Microporous Crystalline γ-Al2O3 Replicated from Microporous Covalent Triazine Framework and Its Application as Support for Catalytic Hydrolysis of Ammonia Borane

Article abstract of DOI:10.1002/asia.201601631

Significant progress has been made on the synthesis and application of mesoporous γ-alumina. To date, little attention has been paid to the synthesis of microporous crystalline alumina. Here, fabrication of microporous crystalline γ-alumina using a microporous covalent triazine framework (CTF-1) as a template is described. Microporous crystalline γ-alumina with a micro-meso binary pore system was replicated by infiltration of aluminum nitrate into the micropores of the CTF-1 template through a NH₃/water-vapor-induced internal hydrolysis method, followed by thermal treatment, and subsequent removal of the CTF-1 template with a 30 % H₂O₂ aqueous solution. The obtained crystalline γ-alumina material exhibits a large surface area (349 m² g^?1) with micropore distribution centered at about 1.27 nm. Ru supported on microporous γ-Al₂O₃ can be employed as catalyst for hydrolytic dehydrogenation of ammonia borane, and it exhibits high catalytic activity and good durability. This finding provides a new benchmark for preparing well-defined crystalline microporous alumina materials by a template method, which can be applied in a wide range of fields.

Full text of DOI:10.1002/asia.201601631

CHEMISTRY
AN ASIAN JOURNAL
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Accepted Article
Title: Microporous crystalline γ-Al2O3 replicated from microporous
covalent triazine framework and its application as support for
catalytic hydrolysis of ammonia borane
Authors: Miao Zhang, Lin Liu, Teng He, Zhao Li, Guotao Wu, and Ping
Chen
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Chemistry - An Asian Journal
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Microporous crystalline γ-Al O replicated from microporous covalent
2
3
triazine framework and its application as support for catalytic hydrolysis
of ammonia borane
[a, b]
[a]
[a]
[a, b]
[a]
[a]
Miao Zhang,
Lin Liu,* Teng He, Zhao Li,
Guotao Wu and Ping Chen*
Abstract: Significant progresses have been made on the synthesis and
application of mesoporous γ-alumina. To date, little attention has been paid
on the synthesis of microporous crystalline alumina. Here, we demonstrated
micropores are very low. Therefore, it is necessary to find a method to
synthesize crystalline microporous alumina with high microporous
surface area and well defined micropore size. Despite great progresses
have been made on the design and synthesis of mesoporous alumina
materials by template approach, it is hard to synthesize crystalline
microporous alumina according to these reasons. Firstly, compared
with mesoporous templates, it remains a great challenge to fill up
solution-based precursors into the pores of the microporous templates
to fabricate microporous crystalline γ-alumina using
a microporous
covalent triazine framework (CTF-1) as a template. Microporous crystalline
γ-alumina with a micro-meso binary pore system was replicated by
infiltration of aluminum nitrate into the micropores of CTF-1 template
through a NH
by thermal treatment, and subsequent removal of CTF-1 template with 30%
solution. The obtained crystalline γ-alumina material exhibits large
3
/water vapor induced internal hydrolysis method, followed
[10]
due to the easily blocking of the micropore channels. Furthermore,
removal of the microporous templates without causing structural
2 2
H O
2
-1
[11]
surface area (349 m g ) with micropore distribution centred at about 1.27
nm. Ru supported on microporous γ-Al can be employed as catalyst for
collapse of the microporous product is also very challenging.
O
2 3
Recently, covalent triazine frameworks (CTFs), a new class of covalent
organic framework materials based on the triazine framework, have
been synthesized by ionothermal trimerization of aromatic nitriles in
hydrolytic dehydrogenation of ammonia borane, and it exhibits high
catalytic activity and good durability. This finding provides a new
benchmark for preparing well-defined crystalline microporous alumina
materials by template method, which is of great interestas it can be applied
in a wide range of fields.
[12]
molten zinc chloride. According to the large specific surface area,
homogeneous pore structure, diverse functionality, as well as high
chemical and thermal stability, CTFs have attracted increasing
attention as promising candidates for adsorbents, gas storage, catalysts
[13]
and catalytic supports. As a class of covalent porous polymers with
regular channel structure, CTFs provide new opportunity for the
preparation of microporous alumina materials through hard template
strategy.
Introduction
Porous alumina materials draw growing attention according to their
large surface area, large pore volume, and high chemical and physical
Here we report the successful synthesis of crystalline microporous
alumina with high surface area using hard template strategy. CTF-1, a
[1]
stability. It is well known that the porosity and crystallinity play the
decisive role in determining the performance of porous alumina
materials in a wide range of targeted applications such as adsorption,
2
-1
representative CTFs which has large surface area (697 m g ) and
uniform micropore with a diameter of ca. 1.3 nm was used as a hard
template. An efficient infiltration of aluminum precursor in the
[
2]
separation, catalysis, and catalyst support. Intensive research efforts
have been paid to the synthesis of porous crystalline alumina materials
with high surface area and well-defined pore size in the past years,
among which template approach has been extensively employed to
synthesize well-structured mesoporous alumina materials with narrow
microporous channels of CTF-1 can be obtained via a NH
3
/water vapor
induced internal hydrolysis method, which has been used to form
[
3]
[14]
uniform ZrO
Constrained by the rigid structure of CTF-1 template, the infiltrated
aluminum precursor can be well crystallized into crystalline γ-Al at
elevated temperatures. After removal of CTF-1 template with 30%
solution, crystalline γ-Al with large surface area, high pore
2 2 3
or Al O layer in the mesopore walls of SBA-15 silica.
2
O
3
[4]
[2c, 5]
pore size distribution. By using surfactants, block copolymers,
[
6]
[7]
colloidal crystals and mesoporous carbon as templates, many novel
mesoporous alumina materials have been synthesized successfully.
These template approaches generally rely on infiltration of precursors
to porous solids or solution-phase co-assembly of soft templates, and
thus can control mesoporosity and crystalline framework of alumina
H
2
O
2
2 3
O
volume, and well-defined micropore centred at about 1.27 nm was
obtained for the first time. Furthermore, the obtained microporous
crystalline γ-Al O was evaluated as support for Ru nanoparticles,
2 3
which exhibits high activity and good durability for hydrolytic
dehydrogenation of ammonia borane.
[8]
materials.
The existence of microporous structures has been confirmed in both
[9]
commercial and synthesized γ-Al
2
O
3
,
however, the percentage of
Results and Discussion
[
a]
b]
M. Zhang, Dr. L. Liu, Dr. T. He,Z. Li, Dr. G. Wu and Prof. P. Chen
Dalian National Laboratory for Clean Energy, State Key Laboratory of
Catalysis,
Dalian Institute of Chemical Physics
Chinese Academy of Sciences, Dalian 116023 (P. R. China)
E-mail: liulin@dicp.ac.cn,pchen@dicp.ac.cn
M. Zhang and Z. Li
University of Chinese Academy of Sciences
University of Chinese Academy of Sciences, Beijing 100049 (P. R. China)
Supporting information for this article is available on the WWW under
http://dx.doi.org/10.1002/chem.2014xxxxx.
Microporous alumina replica of CTF-1 was prepared by infiltration of
aluminum precursor into the micropores of CTF-1 with a NH /water
3
vapor-induced internal hydrolysis method. Microporous CTF-1
template was prepared by ionothermal trimerization of 1,4-
dicyanobenzene in ZnCl
the procedure reported by Kuhn. In a typical procedure, required
amount of Al(NO ·9H O ethanol solution was wet-impregnated into
2
in a quartz ampule at 400 °C according to
[
[12]
3
)
3
2
the micropores of CTF-1 at room temperature. To improve dispersion
and ensure maximum loading of the precursor inside the micropores,
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Chemistry - An Asian Journal
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the impregnation was carried out in step-wise manner. The aluminum
precursor loaded CTF-1 was put in an open glass and kept inside the
reactor which contained a 14 wt% ammonium hydroxide solution
without contact with the sample, and heated at 80 °C for 10 h. After
this hydrothermal treatment, the sample was calcined under Ar
atmosphere. The CTF-1 template can be removed by etching
repeatedly with 30 wt % H
was repeated to remove CTF-1 template completely. The NH
2
O
2
at 100 °C. The above H
2
O
2
treat process
/water
3
vapor treatment is critical for the sufficient infiltration of aluminum
precursor into the micropores of CFT-1. It is suggested that hydrolysis
of the pre-dispersed precursor out/inside the micropores of CFT-1 in
the presence of NH
hydroxide into the micropores. As a result of sufficient infiltration of
precursors in the micropores, microporous γ-Al materials can form
3
/water vapor tends to disperse the aluminum
2
O
3
stable connections penetrating the whole micropore system of CTF-1
template.
Scanning electron microscopy (SEM) images show the morphology of
2 3
the CTF-1 template, post-calcinated CTF-1/Al O composite and
Figure 2. (a-c) TEM images of the obtained porous alumina with different resolution.
The inset of (c) shows the SAED pattern of the obtained porous alumina. (d) The
corresponding EDX spectrum of the obtained porous alumina.
alumina particles after removing CTF-1. From those images, it can be
seen that CTF-1 template has agglomerated particles with overall size
approximately ranging from several to tens micrometers (Figure 1a)
and smooth surface structure (Figure 1b). Most of the post-calcinated
shrinkage of aluminum precursor during calcination process is another
possible reason for the discontinuity of the obtained alumina.
Transmission electron microscopy (TEM) image shows that alumina
particles are composed of disorder stacked alumina nanosheets (Figure
2 3
CTF-1/Al O composite particles retain the irregular macroscale
morphology of the CTF-1 particles (Figure S1). No apparent alumina
particles were observed outside of CTF-1, showing the effectiveness of
3
the NH /water vapor induced internal hydrolysis treatment. The CTF-1
2
a). The length of the nanosheets is estimated to be 100-300 nm. TEM
removed alumina particles retain essentially the macroscale
morphology of CTF-1 template (Figure 1c). The SEM image at high
magnification reveals that the alumina material does not perfectly
retain the continuously connected networks of the CTF-1 particles.
Some of the alumina particles have flat surface in a large domain,
however, most of the alumina particles are composed of discontinuous
flake-like particles (Figure 1d). This observation can be reasonably
ascribed to the partial filling of microporous CTF-1 particles during
image with high resolution also reveals that the alumina sheets are
transparent under the electron beam, suggesting an ultrathin thickness
of the sheets (see Figure 2b). The thickness of alumina nanosheets is in
the range of 3-6 nm observed by TEM analysis (Figure 2c). The
selected area electron diffraction (SAED) pattern (Figure 2c, inset)
shows distinctive diffraction rings corresponding to the (311), (400)
and (440) diffractions, which match well to the lattice d-spacing of γ-
alumina, further confirming that the product are composed of γ-phase
alumina polycrystal. The energy-dispersive X-ray (EDX) spectrum
3
aluminum precursor impregnation and the followed NH /water vapor
induced internal hydrolysis process. Additionally, the volume
(
Figure 2d) shows that the framework is only composed of Al and O
with a molar ratio close to the theoretic value of 2/3, confirming the
product is Al . Elemental analysis was also employed to characterize
2 3
O
the chemical composition of the product. The content of C and N
element in the alumina was only about 0.44 wt.% and 0.03 wt.%,
which confirms the nearly complete removal of CTF-1 template.
The porosity of CTF-1 template and the obtained alumina are
confirmed by N
pores in CTF-1 are micropores, a very steep uptake can be observed
in the N adsorption isotherm below P/P = 0.01. Similar steep uptake
can also be observed in the N adsorption isotherm of the obtained
alumina material, indicating the alumina is microporous material.
Compare to CTF-1, the N adsorption isotherms below P/P = 0.01 in
the obtained alumina show a much lower N adsorption amount, which
2
adsorption-desorption experiments. As most of the
[12]
2
0
2
2
0
2
means fewer amount of micropores in alumina (Figure 3a). Here, we
use nonlocal density functional theory (NL-DFT) method to determine
the micropore size distributions of both CTF-1 template and alumina,
and isotherm data acquisition at very low pressure in the region of
0
micropore filling (P/P < 0.01) is necessary for the DFT method. As
Figure 1. SEM images of (a, b) CTF-1 template and (c, d) the obtained porous alumina
materials with different resolution.
shown in Figure 3b, both CTF-1 template and alumina have micropore
centred at about 1.27 nm after calculation by DFT method (Table S1),
which indicates aluminum precursor was successfully impregnated into
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Figure 3. (a) N
curve of CTF-1 template and porous γ-Al
from N adsorption was calculated by NLDFT method.
2
adsorption-desorption isotherm and (b) micropore size distribution
27
2
O
3. The micropore size distribution derived
Figure 4. (a) XRD patterns and (b) Al MAS NMR spectra of the porous γ-Al
2 3
O and
2
the commercial γ-Al
2 3
O .
the micropores of CTF-1 with a NH
3
/water vapor-induced internal
2 3
ppm can be observed in the spectrum of the porous γ-Al O (Figure 4b).
hydrolysis method. As the volume shrinkage during crystallization at
high temperatures, it is difficult to fully fill in all the micropores of
CTF-1 with alumina. As a result, broad distribution of micropore can
be detected in the obtained alumina. The micropore volume and
No peak of penta-coordinated aluminum sites can be detected, showing
a well crystallized γ-alumina framework. The peak at about 60 ppm
can be attributed to the tetrahedral aluminium species in γ-Al
2 3
O and
the peak at 9 ppm can be assigned to octahedral aluminium species in
2
7
isosteric heat of adsorption derived from N
2
adsorption by Dubinin-
γ-Al
2
O
3
. These Al MAS NMR spectra show that porous γ-Al
2
O
3
are
3
[15]
Astakhov analysis are 0.14 cm /g and 14.4 kJ/mol, respectively.
The N adsorption/desorption isotherm of the CTF-1 template shows
typical type I isotherm according to the IUPAC classification, so CTF-
templates are uniform microporous solids. However, the porous
identical to that of the commercial γ-Al O , which is consistent with
2 3
2
the XRD result (Figure 4a).
Fourier transform infrared (FT-IR) pyridine adsorption measurements
1
were conducted to test the surface acidity of the obtained porous γ-
[16]
alumina exhibits an associated H2 type hysteresis at higher pressures,
indicating the presence of mesopores in the material. The porous
alumina has a mesopore size distribution centered at about 6.27 nm,
which is calculated by the adsorption branch of the isotherm (Figure
S2). The presence of these mesopores may be caused by the incomplete
filling of the microporous CTF-1 template with alumina, which has
been observed from the SEM and TEM results. The specific BET
Al
O
2 3
.
As shown in Figure 5a, several characteristic pyridine
absorption bands can be detected in FT-IR spectraat room temperature.
-1
The bands at 1489 and 1590 cm can be attributed to the aprotic sites,
indicating pyridine adsorption via hydrogen-bonding with the surface
2 3
OH groups of porous γ-Al O . Meanwhile, the bands at 1444 and 1612
-1
cm are characteristic of Lewis acid sites, which can be ascribed to the
interaction between nitrogen-long-pair electrons and the coordinatively
2
3+
surface area of the obtained porous alumina is about 349 m /g, which is
unsaturated Al ions in octahedral and tetrahedral coordination.
-1
comparable to those of the reported mesoporous Alumina (Table S2).
The crystal structure of the porous Al O was further characterized by
2 3
powder X-ray diffraction (XRD). As shown in Figure 4a, three
diffraction peaks at about 37º, 46º and 67º, which represent the (311),
Furthermore, the band at about 1576 cm can be contributed to both of
aprotic sites and Lewis acid sites. After the desorption of pyridine in
vacuum at room temperature (Figure 5b), the intensities of the
characteristic bands are decreased, meaning some weakly absorbed
pyridine were desorbed. When desorbing pyridine in vacuum at higher
temperatures (Figure 5c-5g), the characteristic bands shift to higher
frequencies with the increasing temperature as more coordination bond
energy are needed. The strong interactions between pyridine and the
porous alumina owning to the presence of micropores and mesopores,
so the absorption bands of Lewis acid sites and aprotic sites can be
clearly detected even at 300 °C. Furthermore, the characteristic bands
(
400) and (440) reflections of γ-phase alumina can be detected in the
obtained Al . The crystal structure of the obtained hierarchical
porous Al is similar to that of the commercial γ-Al . These
results indicate crystalline γ-Al is formed after calcination at high
temperatures and removal of template.
2
O
3
2
O
3
2 3
O
2
O
3
27
Al MAS NMR spectroscopy was also employed to study the local
structure of the porous γ-Al . Two resonances centered at 9 and 60
2
O
3
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2 3
Table 1. Ru/Al O catalysts tested in the hydrolysis of ammonia borane
-
1
Catalysts
TOF/mol(H
2
) min
Ref.
-1
mol(Ru)
228.2
1
2
5
wt % Ru/γ-Al
wt % Ru/γ-Al
wt % Ru/γ-Al
2
2
2
O
O
O
3
3
3
This work
This work
This work
18a
256.8
205.4
Ru/γ-Al
2
O
3
23.05
Ru@Al
2
O
3
39.6
77
18b
Ru/γ-Al
2
O
3
18c
catalysts have higher TOF values than those of the reported catalysts,
which may be attributed to the high surface area and hierarchical pore
structures of the microporous γ-Al
important role for catalysts. Further recycling tests were detected to
test the durability of 5wt %Ru/γ-Al catalyst for the hydrolysis of
NH BH . The activity of Ru/γ-Al catalyst decreases to 40% in the
second cycle and remains at the same level in the following cycles
Figure S3). After the first cycle, some avtive sites of the catalyst may
2 3
O . The durability also play an
Figure 5. FTIR spectra of pyridine adsorption on the obtained hierarchical porous γ-
2 3
O
Al
2
3
O measured at (a) 25 °C after adsorption of pyridine and after desorption at (b) 25,
(c) 100, (d) 150, (e) 200, (f) 250 and (g) 300 °C for 0.5 h.
3
3
2 3
O
(
-1
of Brønsted acid sites at about 1540 cm can not be observed in FTIR
spectra, indicating there is no Brønsted acid sites in this hierarchical
be covered by boron species,[19] which leads to the decrease of the
activity. However, the absorption of boron species may be saturated at
porous γ-Al
Ammonia borane (NH
for hydrogen storage owing to its high hydrogen content (19.6
wt%).[17] In recent reports, Ru/Al has been used as catalysts to
hydrolyze NH BH and the hydrolysis mechanism has also been
discussed.[18] In our experiment, the hydrolytic dehydrogenation of Conclusions
NH BH was chosen to evaluate the catalytic activity and durability of
Ru/γ-Al catalyst. H evolution for the hydrolysis of NH BH at
0 °C with different Ru concentrations are shown in Figure 6, the rate
2
O
3
.
2 3
the following cycles, so Ru/γ-Al O catalyst have good durability for
catalytic hydrolysis of ammonia borane from the secone to the sixth
cycle.
3
BH
3
) has been regarded as a promising material
2
O
3
3
3
3
3
2
O
3
2
3
3
In summary, we demonstrate an effective method to synthesize
2
3
hierarchical porous γ-Al
CTF-1 as a template. The hierarchical porous γ-Al
micropore (1.27 nm) and mesopore (6.27 nm). The obtained porous γ-
Al with high surface area and hierarchical pore structures can be
2
O
3
with surface areas up to 349 m /g by using
of hydrogen generation increases by increasing Ru concentration as
expected, and the reaction can be completed in approximately 3.8, 1.7,
2
O
3
has both
0
.78 min when the molar ratios of Ru and NH
and 0.020, respectively. The initial turnover frequency (TOF) values of
Ru/Al catalysts were listed in Table 1, Ru/microporous γ-Al
3 3
BH are 0.004, 0.008
2 3
O
employed as an effective support for Ru particles and it exhibited high
catalytic activity and good durability for catalytic hydrolysis of ammonia
borane. This replication procedure is a facile and highly effective
2
O
3
2 3
O
2 3
approach for preparation of microporous γ-Al O with hierarchical
porosity and high density of Lewis acidic sites. These properties are of
significant importance for the application of the porous alumina in
catalysis, sorption, separation, and other promising fields.
Experimental Section
Materials
1
,4-dicyanobenzene (DCB) and Zinc chloride (anhydrous, 98 %) were purchased
from alfa and stored in a glove box filled with purified argon. Al(NO ·9H O,
3
)
3
2
ammonia solution (~28%), hydrogen peroxide (30%), NaOH, concentrated HCl
and ethanol were purchased from Kermel chemicals of Tianjin. Ammonia
[
20]
borane was synthesized according the previous report.
Ruthenium chloride
was purchased from Tianjin Jinbolan Fine Chemical Co., Ltd.
2 3
Synthesis of microporous Al O
Figure 6. Hydrogen evolution for the hydrolysis of NH
3 3
BH in the presence of Ru/γ-
Al catalysts at 30 °C with different Ru concentrations.
2 3
O
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FULL PAPER
[
12]
CTF-1 template was synthesized through ionothermal method,
1,4-
CP/MAS probe with methyl carbon of hexamethylbenzene as an external
reference.
2
dicyanobenzene (DCB) and ZnCl were mixed with a molar ratio of 1/1 and
heated at 400 °C for 40 h. After the reaction, the product was grinded and
washed thoroughly with 5wt % HCl and deionized water for three times to
remove the ZnCl
for 2 h and calcinated under argon at 500 °C for 2 h in tube furnace to remove
the adsorbate in the micropore. 0.76g Al(NO ·9H O was dissolved in 10 ml
ethanol and then 1.0 g calcinated CTF-1 was dispersed in the solution. The
amount of added Al(NO ·9H O was based on the reported pore volume of the
2
in the product. Then the product was filtrated, dried at 80 °C
Acknowledgements
3
)
3
2
This work is financially supported by Project of National Natural
Science Fund for Distinguished Young Scholar (51225206), Project of
National Science Foundation of China (21273229 and U1232120).
3
)
3
2
3
CTF-1 (0.40 cm /g) and the density of the aluminum precursor. After stirring in
a fume cupboard to evaporate the ethanol in the solution, the sample was dried at
8
0 °C for 2 h. The obtained sample was put into an open glass, then the open
Keywords: Catalytic hydrolysis of ammonia borane • CTF-1
glass was put into a stainless steel reactor with glass liner, which containing 20
mL 14wt % ammonia solution, the sample and the ammonia solution did not
direct contact. The stainless steel reactor was sealed and heated in an oven at
2 3
template • Microporous γ-Al O • Microporous materials •
Template synthesis
8
0 °C for 10 h to hydrolyze the aluminum precursor. After the reaction, the
sample was filtrated and washed with deionized water and ethanol. The product
was dried at 80 °C for 2 h and calcined at 500 °C for 2 h to obtain CTF-1/Al
The composites were then further treat with different amount of aluminum
precursor (0.52 Al(NO ·9H for the second cycle and 0.39
Al(NO ·9H O for the third cycle) in the same procedure in order to improve
[
[
1]
2]
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Schuth, Chem. Soc. Rev. 2014, 43, 313-344.
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g
3
)
3
2
O
g
3
)
3
2
the dispersion and ensure maximum loading of the precursor inside the
micropores. After three cycles of the reaction, the sample was calcined at 600 °C
for 2 h and then treated in hydrogen peroxide (30 %) at 100 °C for 6 h to remove
CTF-1 template (0.3 g product in 50 mL H O ). CTF-1 template can be removed
2 2
after treated with hydrogen peroxide (30 %) for 4 times, and then the product
was washed with deionized water, filtrated and dried at 80 °C for 2 h.
3
418-3421; e) A. M. Karim, V. Prasad, G. Mpourmpakis, W. W.
Lonergan, A. I. Frenkel, J. G. Chen, D. G. Vlachos, J. Am.
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Catal. Rev. 2008, 50, 222-286.
[
3]
Hydrolysis of ammonia borane
[4]
a) V. González-Peña, I. Dıaz, C. Márquez-Alvarez, E. Sastre, J.
́
Pérez-Pariente, Microporous Mesoporous Mater. 2001, 44–45,
2
03-210; b) J. C. Ray, K.-S. You, J.-W. Ahn, W.-S. Ahn,
2
2 3 3
5 mg porous γ-Al O was kept into a flask, 10 mL RuCl solution (contains
Microporous Mesoporous Mater. 2007, 100, 183-190; c) S.
Valange, J. L. Guth, F. Kolenda, S. Lacombe, Z. Gabelica,
Microporous Mesoporous Mater. 2000, 35–36, 597-607.
a) Q. Yuan, A.-X. Yin, C. Luo, L.-D. Sun, Y.-W. Zhang, W.-T.
Duan, H.-C. Liu, C.-H. Yan, J. Am. Chem. Soc. 2008, 130,
1
wt %, 2wt % and 5wt % Ru) was added into the flask. The solution was stirring
3+
0
for 5 h and Ru was in situ reduced to Ru by NH
started when the aqueous ammonia borane solution (contains 20 mg NH
mL DI water) was injected into the reaction flask with a syringe under
3
BH
3
solution. The reaction
3
BH in
3
[
5]
2
vigorous stirring at 30 °C, and a burette filled with water was connected to the
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Chemistry - An Asian Journal
10.1002/asia.201601631
FULL PAPER
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For internal use, please do not delete. Submitted_Manuscript
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FULL PAPER
FULL PAPER
Miao Zhang,
Lin Liu,*
Teng He,
Zhao Li
Guotao Wu
Ping Chen*
Microporous crystalline γ-alumina can be synthesized by using a microporous covalent
triazine framework (CTF-1) as a template. The hierarchical porous γ-Al
both micropore (1.27 nm) and mesopore (6.27 nm), large surface area (349 m g ), as well as
2
O
3
2
particles have
-1
Page No. – Page No.
2 3
high density of Lewis acidic sites. Furthermore, Ru/microporous γ-Al O catalyst exhibited
2 3
Microporous crystalline γ-Al O replicated
high catalytic activity and good durability for catalytic hydrolysis of ammonia borane.
from microporous covalent triazine
framework and its application as support
for catalytic hydrolysis of ammonia borane
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