Coordination of manganese porphyrins on amino-functionalized MCM-41 for heterogeneous catalysis of naphthalene hydroxylation

Article abstract of DOI:10.1016/S1872-2067(15)60836-1

The different amounts of [5,10,15,20-tetrakis-(pentafluorophenyl)porphyrin] manganese chloride (TF₂₀PPMnCl) were immobilized on amino-functionalized MCM-41 for catalysis of the hydroxylation of naphthalene. The samples were characterized by X-ray powder diffraction, N₂ adsorption/desorption isotherms, Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy, scanning electron microscopy, diffuse reflectance ultraviolet-visible spectroscopy, thermogravimetric and differential scanning calorimetry, and inductively coupled plasma mass spectrometry. The results indicated that the manganese porphyrins were axially coordinated on amino-functionalized MCM-41. The prepared samples showed remarkable catalytic activity in the hydroxylation of naphthalene with meta-chloroperbenzoic acid as the oxidant. The catalyst could be reused several times without loss of its activity.

Full text of DOI:10.1016/S1872-2067(15)60836-1

Chinese Journal of Catalysis 36 (2015) 1035–1041
a v a i l a b l e a t w w w. s c i e n c e d i r e c t . c o m
j o u r n a l h o m e p a g e : w w w. e l s e v i e r. c o m / l o c a t e / c h n j c
Article
Coordination of manganese porphyrins on amino-functionalized
MCM-41 for heterogeneous catalysis of naphthalene hydroxylation
Fu Yang, Shuying Gao, Cuirong Xiong, Haiqing Wang, Jin Chen, Yan Kong *
State Key Laboratory of Materials-Oriented Chemical Engineering, College of Chemistry and Chemical Engineering, Nanjing Technology University,
Nanjing 210009, Jiangsu, China
A R T I C L E I N F O
A B S T R A C T
Article history:
The different amounts of [5,10,15,20-tetrakis-(pentafluorophenyl)porphyrin] manganese chloride
(TF20PPMnCl) were immobilized on amino-functionalized MCM-41 for catalysis of the hydroxylation
of naphthalene. The samples were characterized by X-ray powder diffraction, N2 adsorption/de-
sorption isotherms, Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy,
scanning electron microscopy, diffuse reflectance ultraviolet-visible spectroscopy, thermogravimet-
ric and differential scanning calorimetry, and inductively coupled plasma mass spectrometry. The
results indicated that the manganese porphyrins were axially coordinated on amino-functionalized
MCM-41. The prepared samples showed remarkable catalytic activity in the hydroxylation of naph-
thalene with meta-chloroperbenzoic acid as the oxidant. The catalyst could be reused several times
without loss of its activity.
Received 9 January 2015
Accepted 17 March 2015
Published 20 July 2015
Keywords:
Manganese porphyrin
Immobilization
Axial coordination
Naphthalene hydroxylation
Heterogeneous catalysis
© 2015, Dalian Institute of Chemical Physics, Chinese Academy of Sciences.
Published by Elsevier B.V. All rights reserved.
1. Introduction
homogeneous catalysts are difficult to recycle, which may hin-
der their practical application. Heterogeneous catalysts, such as
The products of selective oxidation of aromatic compounds
are often used as raw materials and intermediates in chemical
industries [1–6]. For example, naphthol from the oxidation of
naphthalene is widely used in medicines, dyes, perfumes, and
antioxidants. Currently, naphthol is mainly produced by sul-
fonation/alkali-fusion from isopropyl naphthalene. However,
these methods are time consuming and can produce toxic by-
products that cause environmental pollution. Thus, direct hy-
droxylation of naphthalene to naphthol has attracted consid-
erable attention [7]. In particular, research has focused on the
use of efficient catalysts for this reaction.
mesoporous silica loaded with transition metals, have been
investigated for direct catalysis of the hydroxylation of naph-
thalene, but the final yields are low [12,13].
Therefore, a heterogeneous catalyst with both high catalytic
performance and good reusability needs to be developed.
Mesoporous silica, such as MCM-41, is an ideal matrix for the
base support material of such a catalyst because it has high
specific surface area, appropriate pore size, and large pore
volume and its surface is easy to modify.
The aim of this study was to produce a heterogeneous cata-
lyst by immobilizing [5,10,15,20-tetrakis-(pentafluorophenyl)
porphyrin] manganese chloride (TF20PPMnCl) on amino-func-
tionalized MCM-41. Various characterization techniques were
chosen to confirm anchorage of TF20PPMnCl on the MCM-41
Many studies have looked at homogeneous catalysts, such as
metalloporphyrins, because of their excellent catalytic activity
in the direct hydroxylation of naphthalene [8–11]. However,
* Corresponding author. Tel/Fax: +86-25-83587860; E-mail: kongy36@njtech.edu.cn
This work was supported by the National Natural Science Foundation of China (21276125, 21476108).
DOI: 10.1016/S1872-2067(15)60836-1 | http://www.sciencedirect.com/science/journal/18722067 | Chin. J. Catal., Vol. 36, No. 7, July 2015

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Fu Yang et al. / Chinese Journal of Catalysis 36 (2015) 1035–1041
support. In addition, the catalytic activity and reusability of
materials in direct hydroxylation of naphthalene with me-
ta-chloroperoxybenzoic acid (m-CPBA) as an oxidant were
studied.
mass ratio at 0.2, 0.3, 0.4, and 0.5. The synthesis of
Mn(TF5PP)-MCM-41 was carried out as described previously
[18]. Briefly, 0.1 g of N-MCM-41 was dispersed in 20 mL of a
mixed solution of dichloromethane and ethanol (1:2, V/V) con-
taining a set amount of TF20PPMnCl. The solution was stirred
for 24 h in 50 °C water bath equipped with magnetic stirrer and
a reflux condenser. Finally, the product was isolated by filtra-
tion and washed with ethanol several times to obtain the cata-
lyst Mn(TF5PP)-MCM-41. For the TF20PPMnCl/N-MCM-41 mass
ratios of 0.2, 0.3, 0.4, and 0.5, the products were labeled as
x-Mn(TF5PP)-MCM-41, where x = 2, 3, 4, or 5, respectively.
2. Experimental
2.1. Materials
Cetyltrimethylammonium bromide, manganese chloride
tetrahydrate (MnCl2·4H2O), sodium silicate nonahydrate, etha-
nol, acetonitrile, toluene, propionic acid, dimethylformamide
(DMF), naphthalene, dichloromethane and pyrrole were pur-
chased from Sinopharm Chemical Reagent Co. Ltd (Shanghai,
China). Perfluorobenzaldehyde and 3-aminopropyltriethox-
ysilane (APTES) were purchased from Tokyo TCI (Shanghai)
Development Co. Ltd (Shanghai, China). All reagents were of
analytical grade. m-CPBA (purity 75%) was purchased from
Aladdin (Shanghai, China).
2.3. Characterization
X-ray powder diffraction (XRD) patterns were recorded on a
Bruker AXS D8 Advance (Billerica, MA) powder diffractometer
with Ni filtered Cu Kα radiation (λ = 0.154178 nm).
Nitrogen adsorption/desorption measurements were car-
ried out at 196 °C on a Micromeritics ASAP-2000 (Norcross,
GA). Before the measurements, the calcined samples were out-
gassed under vacuum at 100 °C for 4 h. The specific surface
area and the pore size distribution were calculated by the
Brunauer-Emmet-Teller (BET) and Barrett-Joyner-Halenda
methods, respectively.
Fourier transform infrared (FT-IR) spectra of the samples
were obtained in the range 400–4000 cm−1 with powders dis-
persed in KBr using a Bruker VECTOR 22 spectrometer.
X-ray photoelectron spectroscopy (XPS) was conducted on a
PHI 5000 Versa Probe spectrometer (Physical Electronics,
Chanhassen, MN) with Al Kα radiation (1486.6 eV). The C 1s
peak at 284.6 eV was used as the reference for binding energy.
Field emission scanning electron microscopy images of the
samples were recorded using a Hitachi S4800 (Tokyo, Japan).
Diffuse reflectance ultraviolet-visible (UV-Vis) spectra of the
samples were obtained in the range of 200–800 nm by a Per-
kin-Elmer Lambda 35 spectrometer.
2.2. Preparation of the catalysts
2.2.1. Synthesis of MCM-41
Pure MCM-41 was prepared as reported previously [14].
Typically, 3.64 g of cetyltrimethylammonium bromide and
11.36 g of Na2SiO3·9H2O were dissolved in 100 mL of distilled
water at 80 °C. After cooling to room temperature, the solution
was adjusted to pH = 9.5 using sulfuric acid (1 mol/L). The ob-
tained gel was transferred to a Teflon stainless autoclave and
aged at 100 °C for 3 d. The product was centrifuged and
washed with distilled water three times and then with ethanol
three times. The sample was calcined at 550 °C for 5 h in a
stream of dry air to obtain MCM-41.
2.2.2. Amino-functionalization of MCM-41
According to the literature [15], 40 mL of toluene, 0.3 g of
MCM-41, and 0.1 mL of APTES were added to a three-neck
round-bottom flask equipped with a magnetic stirrer and a
reflux condenser. After stirring in a 70 °C water bath for 12 h,
the product was filtered, washed and dried at 60 °C. The prod-
uct was labeled as N-MCM-41.
Thermogravimetric and differential scanning calorimetry
(TG-DSC) patterns were obtained using a Hitachi TGA inte-
grated thermal differential thermal analyzer (simultaneous
thermal analyzer, EXSTAR TG/DTA7000).
Manganese contents in the catalysts were measured using a
Jarrell-Ash 1100 inductively coupling plasma mass spectrome-
ter.
2.2.3. Synthesis of porphyrins and metalloporphyrins
The free base porphyrin [5,10,15,20-tetrakis(pentafluoro-
phenyl)porphyrin] (H2TF20PP) was prepared according to an
established procedure [16]. For the metallation of H2TF20PP
[17], in a three-neck flask, 200 mg of H2TF20PP and 1 g of
CH3COONa were dissolved in 100 mL of DMF. Manganese chlo-
ride tetrahydrate (20 mmol) was added, and the mixture was
refluxed at 80 °C under a nitrogen atmosphere for 2 h. After
cooling the resulting solution to room temperature, the product
was collected by centrifugation and washed with DMF and wa-
ter, and the product was labeled as TF20PPMnCl.
2.4. Catalysis tests
Hydroxylation of naphthalene was carried out with 1 g of
naphthalene, 20 mL of dichloromethane, 20 mL of acetonitrile,
0.1 g of catalyst, and 1.35 g of m-CPBA. After 4 h at 30 °C, the
products were analyzed by an SP-6890 gas chromatograph
(Lunan Ruihong Chemical Instrument Co. Ltd, Lunan, China)
with an SE-54 capillary column (0.32 mm × 30 m). The conver-
sion and selectivity were calculated by the internal standard
method with 1,2-dimethoxybenzene.
2.2.4. Synthesis of Mn(TF5PP)-MCM-41
Different amounts of TF20PPMnCl were immobilized on the
MCM-41 support by controlling the TF20PPMnCl/N-MCM-41
To investigate reuse of the Mn(TF5PP)-MCM-41, the solid
catalyst was separated from the reaction mixture by centrifu-
gation and used again in a new reaction.

Fu Yang et al. / Chinese Journal of Catalysis 36 (2015) 1035–1041
1037
+
O
O
MCM-41
Mn(TF5PP)-MCM-41
N-MCM-41
F
F
Si
NH2
F
F
F
F
O
F
F
F
F
F
F
F
Manganese
chloride
F
F
F
F
F
F
F
F
N
N
F
F
NH
N
F
Mn2+
F
F
F
F
+
N
N
HN
F
N
F
F
F
F
F
F
N
F
F
O
F
F
F
F
F
F
F
F
TF20PPMnCl
H2TF20PP
Scheme 1. Synthesis of the Mn(TF5PP)-MCM-41 catalyst.
ganic compounds on the surface of MCM-41. Although the
(110), (200), and (210) peaks were unable to be identified be-
cause of their low intensity, the existence of (100) diffraction
peaks of N-MCM-41 and 5-Mn(TF5PP)-MCM-41 revealed that
the mesophase of the host materials was still maintained.
3. Results and discussion
Scheme shows the procedure for immobilizing
TF20PPMnCl on APTES modified MCM-41. First, N-MCM-41 was
prepared by reaction of APTES with MCM-41. In the next step,
TF20PPMnCl was reacted with N-MCM-41, and this resulted in
axial coordination to provide the catalyst.
1
3.2. N2 adsorption/desorption results
The N2 adsorption/desorption isotherms and pore size dis-
tributions of MCM-41, N-MCM-41, and 2-Mn(TF5PP)-MCM-41
are shown in Fig. 2. Pure MCM-41 exhibited a typical IV iso-
therm with an H1 hysteresis loop. A steep increase in the ab-
sorption volume at relative pressures (p/p0) ranging from 0.2
to 0.4 indicated that the sample had a highly ordered mesopo-
3.1. XRD results
Fig. 1 shows the small-angle XRD patterns of some samples.
The (100) diffraction peak at 2θ = 2°–3° indicated that all the
samples exhibited the characteristics of a typical mesoporous
structure. As for pure MCM-41, three weak peaks ascribed to
(110), (200), and (210) reflections confirmed a highly-ordered
two-dimensional hexagonal (p6mm) structure [19]. The peaks
of N-MCM-41 and 5-Mn(TF5PP)-MCM-41 were weaker and
broader than those of the matrix MCM-41, which demonstrated
that the long-range order in the mesoporous material de-
creased with addition of APTES and TF20PPMnCl. Meanwhile,
the (100) reflection peak shifted to a higher 2θ value, revealing
a decrease in the d100 spacing, which may be caused by the or-
700
(a)
600
500
400
300
200
100
0
MCM-41
N-MCM-41
5-Mn(TF5PP)-MCM-41
0.0
0.2
0.4
0.6
0.8
1.0
(100)
Relative pressure (p/p0)
(b)
MCM-41
N-MCM-41
2-Mn(TF5PP)-MCM-41
(110)
(200)
(210)
(1)
(2)
(3)
2
3
4
5
6
7
8
2
4
6
8
10 12 14 16 18 20 22 24
(o )
Pore size (D/nm)
Fig. 1. XRD patterns of MCM-41 (1), N-MCM-41 (2) and
Fig. 2. N2 adsorption/desorption isotherms (a) and pore size distribu-
5-Mn(TF5PP)-MCM-41 (3).
tion (b) of MCM-41, N-MCM-41, and 2-Mn(TF5PP)-MCM-41.

1038
Fu Yang et al. / Chinese Journal of Catalysis 36 (2015) 1035–1041
Table 1
Structural properties of MCM-41, N-MCM-41 and 2-Mn(TF5PP)-
MCM-41.
(2)
(1)
ABET
(m2/g)
1183
527
Pore diameter Pore volume
Sample
(nm)
2.65
2.12
1.77
(cm3/g)
0.8562
0.3221
0.2434
MCM-41
N-MCM-41
2-Mn(TF5PP)-MCM-41
317
rous structure. The N2 adsorption volumes of N-MCM-41 and
2-Mn(TF5PP)-MCM-41 decreased sharply, and the capillary
condensation step shifted to a lower relative pressure, which
indicated a gradual decrease in the pore size. Some structural
parameters of the samples are summarized in Table 1. Com-
pared with MCM-41, the N-MCM-41 and 2-Mn(TF5PP)-MCM-41
samples exhibited relatively low BET surface areas and pore
volumes. Moreover, it should be noted that the pore size
showed a significant decrease from 2.65 nm for MCM-41 to
2.17 nm for N-MCM-41 and 1.77 nm for 2-Mn(TF5PP)-MCM-41
(Fig. 2(b)). This decrease in pore size supports the small-angle
XRD results (Section 3.1). These observations confirm that
APTES and TF20PPMnCl were successfully incorporated into
the substrate MCM-41.
635
640
645
650
655
660
665
Binding energy (eV)
Fig. 4. Mn 2p XPS spectra of TF20PPMnCl (1) and 5-Mn(TF5PP)-MCM-41
(2).
In the spectrum of 5-Mn(TF5PP)-MCM-41, absorption peaks
were observed at 1561 and 1490 cm−1. According to Zhu et al.
[17], these two peaks are caused by the vibrations of C=N and
C=C. Therefore, these results indicated that the porphyrin
tetrapyrrole ring is anchored on the surface of the mesoporous
silica. The red shift of the out-of-plane bending vibration of N–H
from 800 to 795 cm−1 could be ascribed to a decrease in the
electron density of N resulting from the coordination of N and
Mn atoms. The additional band at 583 cm−1 could be attributed
to Mn–N vibration because of axial coordination between Mn
and N atoms [21,22].
3.3. FT-IR results
The FT-IR spectra of TF20PPMnCl, MCM-41, N-MCM-41, and
5-Mn(TF5PP)-MCM-41 are shown in Fig. 3. The peaks at around
1090 (shoulder at 1250) and 800 cm−1 could be attributed to
asymmetric and symmetric stretching vibrations of Si–O, re-
spectively. The broad band at approximately 3400 cm−1 could
be attributed to the stretching vibration of surface O–H. For
N-MCM-41, the peak around 2923 cm−1 was assigned to the
stretching vibration of CH2. The intensity of the peak at 800
cm−1 increased for N-MCM-41 compared to MCM-41, which
was attributed to the emergence of an out-plane bending vibra-
tion of N–H in N-MCM-41 [20]. Based on these findings, we
concluded that APTES was successfully grafted on MCM-41.
3.4. XPS results
The Mn 2p XPS spectra of the samples are shown in Fig. 4. A
peak centered at 642.1 eV was observed for TF20PPMnCl, which
was in accordance with the binding energy of Mn 2p3/2 report-
ed for Mn(III) porphyrins [23]. Meanwhile, a peak centered at
642.4 eV was observed for 5-Mn(TF5PP)-MCM-41. The slight
shift (0.3 eV) demonstrated the difference in the coordination
environment of the Mn atoms, which seemed to indicate axial
coordination of manganese porphyrins with –NH2 grafted on
the mesoporous MCM-41.
(1)
3.5. SEM results
796
1561
1490
Fig. 5 shows SEM images for MCM-41 and 5-Mn(TF5PP)-
MCM-41. Compared with MCM-41, 5-Mn(TF5PP)-MCM-41 had
an irregular surface, possibly because of the formation of or-
ganic species on the surface of the catalyst. This observation
may support the FT-IR results.
(2)
800
800
460
3440
3440
(3)
(4)
1090
2923
2943
（a）
(a)
460
460
(b)
(b)
1090
1090
795
583
1561
1490
3440
4000 3500 3000 2500 2000 1500 1000 500
Wavenumber (cm1)
Fig. 3. FT-IR spectra of TF20PPMnCl (1), MCM-41 (2), N-MCM-41 (3),
and 5-Mn(TF5PP)-MCM-41 (4).
Fig. 5. SEM images of MCM-41 (a) and 5-Mn(TF5PP)-MCM-41(b).

Fu Yang et al. / Chinese Journal of Catalysis 36 (2015) 1035–1041
1039
427
423
100
90
80
70
60
50
15
TG
653
524
560
601
(1)
10
5
543
590
620
(2)
(3)
DSC
0
-5
400
500
600
700
800
100 200 300 400 500 600 700 800
Temperature (oC)
Wavelength (nm)
Fig. 6. Diffuse reflectance UV-Vis spectra of H2TF20PP (1), TF20PPMnCl
(2), and 5-Mn(TF5PP)-MCM-41 (3).
Fig. 7. TG-DSC curves of 5-Mn(TF5PP)-MCM-41.
3.6. UV-Vis results
different Mn contents was evaluated in the hydroxylation of
naphthalene using m-CPBA as the oxidant. The results in Table
2 demonstrated that increasing the loading of manganese por-
phyrin led to an increase in the catalytic activity of the material.
The best overall result was obtained with 5-Mn(TF5PP)-
MCM-41, which gave a maximum yield of 22.5% for 1-naphthol.
Compared with other heterogeneous catalysts from earlier
studies, the heterogeneous manganese porphyrins catalysts
from the present study showed relatively high catalytic activity.
This may be attributed to the unique catalytic process of the
Mn(TF5PP)-MCM-41 catalyst. In aprotic solutions, manganese
porphyrins are oxidized to manganese peroxy complexes
(TF5PP)MnOOAr, which react with substituted sites on the
naphthalene ring. During this reaction, manganese porphyrins
play a role in transferring oxygen. The presence of fluorine
substituents may lead to higher stability of manganese porphy-
rins and reduce over-oxidation. Meanwhile, fluorine substitu-
ents can reinforce the redox potential of manganese porphyrins
and improve the catalytic activity [28].
Diffuse reflectance UV-Vis spectra of H2TF20PP, TF20PPMnCl
and 5-Mn(TF5PP)-MCM-41 are shown in Fig. 6. The UV-Vis ab-
sorption bands of porphyrins are attributed to electronic tran-
sitions from the ground state (S0) to the two lowest singlet ex-
cited states, S1 (Q state) and S2 (Soret state) [24]. The S0→S1
transition exhibits weak Q bands in the visible light region,
while the S0→S2 transition produces a strong Soret band in the
near UV region [25,26]. In Fig. 5, H2TF20CPP showed a Soret
band at 427 nm and four Q bands at 524, 560, 601, and 653 nm,
which correspond to four characteristic absorptions of the
transitions Qx(0,0), Qx(0,1), Qy(0,0), and Qy(0,1), respectively.
For TF20PPMnCl, when Mn ions were anchored to the
tetrapyrrole ring of the porphyrins, the symmetry of the mole-
cule was changed from D2h to D4h [27]. Accordingly, the absorp-
tion spectra were also altered to some extent. Moreover, be-
cause of coordination between Mn and porphyrins, the fourth Q
band (653 nm) disappeared while the other three Q bands be-
came weaker and red shifted.
Compared with homogeneous manganese porphyrin cata-
lysts, Mn(TF5PP)-MCM-41 showed relatively low catalytic ac-
tivity. This could be explained by the axial coordination be-
tween Mn ions and NH2– reducing the possibility of collisions
between reactants and active metal ions [29]. However, the
heterogeneous manganese porphyrin catalyst exhibited good
reusability. As shown in recycling tests (Table 3), Mn(TF5PP)-
The spectrum of 5-Mn(TF5PP)-MCM-41 was similar to that
of TF20PPMnCl, indicating that the structure of the manganese
porphyrin did not alter after incorporation into the composite
system.
3.7. TG-DSC results
TG-DSC was conducted quantitatively to evaluate the con-
tent of the modifiers (Fig. 7). Several maxima were observed in
the obtained DSC curve. The first change in the curve between
50 to 100 °C was assigned to removal of physically adsorbed
water on the surface; this corresponded to an approximately
10% mass loss. Additional mass losses centered at 300, 425,
and 542 °C were observed, which were attributed to elimina-
tion of surface bound organic groups. The results also indicated
that the Mn(TF5PP)-MCM-41 catalysts were thermally stable up
to 300 °C.
Table 2
Catalytic activity of Mn(TF5PP)-MCM-41 for hydroxylation of naphtha-
lene.
Selectivity (%)
1-Naphthol 2-Naphthol
Mn/Si
molar ratio
Conversion
(%)
Catalyst
2-Mn(TF5PP)-MCM-41 0.0046
3-Mn(TF5PP)-MCM-41 0.0084
4-Mn(TF5PP)-MCM-41 0.0092
5-Mn(TF5PP)-MCM-41 0.0093
TF20CPPMnCl [8]
Fe-MCM-41 [12]
V-MCM-41 [13]
19.4
24.3
30.6
31.2
54.5
5.1
70
71
70
72
93
3
4
5
3
—
—
—
trace
3.5
—
6.5
—
10
3.8. Catalytic tests
Reaction conditions: Substrate/m-CPBA = 1/1.2 (molar ratio), 30 °C, 4
h, 1 g of substrate and 0.1 g of catalyst in 40 mL of CH3CN/CH2Cl2 (1:1,
V/V) mixed solvent.
The catalytic activity of Mn(TF5PP)-MCM-41 catalysts with

1040
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Table 3
46
Reusability of Mn(TF5PP)-MCM-41 for naphthalene hydroxylationa
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2315
Selectivity (%)
Run
Conversion (%)
1-Naphthol
2-Naphthol
1
2
3
4
5
31.2
29.3
27.8
27.6
27.3
72
71
68
68
70
3
3
5
4
4
Reaction conditions: Substrate/m-CPBA = 1/1.2 (molar ratio), 30 °C, 4
h, 1 g of substrate and 0.1 g of catalyst in 40 mL of CH3CN/CH2Cl2 (vol-
ume ratio = 1/1) mixed solvent, sample 5-Mn(TF5PP)-MCM-41 was
reused in naphthalene hydroxylation.
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MCM-41 showed high conversion and selectivity without ob-
servable leaching of the complex (Mn/Si mole ratio after five
runs was 0.0072). The obtained catalytic results highlight the
potential of the synthesized Mn(TF5PP)-MCM-41 as a catalyst
for the catalytic oxidation of naphthalene in a heterogeneous
system.
4. Conclusions
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A catalyst was constructed by immobilizing manganese
porphyrins on amino-functionalized MCM-41. The catalytic
activity of this material could be changed by altering the
amounts of metalloporphyrin immobilized on the MCM-41.
Compared with existing homogeneous manganese porphyrins
systems, the produced catalyst showed better stability and
comparable catalytic activity. It gave much higher naphthalene
conversion than other heterogeneous catalysts. The catalyst
could be reused more than five times without obvious loss in its
activity and selectivity.
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Graphical Abstract
Chin. J. Catal., 2015, 36: 1035–1041 doi: 10.1016/S1872-2067(15)60836-1
Coordination of manganese porphyrins on amino-functionalized MCM-41 for heterogeneous catalysis of naphthalene
hydroxylation
Fu Yang, Shuying Gao, Cuirong Xiong, Haiqing Wang, Jin Chen, Yan Kong *
Nanjing Tech University
TF20PPMnCl
+
MCM-41
Mn(TF5PP)-MCM-41
N-MCM-41
Polyhalogenated manganese porphyrins with fluorine substituents were anchored on amino-functionalized MCM-41 to produce a heter-
ogeneous catalyst, which exhibited remarkable catalytic activity and desirable reusability in the hydroxylation of naphthalene.

Fu Yang et al. / Chinese Journal of Catalysis 36 (2015) 1035–1041
1041
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