An Efficient Catalyst Based on a Metal Metalloporphyrinic Framework for Highly Selective Oxidation

Article abstract of DOI:10.1007/s10562-014-1433-z

An efficient metal-organic framework catalyst was developed with manganese tetrakis(4-carboxyphenyl)porphyrin as either bridging moiety or catalytically active sites under a hydrothermal condition. Surprisingly, the X-ray diffraction details showed that this porous network, MMPF (MMPF denotes iron-connected metal metalloporphyrinic framework) was successfully constructed with a physically flexible framework and resistance to basic solution. Accordingly, catalytic studies have demonstrated that MMPF can catalyze the selective oxidation of a variety of substrates with PhIO as oxidant in acetonitrile solution under mild temperature. More importantly, the MMPF outperformed the homogeneous Mn-TPP in catalyzing epoxidation of cyclohexene, mainly due to its high efficiency of 3D network-based nanochannel-reactor in MMPF. This gave rise to a structural resistance to formation of catalytically inactive species. Graphical Abstract: [Figure not available: see fulltext.]

Full text of DOI:10.1007/s10562-014-1433-z

Catal Lett (2015) 145:589–595
DOI 10.1007/s10562-014-1433-z
An Efficient Catalyst Based on a Metal Metalloporphyrinic
Framework for Highly Selective Oxidation
Weijie Zhang
•
•
Pingping Jiang
Jian Zhang Pingbo Zhang
•
Ying Wang
•
Received: 24 August 2014 / Accepted: 9 November 2014 / Published online: 19 November 2014
Ó Springer Science+Business Media New York 2014
Abstract An efficient metal–organic framework catalyst
was developed with manganese tetrakis(4-carboxy-
phenyl)porphyrin as either bridging moiety or catalytically
active sites under a hydrothermal condition. Surprisingly,
the X-ray diffraction details showed that this porous net-
work, MMPF (MMPF denotes iron-connected metal met-
alloporphyrinic framework) was successfully constructed
with a physically flexible framework and resistance to
basic solution. Accordingly, catalytic studies have dem-
onstrated that MMPF can catalyze the selective oxidation
of a variety of substrates with PhIO as oxidant in aceto-
nitrile solution under mild temperature. More importantly,
the MMPF outperformed the homogeneous Mn-TPP in
catalyzing epoxidation of cyclohexene, mainly due to its
high efficiency of 3D network-based nanochannel-reactor
in MMPF. This gave rise to a structural resistance to for-
mation of catalytically inactive species.
1 Introduction
Metalloporphyrins are well known for a remarkable class
of candidate materials with a range of applications, such as
light harvesting, oxygen transportation and catalysis [1–3].
Due to their excellent catalytic performance and high
product selectivity, synthetic metalloporphyrins have been
utilized in epoxidation to mimic cytochrome P450 as bio-
mimetic catalyst in the last decade. However, the appli-
cation of metalloporphyrins as catalyst in solution is
usually challenging because of the formation of catalyti-
cally inactive dimers and fast degradation in homogeneous
catalysis [4].
Metal–organic frameworks (MOFs) constructed from
organic bridging ligands and metal ions/clusters constitute
an outstanding and steadily expanding group of porous
crystalline materials [5–9]. In terms of catalytic functions,
MOFs have been successfully projected to bridge the gap
between heterogeneous materials and enzymes. To date,
several MMPFs with uncoordinated metalloporphyrin-
based building synthons, including carboxylic acid groups
or pyridyl moieties, have been applied to mimic properties
of cytochrome P450 [10–16]. Indeed, this will bring an
advantage that these metalloporphyrinic MOFs (MMPFs)
can be considered as self-supported catalysts with an
enhanced performance, due to their high-density active
sites into frameworks. Therefore, this motivated us to use
MMPF approach to target efficient heterogeneous catalysts
with open coordination frameworks, which is essential to
catalysis application.
Keywords Metal–organic framework Á Biomimetic
catalysis Á Selective oxidation Á Porphyrin
Electronic supplementary material The online version of this
article (doi:10.1007/s10562-014-1433-z) contains supplementary
material, which is available to authorized users.
W. Zhang Á P. Jiang (&) Á Y. Wang Á P. Zhang
The Key Laboratory of Food Colloids and Biotechnology,
Ministry of Education, School of Chemical and Material
Engineering, Jiangnan University, Wuxi 214122, China
e-mail: ppjiang@jiangnan.edu.cn
Noteworthy, most MMPFs based on divalent cations
2
?
(
especially M = Cu, Zn, Co and Cd) are often less stable
than those based on trivalent and more charged cations
J. Zhang
School of Chemistry and Environmental Science, Lanzhou City
University, Lanzhou 730000, China
3
?
4?
= Al, Fe, Cr, M = Ti, Zr), especially regarding to
(
M
hydrolysis [17–19]. Among them, recent studies have
123

5
90
W. Zhang et al.
shown that for a given carboxylate linker, the Fe ion as
node is a candidate in MOFs because of its low toxicity
using a rotary evaporator. To this solution, silica gel
(60–200 mesh) was added and the slurry was evaporated to
give a dry black powder, which was loaded on a silica
column using CHCl . First CHCl fraction removed any
[
20], redox potential [21, 22] and rich coordination
geometries [21–24]. Nevertheless, the Fe ion exhibits a
tendency to undergo hydrolysis to afford hydrated iron
oxides, making it difficult to obtain a desirable crystalline
coordination network in pure phase. Only a few Fe-based
MOFs (MIL-141 (A), A = Li, Na, K, Rb, Cs within the
pores) built from porphyrinic linkers, and even fewer
reports on their catalytic properties have been investigated
so far [25].
3
3
poly (pyrrole) impurity and the porphyrin was eluted with
2–4 % acetone in CHCl . It was then further purified by
3
recrystallization from a 1:4 CHCl /methanol mixture (v/v).
3
1
Yield: 0.55 g (35 %). H NMR (400 MHz, CDCl ) d
3
9.08–8.64 (m, 8H), 8.62–8.37 (m, 8H), 8.39–8.13 (m, 8H),
4.34–3.88 (m, 12H), –2.79 (s, 2H).
A solution of H TCPP 0.42 g (0.50 mmol) and MnCl
2
2-
Herein, we reported a novel metal metalloporphyrinic
framework catalyst, namely MMPF, based upon Mn-TCPP
4H O (0.24 g, 1.00 mmol) in 50 mL of DMF was refluxed
2
for 12 h. After the mixture was cooled to room tempera-
(
TCPP = tetrakis(4-carboxyphenyl)porphyrin) as a bridg-
ture, 500 mL of H O was added. The resultant precipitate
2
ing ligand and Fe as metal ion under hydrothermal condi-
tion. The new compound, MMPF (MMPF denotes iron-
based metalloporphyrinic metal organic framework) was
successfully constructed with a stable 3D framework. The
resulting purple block crystals were washed and obtained.
Interestingly, a solvent-induced breathing effect of MMPF
has been founded by a detailed XRD study. Simulta-
neously, MMPFs showed an unprecedented high robust-
ness not only in boiling water but also in basic aqueous
solutions with pH values in the range of 7–12. Moreover, a
range of substrates have been employed as substrates to
investigate catalytic efficiency of MMPF.
was filtered and washed with 200 mL of H O for three
2
times. The obtained solid was dissolved in CHCl , fol-
3
lowed by washing three times with water. The organic
layer was dried over anhydrous magnesium sulfate and
evaporated to afford quantitative dark green crystals [27].
In the next stage, 0.45 g (0.50 mmol) of the latter
product was dissolved in 20 mL of THF. To this, 1.60 g of
NaOH in 20 mL of water was added and the solution was
stirred at room temperature for 3 days. At the end of this
period, THF was removed by rotary evaporation. The crude
porphyrin was treated with 20 mL of 2 N HCl solutions,
yielding a green precipitate, which was filtered, washed
with water, and dried. Protonated porphyrin was neutral-
ized by adding 10 mL of pyridine and subsequently
removed by vacuum distillation. Then, purple solid was
washed with water and dried under a vacuum. Yield:
0.39 g (88 %).
2
Experimental
2
.1 Materials and Reagents
Methyl 4-formylbenzoate, fresh distilled pyrrole, propionic
acid, N,N-dimethylformamide (DMF), iron(II) chloride
tetrahydrate (FeCl Á4H O), manganese(II) chloride tetra-
2.3 Synthesis of MMPF
FeCl Á4H O (2.0 mg, 0.01 mmol) and Mn-TCPP (8.8 mg
2
2
3
2
hydrate (MnCl Á4H O). All commercial chemicals were
0.01 mmol) in 5 mL of DMF were ultrasonically dissolved
in a 25 mL Pyrex vial. The mixture was heated in 150 °C
oven for 72 h. After cooling down to room temperature,
purple block shaped crystals were harvested by filtration
(6 mg, 60 % yield). As synthesized samples of MMPF
were dispersed onto a glass plate for imaging. The crystals
of MMPF were shown to be cubic in morphology with
sizes from 25 to 50 lm (Fig. S1). Crystallographic data
have been deposited with the Cambridge Crystallographic
Data Centre: CCDC 941505, this data can be obtained free
of charge from The Cambridge Crystallographic Data
Center via www.ccdc.cam.ac.uk/data_request/cif. It should
be mentioned that the catalyst was used as prepared.
2
2
used without further purification unless otherwise
mentioned.
2
.2 The Porphyrin Synthesis
The 5, 10, 15, 20-tetrakis(4-carboxyphenyl)porphyrin (H2-
TCPP) was synthesized by the modified Lindsey method
[
26], involving NaOH hydrolysis of the corresponding
intermediate.
Thus, 1.22 g (7.46 mmol) of 4-carbomethoxybenzalde-
hyde and 0.50 g of distilled pyrrole (7.46 mmol) were
added to 750 mL of dry CH Cl for 30 min. Then, BF
3
2
2
etherate (92 uL) was added via syringe, and the reaction
mixture was protected from light. After stirring at room
temperature for 1 h, 1.37 g (5.62 mmol) of p-chloranil was
added in the solid form and the solution was stirred over-
night. The solution was concentrated to a small volume
2.4 Stability Measurements for MMPF
Experimental details of stability test: pH 0, pH 2, pH 4, pH
7, pH 10 and pH 12 aqueous solutions were prepared.
1
23

Efficient Catalyst Based on MMPF
591
Then, 50 mg of sample was soaked in each solution and
also in boiling water for 1 day. After that, all the samples
are centrifuged and the filtrates are kept. Samples soaked in
the acidic aqueous solutions (ligand is insoluble in acidic
aqueous solution, while soluble in basic solution), and then
they were taken pictures (Fig. S2).
Table 1 Crystal data and structure refinements for Fe-MMOF
Formula
96 3 2 8 18
C H48Fe Mn N O
Fw
1,878.85
purple
Color
Crystal system
Space group
monoclinic
P12/c1 (13)
14.908 (6)
15.345 (6)
27.753 (11)
90
˚
a (A)
2
.5 Catalytic Activity Test
˚
b (A)
˚
c (A)
Biomimetic epoxidation studies: Olefin (500 mM), PhIO
10 mM), catalyst (5 mM), acetonitrile (5.0 mL) and bro-
(
a, c (8)
mobenzene 50 mg as internal standard sealed in a Teflon-
lined screw cap vial were stirred at room temperature. This
epoxidation procedure was routinely employed according
to previous literatures with a minor modification [28–30].
For other substrates, similar assays were performed.
Thereafter, conversion and selectivity were determined by
GC using an SE-54 column (50 °C for 1 min, then 10 °C
b (8)
b = 90.424 (6)
6,348.69 (400)
2
V ( A˚ 3)
Z
3
dcalcd.(g/cm )
0.982791
0.579
-
1
)
l (mm
T (K)
173 (2)
F (000)
1,904
-
1
min up to 140 °C and 140 °C for 15 min) based on the
conversion of oxidant rather than olefins. To be more
precise, the progress of the reaction was monitored by GC
with internal standard method, by taking a small sample of
the reaction mixture and centrifugation. The product
selectivity was defined as follows (epoxide as an example):
Epoxide selectivity = GC peak area of epoxide/RGC peak
area of all products 9 100 %. In addition, the data of
catalytic performance were an average of at least three
measurements. A standard deviation of ± 4 % has to be
considered on average for the conversion and selectivity.
Reflns collected
35,928
Independent reflns
Obsd data [I [ 2r (I)]
Data/restraints/parameters
Completeness
11,276
5,501
11,276/0/573
11,276
2
GOF on F
1.039
R1, wR2 [I [ 2r (I)]
R1, wR2 (all data)
0.0555,0.1313
0.1039,0.1223
to remove the guest molecules, like DMF. By heating at
50 °C, the high temperature phases were stable after cool-
1
3
Results and Discussion
ing down again to room temperature. Of further significance,
the solvent-induced breathing effect of MMPF has also been
demonstrated after being immersed in different solvents
3
.1 Characterization of MMPF
(Fig. 2), which may lead to the difference on XPD pattern.
MMPF crystallized in the monoclinic P12/c1(13) space
group (Table 1). It contains manganese (III) tetra (p-car-
boxyphenyl) porphyrins (Fig. 1a) and a bridging bent tri-
nuclear iron cluster (Fig. 1b). Each trinuclear cluster is
coordinated by eight separate Mn-TCPP carboxylate moi-
eties; each Mn-TCPP carboxylate coordinates four distinct
Fe(III) trinuclear clusters. Compared with ever iron cluster
in MOFs [22–24], this bent trinuclear iron cluster has not
been presented in existing MOF structures. In the overall
MOFs with a breathing behaviour combine ‘‘regularity’’
with ‘‘softness’’ by exhibiting large, reversible structural
deformations (softness) without loss of crystallinity or bond
breaking. A recent research revealed that, expanding and
shrinking of the pores within the coordination networks is
concomitant with the removal and addition of coordinated
solvent [25, 31]. In particular, the peak value moved to a
higher angle region, which was indicative of an expansion in
structure. A remarkable cell volume reduction was observed
upon removal of free and coordinated DMF ligands from the
as-prepared framework without cleavage of any coordina-
tion bonding. Another interesting phenomenon was
observed that the pores within MMPF shrank when being re-
˚
network of MMPF, there are alternating 5A 9 9A and
˚
˚ ˚
A 9 8A pores down the crystallographic an axis and
7
3
˚
A 9 5A pores down the c axis. Calculations using the
˚
PLATON program indicated that the total volume of
MMPF was 47.3 % occupied by solvent molecules, which
would provide a potential micro-environment for catalysis.
It should be mentioned here that, the samples being heated
at 150 °C after a solvent exchange with methanol was the
standard for activation throughout the experiments, in order
immersed in some other solvents, like CHCl (Fig. 2). The
3
aforementioned test provides a fundamental understanding
of this heterogeneous catalyst.
On the other hand, most MOFs are more or less sensitive
to moisture, which could be one of the key limitations to
123

5
92
W. Zhang et al.
Fig. 1 a Mn-TCPP
TCPP = tetrakis(4-
(
carboxyphenyl)porphyrin) as a
bridging ligand; b Bridging bent
trinuclear iron cluster in MMPF
(
Fe atoms: purple, Mn atoms:
green, O atoms: red, C atoms:
gray); c The MMPF network
viewed along the
crystallographic a-axis; d The
MMPF network viewed along
the crystallographic c-axis
Ethanol
pH=12
Methanol
DMAc
pH=10
pH=7
CHCl3
Re-acꢀvated
DMF
Immersed in CHCl3
pH=4
o
Acꢀvated at 150 C
o
Simulated
Acꢀvated at 150 C
10
15
20
25
30
10
15
20
25
30
Degrees (2-theat)
Degrees (2-theat)
Fig. 2 PXRD patterns of the MMPF after immersion in different
solvents
Fig. 3 Powder X-ray diffraction (XRD) profiles for experimental
MMPF soaked in boiling water and aqueous solutions with pH values
ranging from 4 to 12 for 24 h
meet the requirements of applications. Thus, seldom were
MOFs reported to be chemically resistant in basic or acid
medium. Strikingly, MMPF also exhibited amazing
chemical stability and powder XRD results have suggested
that they remained stable not only in boiling water but also
in basic aqueous solutions with pH values in the range of
was also clear as shown in the Fig. S2, the MMPF has
already decomposed in acid solution and turned into the
metalloporphyrinic monomers. Hence, there was no obvi-
ous peak in XRD pattern (pH 4). Therefore, MMPFs
showed an unprecedented high robustness in 3D frame-
work in basic condition.
7
–12 (Fig. 3 and Fig. S2). In fact, although the solution
1
23

Efficient Catalyst Based on MMPF
593
3
.2 Catalytic Activity
cyclohexene
cyclooctene
1-hexene
8
6
4
0
0
0
Under present reaction condition, a range of alkenes were
selected to be oxidized in this catalytic system (Table 2,
entry 1–7). For substrates with different sizes, cyclohexene
with a smaller steric size triggered a higher conversion with
respect to cyclooctene as substrate (Table 2, entry 1–2).
This observation highlighted that MMPF offered channels
with accessible catalytic sites for the substrates, which
greatly facilitated their diffusion. It should be mentioned
that, increasing the length of linear alkenes triggered lower
epoxide yield (Table 2, entry 3–5). Additionally, the low
electron density of conjugated alkenes usually reduced
their nucleophilicity towards electrophilic oxygen of por-
1-octene
1
-dodecene
styrene
trans-sꢀlbene
20
0
0
100
200
300
400
500
Time (min)
V
Fig. 4 Kinetic traces of various substrates epoxidation catalyzed by
MMPF
phyrin-Mn = O. Therefore, the conversion of styrene and
trans-stilbene was very low, almost 50 % selectivity of
epoxide existed during the oxidation (Table 2, entry 6–7).
The kinetic profiles for the selective oxidation of sub-
strates were also represented in Fig. 4 to gain insight into
the catalytic behaviour. In fact, cyclohexene as substrate
gave rise to a faster reaction, relative to cyclooctene as
substrate. In addition, evident from Fig. 4, it was shown
that the conversion increased in the order of cyclohex-
ene [cyclooctene [1-hexene [styrene [trans-stilbene [
The excellent heterogeneous catalysts should not only
have high catalytic activity and selectivity, but should also
be structurally stable and thus be easily recovered for
continuous usage. Compound MMPF can be simply recy-
cled by filtration, which was subsequently reused in suc-
cessive runs. As expected, MMPF exhibited high catalytic
activity in which 93 % cyclooctene could be oxidized into
the cyclooctene epoxide product with 99 % selectivity after
1-octene [1-dodecene.
a
Table 2 Scope of MMPF-catalyzed epoxidation of alkenes
b
c
Entry
1
Substrate
Catalyst
MMPF
Conversion (%)
93
Selectivity (%)
[99
2
MMPF
100
[99
3
4
5
MMPF
MMPF
MMPF
65
4
[99
[99
–
–
6
MMPF
MMPF
40
31
54
50
7
a
Olefin (500 mM), PhIO (10 mM), catalyst (5 mM), acetonitrile (5.0 mL) sealed and bromobenzene 50 mg as internal standard in a Teflon-
lined screw cap vial were stirred at room temperature for 24 h
b
Conversion [%]
c
-1
Selectivity [%] were determined by GC using an SE-54 column (50 °C for 1 min, then 10 °C min up to 140 °C and 140 °C for 15 min)
based on the oxidant
123

5
94
W. Zhang et al.
a
1
00
Table 3 Selective oxidation of cyclohexene catalyzed by MMPF
b
c
8
6
4
2
0
0
0
0
0
Entry
Catalyst
MMPF
Conversion (%)
Selectivity (%)
1
2
3
4
5
6
7
a
100
–
[99
–
Conversion
Selecꢀvꢀy
MnCl2
FeCl2
38
17
40
4/52
4
10
Mn-TCPP
[99
12
Mn-TCPP ? FeCl
d
Filtrate1 /Filtrate2
2
1
2
e
3
0/99
0
4
Recycling
Blank
Fig. 5 Catalyst recycling in the epoxidation of cyclooctene with
MMPF as catalyst by PhIO
Cyclohexene (500 mM), PhIO (10 mM), catalyst (5 mM), aceto-
nitrile (5.0 mL) and bromobenzene 50 mg as internal standard sealed
in a Teflon-lined screw cap vial were stirred at room temperature for
2
4 h
b
2
4 h in the second run (shown in Fig. 5). After four cycles,
Conversion [%]
the recycled MMPF still exhibited a very high conversion
of 90 % and selectivity of [99 %, thus indicating that
MMPF was indeed a heterogeneous catalyst for cyclooc-
tene epoxidation at room temperature (Fig. 5). As expec-
ted, the initial reaction rate decreased upon reuse (Fig. 6).
According to the above results, it has been supposed that
the active catalytic sites should be the Mn-porphyrin
moieties within the pores in MMPF. To confirm the rela-
tionship between the structure and catalytic activity, we
compared the catalytic activities of MMPF with their
molecular components of MnCl , FeCl and Mn-TCPP,
c
Selectivity [%] were determined by GC using an SE-54 column
-
1
(50 °C for 1 min, then 10 °C min up to 140 °C and 140 °C for
1
5 min) based on the oxidant
d
MMPF catalyst was removed at 0 h and then reaction solution was
analysed after 24 h
e
The filtration time was 4 h
afford any additional oxidation product, which was basi-
cally as inactive as the blank (Table 3, entry 6–7). Another
filtration test in MMPF has also been performed at 4 h
2
2
(
Table 3, entry 6). Accordingly, the epoxidation was
and their mechanically combined mixtures under identical
reaction conditions. MnCl and FeCl showed very low
allowed to proceed for 4 h before being filtered to remove
any solid precipitate. Then, the supernatant was analysed
after 24 h. Finally, the catalytic performance of oxidation
increased slightly. This filtration test confirmed a truly
heterogeneous process. Overall, the MMPF displayed a
prior performance to Mn-TPP in epoxidation of cyclo-
hexene, thus highlighting the high efficiency of 3D net-
work-based nanochannel-reactor in MMPF via its
structural resistance to formation of catalytically inactive
species.
2
2
catalytic activity with conversions of 0 and 38 %, respec-
tively (Table 3, entry 2–3). Mn-TCPP and/or FeCl did
2
show quite moderate catalytic activity that could transform
4
0 % of the cyclohexene into the cyclohexene epoxide but
still were not as efficient as heterogeneous MMPF (100 %
conversion).The low activity observed for homogeneous
Mn-TCPP could be attributed to catalyst deactivation as a
result of the oxo-bridged dimer formation (Table 3, entry
4
). The supernatant from oxidation of cyclohexene after
filtration at the beginning through a regular filter did not
4
Conclusion
4
4
3
3
2
2
1
1
5
0
5
0
5
0
5
0
5
0
Conversion
In summary, we have explored a novel metalloporphyrinic
metal–organic framework, which endows MMPF with a
solvent-induced breathing behaviour and resistance to
basic solution. It has been demonstrated that MMPF was a
good candidate for activation of unsaturated bonds. Note-
worthy, MMPF exhibited high catalytic activity in which
cyclohexene could be almost fully oxidized into the
epoxide product with 99 % selectivity. On the other hand,
various other unsaturated olefins with different steric sizes
were investigated to confirm the catalytically active sites
being located into the nanochannel of MMPF. Therefore,
this work provided a promising platform to design func-
tional networks as catalysts in selective oxidation.
1h 2h 4h
1h 2h 4h
1h 2h 4h
1h 2h 4h
Recycling
Fig. 6 The initial reaction rate of catalyst recycling
1
23

Efficient Catalyst Based on MMPF
595
Acknowledgments Special thanks to Dr. Z.C. Zhang from Huaihai
Institute of Technology, China for his help on analysis of crystal
structure. This work was supported financially by the National
16. Garibay SJ, Weston MH, Mondloch JE, Colon YJ, Farha OK,
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(
(
‘Twelfth Five-Year’’ Plan for Science
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2012BAD32B03), the National Natural Science Foundation of China
20903048) and the Innovation Foundation in Jiangsu Province of
China (BY2013015-10).
(
2013) J Am Chem Soc 135:13934
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