UiO-66 as a catalyst for hydrogen production: Via the hydrolysis of sodium borohydride

Article abstract of DOI:10.1039/d0dt01688h

The exploration of a highly efficient catalyst for the hydrolysis of sodium borohydride (NaBH4) is a valuable step toward a hydrogen economy. UiO-66 (Universitetet i Oslo) was synthesized via a solvothermal method using acetic acid as a modulator. The material was characterized using X-ray diffraction (XRD), nitrogen adsorption-desorption isotherms, Fourier transform infrared (FT-IR) spectroscopy, thermogravimetric analysis (TGA), temperature-programmed desorption (TPD), and transmission electron microscopy (TEM). Data analysis reveals the formation of a pure and highly crystalline phase of UiO-66 with the Brunauer-Emmett-Teller (BET) and Langmuir specific surface areas of 1125 m2 g-1, and 1250 m2 g-1, respectively. UiO-66 was analysed as a catalyst for hydrogen generation via the hydrolysis of NaBH4. The effect of the NaBH4 amount and catalyst loading was investigated. The reaction time decreased with an increase of the amount of NaBH4 or UiO-66. UiO-66 exhibited an average hydrogen generation rate of 6200 mL min-1 g-1. The high catalytic performance of UiO-66 could be due to its large surface area and acidic sites. The results suggested that UiO-66 showed high potential to catalyze the hydrogen production via the hydrolysis of hydrides. This journal is

Full text of DOI:10.1039/d0dt01688h

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UiO-66 as a catalyst for hydrogen production via
the hydrolysis of sodium borohydride
Cite this: DOI: 10.1039/d0dt01688h
Hani Nasser Abdelhamid
The exploration of a highly efficient catalyst for the hydrolysis of sodium borohydride (NaBH4) is a valuable
step toward a hydrogen economy. UiO-66 (Universitetet i Oslo) was synthesized via a solvothermal method
using acetic acid as a modulator. The material was characterized using X-ray diffraction (XRD), nitrogen
adsorption–desorption isotherms, Fourier transform infrared (FT-IR) spectroscopy, thermogravimetric ana-
lysis (TGA), temperature-programmed desorption (TPD), and transmission electron microscopy (TEM). Data
analysis reveals the formation of a pure and highly crystalline phase of UiO-66 with the Brunauer–Emmett–
Teller (BET) and Langmuir specific surface areas of 1125 m2 g−1, and 1250 m2 g−1, respectively. UiO-66 was
analysed as a catalyst for hydrogen generation via the hydrolysis of NaBH4. The effect of the NaBH4 amount
and catalyst loading was investigated. The reaction time decreased with an increase of the amount of NaBH4
or UiO-66. UiO-66 exhibited an average hydrogen generation rate of 6200 mL min−1 g−1. The high catalytic
performance of UiO-66 could be due to its large surface area and acidic sites. The results suggested that
UiO-66 showed high potential to catalyze the hydrogen production via the hydrolysis of hydrides.
Received 10th May 2020,
Accepted 22nd June 2020
DOI: 10.1039/d0dt01688h
rsc.li/dalton
decomposed ZIF-67 supported Pd nanoclusters (Pd/
PD-ZIF-67),19 and copper-1,4-benzenedicarboxylate (CuBDC)20
Introduction
Hydrogen (H2) gas is a renewable and sustainable clean energy were reported as catalysts for hydrogen production via the
source with high combustion efficiency, and environmentally hydrolysis of NaBH4. UiO-66 (Universitetet i Oslo) is an arche-
friendly by-products.1,2 It can be used as a fuel with a specific typal MOF with a high specific surface area and high chemical
energy of 120 MJ kg−1 which is higher than those of diesel and and thermal stability21–23 and is amenable to further modifi-
gasoline (46 MJ kg−1). The production of hydrogen can be cations.24 It can be easily synthesized in the lab with great
achieved using phototrophic microorganisms1 and several potential for commercialization. UiO-66 was used for photo-
methods such as biomass gasification,3 solar hydrogen,4 and dynamic therapy,25 drug delivery,26 CO2 adsorption,27 metal
water oxidation.5 Among these methods, the hydrolysis of adsorption,28 dye adsorption,29 and separation,30 and as a
hydrides such as sodium borohydride (NaBH4) offers several probe for the detection of hydrazine.31 It is used as a catalyst
advantages.6 The hydrolysis process is well known for many or support for a catalyst. UiO-66 was also used for the selective
applications in energy and materials science. NaBH4 has high transformation of alkynes into alkenes,32 photoreduction of
gravimetric and volumetric capacities compared to other metal CO2 to formate,33 and hydrodeoxygenation of vanillin.34 It can
hydrides. It serves as a water-splitting agent since half of the be used as a support for the NiFePd catalyst which exhibited
produced hydrogen is produced from water. The hydrolysis efficient catalytic performance for the generation of hydrogen
process is useful for low energy demand applications such as from hydrous hydrazine in an alkaline solution.35
unmanned airplanes, and small portable devices.6 However, a
catalyst is required to improve and control the rate of the self- hydrogen generation via the hydrolysis of NaBH4. A solvo-
hydrolysis process.6
thermal method with acetic acid as a modulator was used to
Herein, UiO-66 was synthesized and applied as a catalyst for
Metal–organic frameworks (MOFs) are self-assembled synthesise UiO-66. The material was characterized using X-ray
coordination polymers with high porosity and large surface diffraction (XRD), transmission electron microscopy (TEM),
areas.7–13 They have been applied in various methods/tech- nitrogen adsorption–desorption isotherms, thermogravimetric
niques for the production of hydrogen.14,15 Several MOFs such analysis (TGA), temperature-programmed desorption (TPD),
as zeolitic imidazolate frameworks (ZIF-8),16–18 partially and Fourier transform infrared (FT-IR) spectroscopy. A pure
crystalline phase of UiO-66 is obtained with a specific surface
area of Brunauer–Emmett–Teller (BET), and Langmuir of
1125 m2 g−1, and 1250 m2 g−1, respectively. It exhibited a
Advanced Multifunctional Materials Laboratory, Department of Chemistry, Assiut
maximum hydrogen generation rate (HGR) of 12400 mL min−1
University, 71516 Assiut, Egypt. E-mail: hany.abdelhamid@aun.edu.eg
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g−1 with an average HGR of 6200 mL min−1 g−1 using 5 mg of diffractometer (XRD Phillips PW1700 (Rockville, USA)) with
Cu Kα radiation (λ = 0.15405 nm) at an accelerating voltage and
current of 40 kV and 40 mA, respectively.36 The specific surface
areas (BET and Langmuir) were measured using N2 adsorp-
tion–desorption isotherms (at 77 K) by employing an
ASAP2000 surface area analyzer (Micrometric, UK). The pore
size distribution was evaluated using the BJH (Barrett, Joyner,
and Halenda) method. The sample was degassed at 120 °C
under vacuum for 3 h. The Fourier transform infrared spectra
(FT-IR) of UiO-66 were measured using a Nicolet spectrophoto-
meter (model6700). The thermogravimetric analysis (TGA) of
UiO-66 was performed using a TA 60 thermal analyzer appar-
atus (Shimadzu, Japan).
the catalyst at 30 °C. The results may lead to further explora-
tion of the applications of MOFs as catalysts for the generation
of hydrogen using chemical reagents such as NaBH4.
Materials and methods
Acetic acid, dimethylformamide (DMF), 1,4-benzenedicar-
boxylic acid (BDC), and ZrOCl2 were purchased from Sigma-
Aldrich (Germany). All the chemical reagents were used
without further purification.
Synthesis of UiO-66
The catalytic reaction for the hydrolysis of NaBH4
ZrOCl2 (750 mg), 1,4-benzenedicarboxylic acid (BDC, 740 mg),
and acetic acid (4 mL) were mixed in DMF (90 mL) using ultra-
sonication for 30 min. The solution was transferred to a
Teflon-lined stainless steel autoclave (100 mL) and heated at
120 °C for 24 h. The reaction solution was cooled down to
room temperature and washed three times using DMF (3 ×
30 mL), and ethanol (3 × 30 mL). The sample was dried in an
oven overnight (85 °C).
The hydrolysis of NaBH4 was performed at 30 °C using UiO-66
of 5, 10, and 50 mg. NaBH4 of 0.19 g, 0.34 g, 1 g, 2 g, and 3 g
was added to 100 mL of water (corresponding to 0.19 wt%,
0.34 wt%, 1 wt%, 2 wt%, and 3 wt%). Then, a catalyst UiO-66
was added. The reaction solution was stirred at 1000 rpm. The
generated volume of hydrogen was measured using the water
displacement method.20
The effect of temperature was evaluated at temperatures of
30 °C, 50 °C, and 60 °C. The amount of UiO-66 was 50 mg.
Characterization methods
The morphology of UiO-66 was investigated using a trans- Different amounts of NaBH4 were employed such as 0.34 g,
mission electron microscope (TEM, JEOL 2100F). The crystal 1 g, and 2 g. The experimental setups were the same as men-
phase of the sample was determined using a powder X-ray tioned above.
Fig. 1 Solvothermal synthesis of UiO-66; its crystal structure and applications for the hydrolysis of NaBH4; the orange and green spheres refer to
the primary pore size and the secondary pore size, respectively. Zirconium clusters are presented.
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Acidity determination for UiO-66
material (Fig. 1). Thus, nitrogen adsorption–desorption was
used to evaluate the material porosity (Fig. 2).
Thermal analysis was used to determine the surface acidity of
UiO-66 via temperature-programmed desorption (TPD). Basic
probe pyridine (PY) was used. Briefly, the PY molecules were
adsorbed onto 100 mg of UiO-66. The material after adsorption
was analyzed using thermogravimetric analysis (TGA, a TA 60
thermal analyzer apparatus, Shimadzu, Japan) in the gas feed
The porosity of UiO-66 was evaluated using the nitrogen
adsorption–desorption isotherm (Fig. 2b). Data analysis
revealed the BET and Langmuir specific surface areas of 1125,
and 1250 m2 g−1, respectively. These values agree with the
reported values of the BET surface area.37 The pore size distri-
bution using the BJH method was also evaluated as shown in
Fig. 2c. Data analysis suggests a total pore volume of 0.5 cm3
g−1 (Fig. 2c). The nitrogen adsorption–desorption isotherm
confirms the successful synthesis of UiO-66 with a high
surface area and large pore volume (Fig. 2).
The chemical functional groups of UiO-66 are characterized
using FT-IR spectroscopy (Fig. 3a). The FT-IR spectrum of
UiO-66 shows vibrational bands at a wavenumber in the range
of 2922–2847 cm−1 corresponding to C–H (Fig. 3a). The spec-
trum displays strong bands in the 1700–1250 cm−1 range
arising from the carboxylate groups and phenyl ring defor-
mations. The symmetric and asymmetric peaks of CvO can be
observed at 1656 cm−1 and 1385 cm−1, respectively. The band at
403 cm−1 is assigned to the Zr–O bond vibrations. The bands at
603 cm−1 and 665 cm−1 correspond to the Zr–O stretching
mode. The FT-IR data confirm the coordination bonds between
the Zr nodes ([Zr6O4(OH)4]) and carboxylic groups of the linker.
at a total flow rate of 50 mL min−1
.
Results and discussion
Material Characterization
The solvothermal synthesis of UiO-66 was achieved using DMF
as a solvent leading to the formation of a white precipitate
(Fig. 1). The XRD pattern of the formed precipitate was com-
pared to the simulated XRD pattern of UiO-66 (Fig. 2a). The
XRD pattern of the synthesized material and the simulated
XRD pattern of UiO-66 matched very well indicating that a
pure phase of UiO-66 was obtained (Fig. 2a). The data reveal
that UiO-66 exhibits high crystallinity. UiO-66 consists of
[Zr6O4(OH)4] clusters linked by 1,4-benzenedicarboxylic acid
linkers. The crystal structure reveals that UiO-66 is a porous
Fig. 2 Characterization of UiO-66 using (a) XRD and (b) N2 adsorption (closed symbols)-desorption (open symbols) isotherms, and (c) the pore size
distribution using the BJH method.
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Fig. 3 (a) FT-IR spectrum and (b) TEM image of UiO-66.
The morphology and particle size of UiO-66 were deter-
mined using the TEM image (Fig. 2b). The TEM image of
UiO-66 shows a crystal with a particle size of 175 nm (Fig. 3b).
The UiO-66 crystals show an octahedral morphology (Fig. 3b).
There is no observation of the extra crystal phase indicating
that the synthesized material has high purity. This observation
is consistent with the XRD data (Fig. 2a).
The thermal stability of UiO-66 was determined using the
TGA curve (Fig. 4a). Fig. 4a shows three weight-loss steps. The
first weight-loss step observed in the temperature range of
50–150 °C is due to the desorption of physisorbed molecules
such as water. The second weight-loss step was observed in the
temperature range of 150–350 °C. This weight loss is related to
the thermal desorption of DMF or the dehydroxylation of the
Zr nodes ([Zr6O4(OH)4]).38 The third weight lost step at 500 °C
refers to the vaporization of the organic linker in the UiO-66
crystals. The TGA curve indicates that UiO-66 has thermal
stability up to 500 °C (Fig. 4a). The residual material is ZrO4
(found is 52% and calculated is 55% using the molecular
formula C48H28O32Zr6, and formula weight 1664.06 g mol−1).
The TGA result confirms the high thermal stability of UiO-66
and reveals that the material has highly pure crystals of
UiO-66.
Application of UiO-66 for hydrogen generation via the
hydrolysis of NaBH4
The application of UiO-66 for hydrogen generation via the
hydrolysis of NaBH4 was investigated (Fig. 5 and 6). UiO-66
was selected because of the high surface area of its crystals. It
Fig. 4 Thermal analysis of UiO-66 using (a) TGA and (b) PY-TPD.
has also acidic sites that can serve as active catalytic positions Zr node has a flexible coordinative state of the Zr4+ species. It
for the hydrolysis of NaBH4. UiO-66 has a Zr6 node with a fully is possible to have both the hydroxylated and dehydroxylated
reversible hydroxylation group (Fig. 1). The total number of forms (Fig. 1).40 UiO-66 offers the amphoteric nature e.g. acid-
acidic sites over the surface of UiO-66 was quantitatively evalu- base pair properties.41,42 Thus, it can be used as an effective
ated using pyridine-TPD (Fig. 4b). The PY-TPD curve shows a catalyst for the hydrogen generation via the hydrolysis of
weight loss at 58 °C for UiO-66 due to the weak acidic sites NaBH4.
inside the frameworks. Data analysis shows the total acidic
The effect of UiO-66 loading on the hydrolysis of NaBH4
sites of the 0.210 × 1020 site m−2 catalyst.39 Furthermore, the was investigated as shown in Fig. 5. The volume of the gener-
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Fig. 5 The effect of UiO-66 loading on the hydrogen generation using (a) 5 mg, (b) 10 mg, and (c) 50 mg of UiO-66 at 30 °C. (d) hydrogen gene-
ration rate using 5 mg of UiO-66 and 2 wt% of NaBH4.
Fig. 6 The efficiency of the hydrolysis at a temperature of (a) 50 °C and 60 °C using 50 mg of UiO-66.
ated hydrogen increases with time. The time to reach the decreases with the increase of the NaBH4 loading (Fig. 5a–c). It
maximum hydrogen volume i.e. 500 mL decreases with the is also important to note that the rate of hydrogen generation
increase of the catalyst loading (Fig. 5). This observation is decreases over time (Fig. 5d). This is due to the decrease in the
consistent for different concentrations of NaBH4 (0.19 wt%, concentration of NaBH4 in the solution with time (Fig. 5d).
0.3 wt%, 1 wt%, 2 wt%, and 3 wt%). The reaction time The maximum and average hydrogen generation rates (HGR)
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Table 1 Summary of some MOFs which were used as catalysts for hydrogen generation via the hydrolysis of NaBH4
Reaction conditions
Cat
(mg) (wt%)
NaBH4
NaOH
T
HGR
Catalysts
Synthesis conditions
(wt%) (°C) (mL min−1 g−1
)
Ref.
20
CuBDC
Solvothermal, 100 °C for 5h
50 0.05 M
No
25
7620
CuO@C
Carbonization at 600 °C for 3 h
7240
Pd/PD-ZIF-67 Precipitation method, calcination at 200 °C in H2 atmosphere for 2 h 10
CoB@ZIF-8
ZIF-9
150 mM 0.4
20.6 × 106
453.6
3642
19
45
46
16
Solvothermal-reduction using NaBH4
Solvothermal method
Room temperature
1.67
0.5
5
35
40
30
75
ZIF-8
100 0.19
No
3000
TPA@ZIF-8
UiO-66
2333
6200
18
Solvothermal method, 120 °C for 12h
5
2
This study
Notes: TPA, terephthalic acid.
were 12400 mL min−1 g−1, and 6200 mL min−1 g−1, respectively NaBH4. The large surface areas and acidic sites of UiO-66
(Fig. 5d). ensure the high catalytic performance for the hydrolysis of
The effect of temperature was also investigated at tempera- NaBH4. The hydrogen generation rate increases with the
tures of 30 °C (Fig. 5c), 50 °C, and 60 °C (Fig. 6a and b) and increase of the NaBH4 loading. UiO-66 showed an average
with different amounts of NaBH4 with 50 mg of UiO-66. The hydrogen generation rate (HGR) of 6200 mL min−1 g−1. It
reaction time to reach the maximum efficiency decreases with showed a high HGR compared to other MOF-based catalysts. It
an increase of the temperature (Fig. 6a and b). The increase of showed several advantages such as a high HGR, simple syn-
the efficiency with the increase in the temperature is due to an thesis procedure, and low cost. These results may open new
increase in the kinetics of the reactants and the diffusion rate avenues for further exploration of an effective catalyst for
of the generated gas. The reaction time also decreases with an hydrogen generation via the hydrolysis of NaBH4 using MOFs
increase of the amount of NaBH4 (Fig. 6a and b). This effect is as catalysts.
due to the increase in the collision between the reactants.
Both the temperature and NaBH4 amount can increase the
amount of the generated hydrogen gas.
Conflicts of interest
A comparison among different MOFs which were reported as
There are no conflicts to declare.
catalysts for the hydrogen generation via the hydrolysis of
NaBH4 is tabulated in Table 1. The UiO-66 crystals were used as
a support for NiFePd.35 NiFePd@UiO-66 was used as a catalyst
for the generation of hydrogen from hydrous hydrazine in an
alkaline solution.35 CuBDC and CuO@C exhibited a HGR of
Acknowledgements
7620 mL min−1 g−1 and 7240 mL min−1
g
−1, respectively.20
The author would like to thank the Ministry of Higher
Education and Scientific Research (Egypt) and Institutional
Review Board (IRB) of the Faculty of Science at Assiut
University, Egypt, for the support.
However, CuBDC is a water unstable framework.43 NaBH4 could
also reduce CuO@C to a mixture of Cu2O and Cu(0).44 Thus, a
calcination step is required to regenerate the catalyst. Partially
decomposed ZIF-67 supported Pd nanoclusters (Pd/PD-ZIF-67)
were applied for the hydrolysis of NaBH4.19 The material
showed a high HGR. However, it contains expensive noble
metals i.e. Pd. UiO-66 showed a higher HGR compared to ZIF-
based catalysts.16,18,45,46 The UiO-66 catalyst offers several advan-
tages including a high HGR, simple synthesis procedure, and
low cost (Table 1). NaBH4 showed no effect on UiO-66 crystals,
thus it can be used as a reducing agent for metals such as Ru.38
This suggests that UiO-66 can be used as a support for metal
nanoparticles for the generation of hydrogen from hydrous
hydrazine (NiFePd@UiO-66)35 or by the hydrolysis of NaBH4.
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