ꢀ gCꢁo1
4
catalyst for hydrogen generation via NaBH hydrolysis (Fig. 7). This is
mainly due to the presence of active species with high catalytic effi-
.
ciency. It implies no consumption of the hydrogen generated during the
6

H.N. Abdelhamid
Journal of Solid State Chemistry 297 (2021) 122034
hydrolysis using a high loading of Co@ZIF-8.
without the need of separation or activation steps.
The hydrolysis process depends on the reactant’s concentration, i.e.,
water and NaBH
reaction is independent of the concentration of water, i.e., pseudo-first-
order. The effect of NaBH concentration on the generated volume of
hydrogen using two different loadings of Co@ZIF-8, e.g., 5 and 10 mg,
was investigated (Fig. 8). The hydrogen volume increases with the in-
4
. A large volume of water (100 mL) is used. Thus, the
4. Conclusions
4
A simple procedure has been reported for the synthesis of hierarchical
porous Co@ZIF-8. The method was a one-pot procedure without the need
for sophisticated equipment. It required a short time and uses water
molecules. The reaction takes placed at ambient conditions without the
need for heating. The produced material showed unique properties since
it has a hierarchical porous structure. The materials exhibited high cat-
alytic performance for hydrogen gas generation via the hydrolysis of
4
crease of NaBH (Fig. 8). There is no dramatic difference in the efficiency
of Co@ZIF-8 using 10 mg and 5 mg (Fig. 8). This observation agrees with
our previous results shown in Fig. 7. The active species can be used
successively without deactivation (Fig. 8).
Sodium borohydride can be recharged into the reaction solution
without separating the catalyst (Fig. 8). There is no decrease in the ef-
ficiency of the catalyst over time (Fig. 8). The volume of hydrogen in-
NaBH . Co@ZIF-8 exhibited hydrogen generation rate of 7230
4
ꢁ
1
ꢁ1
6
ꢁ1
ꢁ1
mLꢀg ꢀmin (18 ꢂ 10 mLꢀg ꢀmin ). Data may open new avenues
cat
Co
for further exploration of effective and commercial catalysts for on-
demand production of hydrogen using the hydrolysis of NaBH4.
creases with the time and NaBH
4
amount (Fig. 8). The reaction becomes
loading (2–3 g). There
faster and requires a shorter time for high NaBH
4
is an insignificant difference between 10 mg and 5 mg in the catalytic
performance, indicating the investigated catalyst’s high performance.
The hydrogen generation rates (HGR) using Co@ZIF-8 are 2961
CRediT authorship contribution statement
Hani Nasser Abdelhamid: Data curation, Performed experiments,
Supervision, Conceptualization, Methodology, Writing – original draft,
preparation and revision, and leading the project.
ꢁ1
ꢁ1
ꢁ1
ꢁ1
mLꢀgcatꢀmin , and 7230 mLꢀgcatꢀmin for 10 mg, and 5 mg, respec-
tively (Fig. 8).
There are several studies reported that effective transition elements as
catalysts for the hydride hydrolysis are used in boride or phosphide.
These species are electron-rich atoms and can protect the core transition
metals from oxidation via electron transfer from B to Co [61]. Thus,
boride or phosphide-based catalysts alloys showed higher catalytic ac-
tivity compared to the corresponding metals. However, XPS data showed
no presence of B in our system, i.e., Co@ZIF-8. Several mechanisms were
Declaration of competing interest
The authors declare no competing interests.
Acknowledgment
reported to explain the catalysis of NaBH
hydrogen (4 molecules) is produced from water (2 molecules) and BH
4
hydrolysis (Fig. 9). The
Dr. Abdelhamid thanks Science and Technology Development Fund
STDF) for financial support (Project No 35969).
ꢁ
4
(
(
2 molecules) (Fig. 9). The Co site and Zn metal catalyze sodium boro-
hydride’s hydrolysis and the O–H bond cleavage of H
2
O (Fig. 9). The
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3
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ꢁ1
ꢁ1
ꢃ
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