Superior Catalytic Performance of Hierarchically Micro-Meso-Macroporous CuAlPO-5 for the Oxidation of Aromatic Amines under Mild Conditions

Article abstract of DOI:10.1002/cctc.201601157

Aromatic nitro compounds are versatile building blocks for organic synthesis because of easy transformation of the nitro group into other diverse functional groups. Herein, hierarchical mesoporous–macroporous CuAlPO-5 was prepared and found to exhibit excellent catalytic activity and stability for the oxidation of aromatic amines to nitroarenes. For the oxidation of bulky aromatic amine molecules (e.g., 1-naphthalenamine), hierarchical CuAlPO-5 exhibited higher selectivity to the product than homogeneous Cu catalysts and higher catalytic activity than traditional microporous CuAlPO-5; the former was attributed to shape selectivity to the product and the latter was attributed to improved diffusion of bulky molecules inside the meso- and macropores. After CuAlPO-5 was used five times in the oxidation of 4-bromoaniline, >98.6 % conversion and 98.1 % selectivity to the product were obtained. This shows the potential and attractiveness of this method for the preparation of nitroarenes by the selective oxidation of organic amines.

Full text of DOI:10.1002/cctc.201601157

Accepted Article
Title: Superior Catalytic Performance of Hierarchically Micro-Meso-
Macroporous CuAlPO-5 for Oxidation of Aromatic Amines under
Mild Conditions
Authors: Qingping Ke, Mingzhou Wu, and Guanzhong Lu
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ChemCatChem
10.1002/cctc.201601157
ICATION
r Catalytic Performance of Hierarchically Micro-Meso-
orous CuAlPO-5 for Oxidation of Aromatic Amines under
nditions
[
a,b]
[a]
[c]
[a]
,
Mingzhou Wu, Huizhen Yu and Guanzhong Lu*
ional))
atic nitro compounds are versatile building blocks for
hesis, due to easy transformation of the nitro groups
functional groups. Herein, hierarchical mesoporous-
uAlPO-5 was prepared and exhibited excellent
and stability for the oxidation of aromatic amines to
the oxidation of bulky aromatic amine molecules (as
ne), this hierarchical CuAlPO-5 exhibits the higher
oduct than homogeneous Cu catalysts, and the
activity than traditional microporous CuAlPO-5, in
is attributed to the shape selectivity to product and
es the diffusion of bulky molecules inside meso- and
er CuAlPO-5 was used five times in the oxidation of
there are some problems at the product separation and/or usage
of hazardous reagents. Although some metal-based catalysts,
such as iron, manganese, and titanium-based catalysts, are
active for the oxidation of aromatic amines, in addition to the low
selectivity to product, their catalyst stability is another great
challenge.
[
6]
[7]
[8]
As is well-known, aluminophosphate zeolites are crystalline
porous materials with high thermal stability, and Al and/or P
atoms in aluminophosphate (AlPO-n) frameworks can be easily
replaced by metal ions to form metal-doped aluminophosphate
[
9]
(
MAlPO-n) materials.
AlPO-5 zeolite, a typical example,
contains one-dimensional hexagonally arrayed straight channels
>
98.6% conversion and 98.1% selectivity to product
[
9]
with an opening pore of 0.73 nm, and can be potentially used
as the catalyst for the oxidation of aromatic amines. However, as
the catalyst for the oxidation of aromatic amines with two or
more benzene rings (molecule diameter of > 0.7 nm), AlPO-5
zeolite is still restricted, due to its smaller micropores for
limitation of mass transfer or shape selectivity to product. We
have found that mesoporous lanthanum-doped AlPO-5 zeolite
exhibited the superior catalytic performance for the Ullmann
This shows a potential and attractive way for the
nitroarenes by the selective oxidation of organic
versatile building blocks for synthetic organic
d
widely used in several fields of dyes,
s, fine chemicals, and materials etc. Traditional
synthesis of aromatic nitro compounds is direct
aromatic ring under the harsh reaction conditions
[
10]
coupling of 2-naphthol with phenols.
And the hierarchical
micro-mesoporous zeolites is beneficial to the diffusion of bulky
organic molecules inside pores. To the best of our knowledge,
hierarchical micro-meso-macroporous AlPO-5 zeolite as highly
efficient catalyst for the oxidation of aromatic amines with two or
more benzene rings was not reported.
3 2 4
ncentrated HNO /H SO ) or nitration of anionic
riginated from alkyl halides, alkenes or ketones.
se conditions, many aromatic nitro compounds
[
1]
tly synthesized by these traditional methods.
xidation of aromatic primary amines provides an
cinating route for the manufacture of aromatic
ds. In the oxidation of aromatic amines to
Copper has been widely used as the catalyst for many
[11]
important organic syntheses.
However, only there are a few
[12]
successful examples for synthesis of CuAlPO-5, because the
incorporation of Cu into the AlPO-5 zeolite framework mainly
suffers the following difficulties: i) Cu(II) is a very active
component, and it can be reduced to Cu(I) at higher crystalline
temperature (>190 °C); ii) most of the specific structure directing
agents (SDA) are complexed with copper.
[2]
ny catalysts were studied, such as KI-TBHP,
[
4]
[5]
dimethyldioxirane, and Cr-MCM-41. However,
em resulted from these catalysts is the formation
roducts due to their lower selectivity to product.
the catalytic reaction systems mentioned-above,
Herein, we hydrothermally synthesized the first example of
CuAlPO-5 zeolite with hierarchical micro-meso-macropores by
using silane surfactant ([C18H37(CH ) NC H Si(CH O) ]Cl,
3 2 3 6 3 3
[
a]
Q, Ke, M, Wu, Prof. G. Lu
Key Laboratory for Advanced Materials and Research Institute of
Industrial Catalysis
TPOAC) and 1,1,3,3-tetramethylguanidine as SDA. The as-
East China University of Science and Technology
Shanghai 200237, China
E-mail: gzhlu@ecust.edu.cn
Q. Ke
College of Chemistry and Chemical
Gannan Normal University
Jiangxi 341000, China
prepared sample exhibited the color of ice-blue, due to the
[12b]
presence of hydrated Cu(II) ions in octahedral geometry.
It
was found that the calcined CuAlPO-5 zeolite exhibited excellent
catalytic performance for the oxidation of bulky aromatic amines.
Owing to the uniform incorporation of Cu species into zeolite
framework and the presence of micro-meso-macropores, this
hierarchical pore CuAlPO-5 zeolite possesses higher catalytic
activity and selectivity than the homogeneous Cu catalysts.
[
[
b]
c]
H, Yu
College of Chemistry and Materials Engineering
Wenzhou University
Zhejiang 325035, China
As shown in Figure 1a, the CuAlPO-5 sample has the strong
X-ray diffraction peaks of the AFI structure, which indicates
Supporting information for this article is given via a link at the end of
the document.
[9]
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ChemCatChem
10.1002/cctc.201601157
ICATION
e with high crystallinity and purity has been
he doping of copper species does not change the
rk structure. Meanwhile, the diffraction peaks of
mesopore volume was increased with the increase in the
TPOAC content in the gel. On the contrary, the BET surface
area and micropore volume were decreased. These results
above show that the hierarchically micro-meso-macroporous
CuAlPO-5 zeolite with uniform morphology and highly dispersed
Cu species and has been prepared. And the crystallization
process of this hierarchically porous CuAlPO-5 zeolite in the
presence of TPOAC is proposed as Figure S3.
35.6 and 38.8° for CuO; 2θ = 36.4 and 42.3° for
observed, indicating that the Cu elements are
d in the CuAlPO-5 sample. This was further
e EDS mapping (Figure S1). The band centered
V-Vis diffuse reflectance spectrum of CuAlPO-5
lated to the charge-transfer between oxygen and
ns, involving isolated framework Cu species in
Table 1. Textural parameters of MAlPO- 55 samples.
[
13]
ral geometry.
In its EPR spectrum only the
M amount (wt.%)
2+
ed Cu ions can be observed, and there is on
er Cu species including CuO and Cu ions.
x
SS BET
(( m /g)
V
micro
3
V
meso
3
d
100
(Å)
Sample
2
+
[12b]
(cm /g) (cm /g)
In gel
In sample
als (Figure 1c) of g//=2.539 and g =2.054 are
┴
AlPO-5
‒
‒
323
226
195
281
286
291
283
310
251
244
297
275
0.08
0.06
0.05
0.08
0.05
0.07
0.07
0.10
0.08
0.06
0.09
0.08
0.26
0.34
0.36
0.22
0.40
0.31
0.30
0.10
0.24
0.27
0.25
0.26
11.85
11.76
11.77
11.88
11.77
11.78
11.77
11.85
‒
isolated Cu(II) species located in the framework
[
12b]
coordinated copper.
AlPO-5 is a typical adsorption curve of type IV
which a step can be identified at 0.45<P/P <0.95,
The nitrogen sorption
CuAlPO-5
CuFeAlPO-5
LaAlPO-5
CuZnAlPO-5
NiAlPO-5
FeAlPO-5
3.0
6.0
2.5
6.0
3.0
3.0
3.0
1.0
5.0
7.0
9.0
1.75
3.35
2.47
3.49
2.43
2.38
2.16
0.72
3.19
3.79
4.83
[
a]
b]
0
esence of mesopores and macropores in the
ts BET surface area, microporous volume,
[
2
-1
3
-1
ume, and d100 are 226 m ·g , 0.06 cm ·g , 0.34
6 Å, respectively (Table 1, CuAlPO-5).
7
0.4
0.3
0.2
0.1
0.0
235 nm
a
b
[
c]
T-CuAlPO-5
1%CuAlPO-5
5
%CuAlPO-5
%CuAlPO-5
‒
7
‒
-0.1
3
0
40
50
200
300
400
500
9%CuAlPO-5
‒
o
2
θ ( )
Wavelength (nm)
5.85 nm
250
200
150
100
0
0
0
.3
.2
.1
d
[a] The molar ratio of Cu/Fe is 1/1; [b] TT he molar ratio of Cu/Zn is 1/1; [c] T-
CuAlPO-5 indicates the traditional CuAl PP O-5 microporous zeolite.
0.0
1
10
100
Pore diameter (nm)
50
G =2.054
⊥
3500
4000
4500
0.0
0.2
0.4
0.6
0.8
1.0
field (Guass)
Relative pressure (P/P )
o
pattern, (b) UV-Vis diffuse reflectance spectrum, (c) EPR
sorption isotherm and pore size distribution curve (inset)
N
2
mple.
n the SEM images (Figure 2a), the sample is
like particle of 4~6 μm, which are composed of
igure 2b). Its TEM images show that lengths of
ets are 50-300 nm (Figure S2), and verify clearly
gation and assembly of these micro-sheets
e
formation of macropores (Figure 2c) and
ure S2a). And the mesopores can be also found
-5 crystallites (Figure S2b). These results are
the sorption isotherm and pore size
N
2
ure 1d). Its sizes of most probable mesopores
d ~37 nm, and the macropore size is 50~100 nm,
orous pores. Note that silane plays a key role in
of mesopores. As shown in Table S1, the
Figure 2. (a,b) SEM and (c) TEM imag ee s of CuAlPO-5 sample.
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ChemCatChem
10.1002/cctc.201601157
ICATION
u amount in the sample was increased from 3 to
phology was changed obviously (Figure S4), for
fine structures on sphere-like particles were
micro-sheets (3%Cu, Figure 2a) to polygon-like
6), in which the 3%CuAlPO-5 catalyst exhibited the best catalytic
performance for this title reaction. In comparison with the
[
7b,15]
reported results
(Table 2, entries 8 and 9), 3%CuAlPO-5
catalyst exhibits much higher catalytic performance. Related
with the UV-Vis spectra (Figure S6), the high selectivity should
be ascribed to the uniform Cu electronic state of 1-5%CuAlPO-5
catalyst. For the 7-9%CuAlPO-5 catalysts, the Cu species are
located inside mesoporous channels, resulting in the reduction
in the product selectivity.
%
Cu, Figure S4b), and then to nanorods (9%Cu,
or the other element doped AlPO-5 sample, its
d particle size would be varied, because of
elements (Figure S5). The particles of AlPO-5
re obviously larger than the particles of CuAlPO-
CuZnAlPO-5 and CuFeAlPO-5 (Figure S5).
hen Cu amount in the sample is >7%, the second
at ~480 nm can be observed in its UV-Vis diffuse
ctrum (Figure S6). This band is related to the
with different electronic states of Cu species
he mesoporous channels, which is also observed
Table 2. Direct oxidation of 4-brom oo aniline to 4-bromonitrobenzene.
Temp./time
(°C/h)
Conv.
(%)
Select.
(%)
GC Yield
(%)
Entry Catalyst
S oo lvent
[14]
olecular sieve.
And the Cu species in the
annels was further testified by TEM images at
Figure S7).
[
a]
[b]
1
2
3
4
5
6
7
8
9
3% CuAlPO-5
60/4
60/4
60/4
60/4
60/4
60/4
60/4
60/4
80/15
M ee CN
M ee CN
M ee CN
M ee CN
M ee CN
M ee CN
M ee CN
C TT AB
M ee CN
99.6
95.5
94.6
85.8
97.8
99.6
96
100
92.9
89.4
100
98.8
89.6
80.2
‒
99.6(91)
88.7
[
2
c]
Cu(OAc)
Table 1, the heteroatom-doped AlPO-5 samples
2
[
c]
h
BET surface areas (205-291 m /g) and
Cu(NO3)2
84.6
3
lumes (0.05-0.08 cm /g), as well as abundant
olumes (0.22-0.40 cm /g). The XRD patterns
3
1%CuAlPO-5
5%CuAlPO-5
7%CuAlPO-5
9%CuAlPO-5
H PW·nH O
85.8
ow that they kept the AFI structure, but the
s of the corresponding metal oxides could not be
there is a little difference in the peak position or
spacing (d100) between these samples (Table 1),
be assigned to the different ionic radii of
96.6
89.3
76.9
]
[
15]
This indicates that the heteroatoms have
‒
58
3
2
zeolite frameworks.
[
7b]
KI
‒
‒
65(54)
direct oxidation of aromatic amines was used as
ion to evaluate the catalytic performances of the
ed AlPO-5 catalysts. When 4-bromoaniline was
ctant in the MeCN solvent, in blank test or using
talyst, no conversion of 4-bromoaniline was
C for 4 h (Table S2); using LaAlPO-5, NiAlPO-5
atalyst, the product yield was hardly obtained;
showed very high catalytic activity, the product
ach 99.6%. Based on the results above, the
y of CuAlPO-5 should be attributed to the
species. The effects of solvent (PhMe, acetone,
nd DMSO) and the reaction time on the product
d. The results (Table S2) show that MeCN is the
e solvent for the oxidation of 4-bromoaniline over
atalyst, and the product yield was increased from
with an increase in the reaction time from 1 h to
Reaction conditions: 4-bromoaniline (1 mm mol). [a] The Cu amount in the gel,
%CuAlPO-5 (0.1g) containing 0.027 mmol Cu ions. [b] Isolate yield. [c] 0.05
mmol Cu ions.
3
100
98
100
98
96
94
92
90
Conversion
Selectivity
96
94
92
90
0
1
2
3
4
5
6
Run (t ii me)
Figure 3. Catalyst recycling usage in the oxidation of 4-bromoaniline. The
used catalyst was calcined at 550 °C for 5 h before being repeatedly used.
optimal conditions, a comparison of the catalytic
etween homogeneous and heterogeneous Cu
one (Table 2). Comparing with the homogeneous
h the yield of 84.6-88.7% (Table 2, entries 2, 3),
CuAlPO-5 catalyst exhibited better catalytic
To investigate the stability of the CuAlPO-5 catalyst, the
oxidation of 4-bromoaniline was performed on the recycled
catalyst at 60 °C for 4 h with high conversion (Figure 3) and for 1
0
0% selectivity and 99.6% yield, Table 2, entry 1). h with low conversion (Figure S9). After CuAlPO-5 was used five
O-5 catalyst, the Cu amount would affect its
mance. When the Cu amount was lower (1-5%),
y was obtained (98.8-100%, Table 2, entries 1, 4
times in the oxidation of 4-bromoaniline, >98.6% conversion and
98.1% selectivity to product were obtained. The excellent
recyclability of this CuAlPO-5 catalyst for the selective oxidation
g
the catalysts containing 3-7%Cu, higher
obtained (97.8-99.6%, Table 2, entries 1, 5 and
of organic amines provides
preparation of nitroarenes. And the results of Sheldon test
a potential method for the
[
16]
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ChemCatChem
10.1002/cctc.201601157
ICATION
w that there is no appreciable leaching of Cu ions
reaction conditions, which was further confirmed
for the Cu loading in the fresh (1.75 wt.%) and
wt.%) catalysts.
2-benzylaniline that its size (>0.8 nm) is larger than the size
(~0.73 nm) of AlPO-5 micropores, was selected as the second
kind of bulky molecule reactant, and the results are shown in
Table 4. It was found that 91.7-98.7% conversion of 2-
benzylaniline were obtained over hierarchical CuAlPO-5 and
homogeneous Cu catalysts (Table 4, entries 1-3), and only 39.5
conversion of 2-benzylaniline was obtained over microporous T-
CuAlPO-5 catalyst (Table 4, entry 4). This indicates that
diffusion of bulky molecules is significantly improved in
hierarchically porous CuAlPO-5 catalyst. Notably, the highest
selectivity (95.1%, Table 4, entry 1) to desired product over
2
xidation of 1-naphthalenamine to 1-nitronaphthalene at
Conv.
%)
Select.
(%)
GC Yield
(%)
CuAlPO-5 was obtained among the CuAlPO-5, Cu(OAc) , and
atalyst
PO-5
Solvent
MeCN
MeCN
MeCN
MeCN
(
3 2
Cu(NO ) catalysts, which is closed to the selectivity (96.6%,
[
a]
99.9
99.9
99.9
99.9
72.4
13.5
0
72.3(71)
13.5
0
Table 4, entry 4) over the microporous T-CuAlPO-5 catalyst.
This also should be attributed to the shape selectivity to product.
In addition, gram scale synthesis over CuAlPO-5 was done with
1 g catalyst and 10 mmol 2-benzylaniline (1.83 g), and the yield
of 2-benzylnitrobenzene reached 80.8% after 12 h of the
reaction at 60 °C.
[
b]
OAc)
2
[
b]
3 2
O )
AlPO-5
36.2
36.1
The mole of Cu species is 0.05 mmol.
To evaluate the applicability of the CuAPO-5 catalyst for the
oxidation of the structurally diverse aniline derivatives, 10 kinds
of aniline derivatives were used as the reactants. The results
(Table S4) showed that, they could be oxidized to the
corresponding nitroarenes at 60 °C for 4 h in the MeCN solvent,
and their yields reached 60-94%. When aromatic amines with
electron-withdrawing groups (such as Br in different positions at
benzene ring) were oxidized, 60-91% yield could be obtained,
which are difficultly obtained by traditional nitration methods. For
the oxidation of 4-cyclohexylbenzenamine, 93% yield was
obtained.
ate the diffusion of reactants and products and
ctivity to product in hierarchically micro-meso-
CuAlPO-5 catalyst, the oxidation of 1-
e
as the bulky molecule reactant to 1-
e was used as the model reaction, in which
0.7 nm) of 1-naphthalenamine is similar to the
~
re size (0.73 nm) of AlPO-5 zeolite. As shown in
ugh high conversion was obtained over both
and heterogeneous Cu catalysts, most of 1-
e was oxidized to naphthalene-1,4-dione over
Cu catalysts. The shape selectivity to the desired
served over hierarchically porous and traditional
ysts (Table 3, entries 1 and 4). For instance, the
In summary, we have successfully synthesized hierarchically
micro-meso-macroporous CuAlPO-5 zeolite, and found that it is
highly efficient heterogeneous catalyst for the oxidation of
aromatic amines including bulky molecule to nitroarenes under
mild reaction conditions. For the oxidation of bulky molecule
amine (as 1-naphthalenarmine), this CuAlPO-5 exhibits the
higher selectivity to product than homogeneous Cu catalysts,
which should be attributed to the shape selectivity to product;
comparing with traditionally microporous T-CuAlPO-5 catalyst,
CuAlPO-5 possesses the higher catalytic activity, because the
presence of meso- and macropores improves the diffusion of
bulky molecules in the catalyst. The good recyclability and
excellently catalytic performance of the CuAlPO-5 catalyst
provides an attractive way for the preparation of nitroarenes by
the oxidation of aromatic amines.
2
%
.4%) over hierarchical CuAlPO-5 is much higher
) over traditionally microporous T-CuAlPO-5
s 1 and 4), which should be ascribed to the fast
reactant and desired product in the hierarchical
O-5.
dation of 2-benzylaniline to 2-benzylnitrobenzene at 60 °C
Conv.
%)
Select.
(%)
GC Yield
(%)
Solvent
Experimental Section
(
[a]
Synthesis of CuAlPO-5
5
MeCN
MeCN
MeCN
MeCN
93.1
95.1
92.9
13.6
96.6
88.5(82.4)
90.5
[
b]
2
97.4
91.7
39.5
CuAlPO-5 sample was synthesized using a gel with the composition of
1
P
2
O
5
:0.8Al
isopropoxide (4.08 g) was added into deionized water (7.9 mL), followed
by the addition of H PO (1.8 mL) under stirring, after that the TMG (1.1
mL), Cu(OAc) (0.19 g) and TPOAC (1 mL) were added under stirring. All
2 3 2
O :0.034Cu:0.6TMG:0.3TPOAC:33H O. Typically, aluminum
[
b]
12.5
3
4
O-5
38.2
2
above operations were run at 15 °C. Finally, the synthesis gel was
transferred into an autoclave and hydrothermally crystallized at 150 °C
The mole of Cu species is 0.05 mmol.
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ChemCatChem
10.1002/cctc.201601157
ICATION
lting solid was collected by filtration, dried at 100 °C
cined at 550 °C for 5 h.
[2]
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[
[
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6]
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re of 4-bromoaniline (1 mmol), TBHP (3 mmol), the
,
and MeCN (1.5 mL) was transferred into a 10 mL
was subsequently sealed and heated at 60 °C for 4 h.
room temperature, the catalyst was separated by
[
[
7]
8]
a) S. Laha, R. G. Luthy, Environ. SS ci. Technol. 1990, 24, 363-373; b) H.
Li, L. S. Lee, D. G. Schulze, C. AA . Guest, Environ. Sci. Technol. 2003,
5
000 rpm for 10 min. The reactant and product
37, 2686-2693.
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ionization detector)-mass spectrometer (GCMS-
1
himadzu, Japan). H NMR (500 MHz, CDCl
3
) δ 8.13 –
) δ 147.06
13
[9]
2
– 7.67 (m, 2H). C NMR (126 MHz, CDCl
.98 (s), 125.01 (s).
3
9
[
[
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gements
s supported by the National Basic Research
na (2013CB933201), and the National Natural
ation of China (21306142).
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ChemCatChem
10.1002/cctc.201601157
ICATION
he Table of Contents (Please choose one layout)
NICATION
icro-Meso-
uAlPO-5 exhibits
y for oxidation
Qingping Ke, Mingzhou Wu, Huizhen Yu
and Guanzhong Lu*
omogeneous Cu
its shape selectivity,
ytic activity than
porous CuAlPO-5
e of the improved
y molecules in the
Page No. – Page No.
Superior Catalytic Performance of
Hierarchically Micro-Meso-
Macroporous CuAlPO-5 for Oxidation
of Aromatic Amines under Mild
Conditions
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