Novel conjugated nanoporous alkynyl metalloporphyrin framework as effective catalyst for oxidation of toluene with molecular oxygen

Article abstract of DOI:10.1002/aoc.3578

A porous alkynylporphyrin conjugated organic polymer (MnE-TPP) was synthesized by Sonogashira coupling reaction with Mn(II) 5,10,15,20-tetrakis(4′-ethynylphenyl)porphyrin and Mn(II) 5,10,15,20-tetrakis(4′-bromophenyl)porphyrin as building blocks. The poly

Full text of DOI:10.1002/aoc.3578

Received: 8 April 2016
DOI 10.1002/aoc.3578
Revised: 30 June 2016
Accepted: 5 July 2016
F U L L PA P E R
Novel conjugated nanoporous alkynyl metalloporphyrin
framework as effective catalyst for oxidation of toluene with
molecular oxygen
*
Yongjin Li | Baoshuai Sun | Yuanrong Zhou | Weijun Yang
Department of Chemistry and Chemical
A porous alkynylporphyrin conjugated organic polymer (MnE‐TPP) was
synthesized by Sonogashira coupling reaction with Mn(II) 5,10,15,20‐tetrakis(4′‐
ethynylphenyl)porphyrin and Mn(II) 5,10,15,20‐tetrakis(4′‐bromophenyl)porphyrin
as building blocks. The polymer was characterized using nitrogen adsorption–
desorption isotherms, field‐emission scanning electron microscopy, high‐resolution
transmission electron microscopy, Fourier transform infrared and UV–visible
spectroscopies, X‐ray diffraction, thermogravimetry and inductively coupled plasma
atomic emission spectrometry. The electrochemical behaviors of MnE‐TPP were
investigated by cyclic voltammetry. MnE‐TPP was developed as a heterogeneous
catalyst for the activation of molecular oxygen to oxidize toluene under mild condi-
tions. The selectivity of total benzaldehyde and benzyl alcohol remained above
70.0% with a conversion of toluene up to 10.2%. The turnover number was as high
as 13 653. Also, MnE‐TPP remained structurally stable and the toluene conversion
rate hardly decreased after 5 h of reaction and five cycles of reuse.
Engineering, Hunan University, Changsha 410082,
Hunan, China
Correspondence
Weijun Yang, Department of Chemistry and
Chemical Engineering, Hunan University,
Changsha, 410082, Hunan, China.
Email: wjyang@hnu.edu.cn
KEYWORDS
alkynylporphyrin polymer, benzaldehyde, catalysis, oxidation, toluene
1
|
INTRODUCTION
well as the selectivity of benzaldehyde and benzyl alcohol,
many problems are still unsolved. For example, monomer
Benzaldehyde and benzyl alcohol are versatile intermediates
in the chemical industry, and the selective oxidation of
toluene with air is the most important way to synthesize them
industrially.[1,2] However, using this method it is easy to
generate benzoic acid because of over‐oxidation of benzalde-
hyde.[3] Therefore, it is of great significance to develop
highly selective catalysts for the oxidation of toluene into
benzaldehyde and benzyl alcohol.
By activating oxygen molecules under mild conditions,
cytochrome P450 enzyme functions as a highly active
catalyst for oxidation reactions. Metalloporphyrin, which
has a similar structure to the active center of cytochrome
P450 enzyme, has been employed as a biomimetic catalyst
for a variety of oxidation reactions.[4–8] The aerobic oxidation
of toluene has been catalyzed by metalloporphyrin to prepare
benzaldehyde and benzyl alcohol.[9–12] Although
metalloporphyrin increases the conversion rate of toluene as
metalloporphyrins can be separated with difficulty from
solvents at the end of reaction, and they are prone to oxidative
damage during the catalysis process and thus cannot be
recycled, which limits their application in practical produc-
tion. As a result, monomer metalloporphyrins have been
immobilized on solid supports to improve stability, but the
bond between porphyrin and solid support surface is not
stable. In addition, the activity of supported metalloporphyrin
declines soon with reuse.[13]
Metalloporphyrin polymerization is another way to
improve the stability of metalloporphyrins,[14–16] such as in
metalloporphyrin‐based metal–organic frameworks (MOFs).
In the structure of MOFs, metal ions at the para‐position of
the metalloporphyrin are bridge sites.[17,18] High density of
open metal sites within the highly ordered structure and
confined nanospace make metalloporphyrin‐based MOFs
useful in the design of materials for gas storage, chemical
Appl. Organometal. Chem. 2016; 1–7
wileyonlinelibrary.com/journal/aoc
Copyright © 2016 John Wiley & Sons, Ltd.
1

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LI ET AL.
separations, light response, sensors and other applica-
tions.[19–22] However, few catalytic metalloporphyrin‐based
MOFs have been reported, which suggests that this kind of
polymerization with metallic ion bridges may weaken the
catalytic activities of monomer metalloporphyrins.
acetate (47.5% Pd, J&K Chemicals), trimethylsilylacetylene
(98%, J&K Chemicals) and pyrrole (analytical grade,
redistilled before use). Other organic reagents were of analyt-
ical grade and purchased from Aladdin Reagents (Shanghai)
Co. Ltd without special treatment. [p‐Br]4PMn and [p‐ethy-
nyl]4PMn were synthesized by our group according to docu-
mented procedures (supporting information).
Recently, monomeric iron porphyrin has been bridged by
a conjugated phenyl group to form a new reusable conjugated
porous porphyrin polymer catalyst.[23,24] In the study
reported here, on the basis of the geometric properties of
porphyrin, Mn(II) 5,10,15,20‐tetrakis(4′‐ethynylphenyl)-
porphyrin ([p‐ethynyl]4PMn) and Mn(II) 5,10,15,20‐tetrakis
(4′‐bromophenyl)porphyrin ([p‐Br]4PMn) were used as
building blocks to synthesize a porous organic conjugated
porphyrin polymer (MnE‐TPP). Through the para‐position
coupling reaction, a super‐conjugated metalloporphyrin
polymer was synthesized with an alkynylphenyl conjugated
bridge and a highly ordered, well‐developed micro‐ and
mesoporous structure. Unlike metalloporphyrins, homoge-
neous catalysts, MnE‐TPP allowed heterogeneous catalysis
and circumvented recycling issues in oxidation. The catalytic
oxidation performance and recyclability of MnE‐TPP were
greatly improved. MnE‐TPP in which porphyrin monomers
are connected with stable covalent bonds was superior to
supported porphyrin or porphyrin polymer with metal ion
bridges. Hence, the polymer has the potential for reuse.
2.2 | Synthesis of MnE‐TPP
A mixture of [p‐ethynyl]4PMn (160 mg, 0.2 mmol), [p‐Br]
4PMn (245 mg, 0.24 mmol), triphenylphosphine (105 mg,
0.4 mmol), palladium acetate (22.45 mg, 0.1 mmol) and
copper iodide (38.09 mg, 0.2 mmol) was added into a
100 ml three‐necked flask and air was removed by three
cycles of argon gas pump–inflation. Air‐removed tetrahydro-
furan (THF; 9 ml) and triethylamine (TEA; 3 ml) were then
injected into the three‐necked flask under stirring and
refluxed at 76°C for 3 h. Finally, the mixture was poured into
plenty of deionized water after being cooled to room temper-
ature. The solid crude product was then collected by filtration,
and carefully washed in turn with water, THF, methanol and
trichloromethane. It was also washed by Soxhlet extraction
with water, THF, methanol and trichloromethane successively
for 24 h, and then dried in vacuum, affording a dark green
solid (MnE‐TPP) with a yield of 90% (Scheme 1).
2
| EXPERIMENTAL
2.3 | Catalyst characterization
The specific surface area and pore size distribution were
determined with a Beckman Coulter Inc. SA3100 accelerated
surface and porosity analyzer with nitrogen as probing gas at
77 K. The specific surface areas were calculated using the
2.1 | Materials
The following chemicals were used: bromobenzaldehyde
(99.77%, Aladdin Reagents (Shanghai) Co. Ltd), palladium
SCHEME 1 Synthesis of nanoporous polymer (MnE‐TPP) with [p‐ethynyl]4PMn and [p‐Br]4PMn

LI ET AL.
3
Brunauer–Emmett–Teller (BET) method, and the NLDFT
theory was utilized to estimate pore size, pore volume and
pore distribution. Field‐emission scanning electron
microcopy (FE‐SEM) images were recorded with a JEOL
model JSM‐5600Lv microscope. High‐resolution transmis-
sion electron microcopy (HR‐TEM) images were recorded
with a JEOL model JEM‐3010 microscope. Fourier transform
infrared (FT‐IR) spectra were obtained with a Shimadzu IR
Prestige‐21 spectrometer. UV–visible absorption spectra were
obtained with an Agilent Cary 100 UV–visible spectropho-
tometer and diffuse reflectance spectra were obtained using
the spectrophotometer equipped with integration sphere, and
samples were diluted with BaSO4. X‐ray diffraction (XRD)
examination was carried out using a Shimadzu 6100 instru-
ment with Cu Kα radiation operated at 40 kV and 30 mA.
with a strong adsorption at low pressure (P/P0 < 0.1)
(Figure1(a)), suggesting coexistence of micropores and
mesopores in the framework. The BET surface area is
determined to be as high as 380 m2 g−1, and the main pore
diameters are about 1.8 and 2.7 nm (Figure 1(b)). The
contributions of 1.8 and 2.7 nm width pores to the pore
volume are 38 and 62%, respectively, based on the cumula-
tive pore volume profile. Therefore, MnE‐TPP is an excellent
microporous and mesoporous polymer.
As shown in Figure 2, the FT‐IR spectrum of MnE‐TPP
is obviously different from that of [p‐ethynyl]4PMn. The
characteristic peak of ─C≡C─ at 2103 cm−1 attenuates and
even disappears because the structure of MnE‐TPP is highly
symmetric. The peak at 3292 cm−1 in the spectrum of
[p‐ethynyl]4PMn is assigned to C─H stretching, which disap-
pears after formation of MnE‐TPP due to the consumption of
C─H. Meanwhile, an intense, broad peak at 3436 cm−1
,
2.4 | Cyclic voltammetry measurements of MnE‐TPP
which typifies polyporphyrins, appears. On the other hand,
the FT‐IR spectrum of MnE‐TPP exhibits a characteristic
N─Mn vibration band at 1009 cm−1, which is close to that
Electrochemical measurements of cyclic voltammetry were
conducted using a CHI66OB electrochemical workstation
with a three‐electrode cell system, in which a glassy carbon
electrode, after loading the MnE‐TPP, was used as the work-
ing electrode, a calomel electrode as the reference electrode
and a Pt wire as the counter electrode. As to electrode prepa-
ration, the MnE‐TPP sample was dispersed in 0.5 ml of
solvent mixture containing 11 μl of Nafion (5 wt%) and
0.49 ml of ethanol by sonication for more than 1 h to obtain
a stable suspension. And then a 10 μl portion of the sample
solution was lightly dropped on the surface of the pre‐
polished gassy carbon electrode. The electrodes were dried
overnight at room temperature for measurement. The electro-
chemical experiments were conducted in 0.1 mol l−1
(CH3CH2)4NBr CH2Cl2 solution. The experiments were
cyclically scanned at a scan rate of 50 mV s−1 at room
temperature after purging with argon gas for 10 min.
2.5 | Catalytic oxidation of toluene
Toluene oxidation with air was catalyzed by MnE‐TPP.
Briefly, 200 ml of toluene and 10 mg of MnE‐TPP were
added into a 250 ml autoclave reactor, into which 0.6 MPa
argon gas was injected before the toluene was heated to
160°C. After the reaction mixture was heated to 160°C along
with stirring, air was injected at a speed of 1000 ml min−1
while the pressure was kept at 0.6 MPa. The mixture was
sampled every 30 min, and benzaldehyde and benzyl alcohol
in the samples were analyzed by GC using chlorobenzene as
internal standard. The contents of benzoic acid and ester were
measured by chemical titration.[25]
3
| RESULTS AND DISCUSSION
3.1 | MnE‐TPP characterization
Nitrogen sorption isotherm measurements of MnE‐TPP at
77 K display a typical type‐III sorption isotherm curve along
FIGURE 1 (a) Nitrogen adsorption and desorption isotherm profiles of
MnE‐TPP at 77 K. (b) Pore diameter examination of MnE‐TPP

4
LI ET AL.
FIGURE 2 FT‐IR spectra of (a) Mn‐TPP and (b) [p‐ethynyl]4PMn
of [p‐ethynyl]4PMn (1001 cm−1). The bands at 3035 and
1599 cm−1 correspond to the C─H and C═C stretches in
phenyls respectively, and that at 1493 cm−1 represents the
C═C stretch in porphyrin. Thus, [p‐ethynyl]4PMn had been
introduced into the MnE‐TPP porous structure in which
manganese ion was still stably coordinated.
FIGURE 4 UV–visible spectra of (a) MnE‐TPP (powder sample) and (b)
[p‐ethynyl]4PMn (CHCl3 solution)
[p‐ethynyl]4PMn monomer, the Soret band in MnE‐TPP
divides at 462 and 496 nm because of the electronic coupling
effects of alkynyl between the porphyrin moieties in
MnE‐TPP.
Electrochemical measurements of cyclic voltammetry
were also conducted. The first reduction potential of
MnE‐TPP is significantly right‐shifted in comparison with
the first reduction potential of [p‐ethynyl]4PMn (from
−0.14 V to 0.04 V; Figure 5), which indicates that porphyrin
monomers are bridged by the structure of ─C≡C─ in four
directions of porphyrin rings.
The morphology and crystallinity investigations of
MnE‐TPP were carried out using FE‐SEM and HR‐TEM.
The FE‐SEM images (Figures 3(a)–(c)) indicate that
MnE‐TPP comprises monoliths of about 1–2 μm originating
from overlapping of circular flakes that are about
150–250 nm in diameter and 1–2 nm in thickness. Such a
transition from a molecular‐level framework to nanoscale
layers and further to microscale monoliths resembles biolog-
ical catalytic systems. The HR‐TEM image (Figure 3(d))
shows that there are nanoholes on the surface of MnE‐TPP.
The UV–visible spectra of MnE‐TPP solid and of [p‐ethy-
nyl]4PMn in CHCl3 solution were also obtained (Figure 4). A
strong absorption band at 480 nm is the Soret band of [p‐ethy-
nyl]4PMn, and those at 580 and 620 nm are the Q‐bands.
MnE‐TPP also shows the same typical UV–visible spectrum
as that of [p‐ethynyl]4PMn, i.e. there are Soret bands at 462
and 496 nm and Q‐bands at 582 and 622 nm. Compared with
The ethyne coupling units in MnE‐TPP are
hyperconjugated with porphyrin rings, thus allowing wide‐
FIGURE 5 Cyclic voltammetry curves of MnE‐TPP on glassy carbon elec-
trodes in 0.1 mol l−1 CH2Cl2 solution of (CH3CH2)4NBr (red curve). Cyclic
voltammetry curves of [p‐ethynyl]4PMn in mol l−1 CH2Cl2 solution of
(CH3CH2)4NBr (black curve). Scan rate: 50 mV s−1
FIGURE 3 (a–c) FE‐SEM images and (d) HR‐TEM image of MnE‐TPP

LI ET AL.
5
range flow of electrons and delocalization.[26] The ethyne
unit transfers electrons between the porphyrin units and
thereby increases the energy‐transfer rate in the macromole-
cule of MnE‐TPP.[27] As a result, Mn2+ ions in the center
of porphyrin rings are further activated compared with those
in the corresponding metalloporphyrin.
The bridge of alkynylphenyl in four directions of porphy-
rin rings allows MnE‐TPP to be a highly ordered, highly
developed
microporous
and
mesoporous,
and
super‐conjugated metalloporphyrin polymer. Hence, the
catalytic oxidation activity of MnE‐TPP towards C─H bond
is significantly augmented. Furthermore, the XRD profile
confirms the amorphous character of MnE‐TPP (Figure S7).
Owing to the covalent attachment and crosslinked structure,
MnE‐TPP is stable, and insoluble in water, dichloromethane,
THF, acetone, methanol, dimethylsulfoxide and some other
organic solvents. The thermal properties of MnE‐TPP were
characterized using thermogravimetric analysis (Figure S8).
MnE‐TPP is stable under 400°C and loses 72.4% of weight
at 430°C, indicating that MnE‐TPP is highly thermally stable.
Accordingly, MnE‐TPP should have excellent catalytic oxi-
dation performance and favorable reusability.
3.2 | MnE‐TPP as catalyst for toluene oxidation
MnE‐TPP was then utilized as a new biomimetic catalyst for
the oxidation of toluene in heterogeneous systems
(Scheme 2). The catalytic oxidation results were compared
with those for porphyrin monomers (Table 1).
Under MnE‐TPP catalysis (Figure 6(a)), benzaldehyde,
benzyl alcohol and benzoic acid continuously increase during
250 min of reaction, and the total yields of benzaldehyde and
benzyl alcohol are higher than that of benzoic acid all the
time. Starting from 210 min, increases of benzaldehyde yield
slow down and the benzoic acid yield continues to grow.
What is more, the yield of benzyl alcohol begins to decrease
which means the deep oxidation of toluene, and the reaction
is not conducive for producing benzaldehyde and benzyl
SCHEME 2 Oxidation of toluene catalyzed by MnE‐TPP, [p‐ethynyl]4PMn
and [p‐Br]4PMn catalysts
TABLE 1 Comparison of toluene oxidation catalyzed by various porphyrin
catalystsa
Selectivity (mol%)
Turnover
Conversion
(mol%)
10.2
(mol mol−
1
Catalyst
MnE‐TPP
Aldehyde
Alcohol
27.8
Acid
16.7
)
42.2
13 653
[p‐ethynyl]
4PMn
46.9
28.6
9.0
7.4
9 905
FIGURE 6 Distribution curves of reaction products in toluene oxidation
catalyzed by (a) MnE‐TPP, (b) [p‐ethynyl]4PMn and (c) [p‐Br]4PMn. Tolu-
ene: 200 ml; catalyst: 10.0 mg; temperature: 160°C; pressure: 0.8 MPa; air-
flow: 1000 ml min−1; time: 300 min
[p‐Br]4PMn
25.2
19.0
44.2
12.0
30 270
aReaction conditions: toluene: 200 ml; catalyst: 10.0 mg; temperature: 160°C;
pressure: 0.8 MPa; airflow: 1000 ml min−1; time: 300 min.

6
LI ET AL.
alcohol. The total selectivity of benzaldehyde and benzyl
alcohol is 73.5% and the conversion of toluene is 9.7% at
210 min.
(380 m2 g−1). In the meantime, the catalyst remains highly
active under the optimized conditions. Particularly, the
conversion rate of toluene exceeds 9.0%, and the total
selectivity of benzaldehyde and benzyl alcohol remains
basically unchanged. Since industrial costs can be reduced
by continuing to increase the number of recycles, the catalyst
is potentially applicable in industry.
When [p‐ethynyl]4PMn is employed as catalyst (Figure 6
(b)), no benzoic acid is generated within 180 min. Even at
300 min, benzoic acid only accounts for 9.0% of the products,
and the total selectivity of benzaldehyde and benzyl alcohol
is as high as 75.5%, but the conversion rate of toluene is just
7.4%. The reaction was so slow that there was little benzalde-
hyde and benzyl alcohol generated before 30 min. Although
benzaldehyde increases rapidly and benzyl alcohol increases
slowly at later time, the total yields of benzaldehyde and
benzyl alcohol at 300 min (5.01%) are only similar to that
of MnE‐TPP as catalyst at 30 min (4.89%).
The total yields of benzaldehyde and benzyl alcohol,
when toluene oxidation was catalyzed by [p‐Br]4PMn,
increase rapidly to a plateau (5.24%) in about 30 min
(Figure 6(c)). With increasing time to 90 min, the yield of
benzoic acid exceeds those of benzaldehyde and benzyl
alcohol and keeps rising significantly thereafter. Although
the conversion rate of toluene is 12.0% at 300 min, the total
selectivity of benzaldehyde and benzyl alcohol is, however,
only 44.2%, which is much lower than that when MnE‐TPP
is used as catalyst (70%).
With MnE‐TPP (Table 1) as catalyst, the total selectivity
of benzaldehyde and benzyl alcohol is 70.0% at 10.2%
conversion of toluene, with a turnover number of about 13
653 mol at 160°C, 0.6 MPa and 1000 ml min−1 airflow rate.
Under the same conditions, the selectivity of total benzalde-
hyde and benzyl alcohol is 75.5% when [p‐ethynyl]4PMn is
used as the catalyst, but the conversion of toluene is only
7.4%. Although the conversion of toluene reaches 12.0% over
[p‐Br]4PMn, the total selectivity of benzaldehyde and benzyl
alcohol is only 44.2%. In comparison, Guo et al.[9] reported
that under catalysis of cobalt(II) tetraphenylporphyrin, the
highest conversion rate of toluene was only 8.9%, and the
maximum selectivity of total benzaldehyde and benzyl alco-
hol was just 60%. Hence, MnE‐TPP, which was synthesized
using [p‐ethynyl]4PMn and [p‐Br]4PMn, combines the
advantages of the two during toluene catalytic oxidation,
elevating the total selectivity of benzaldehyde and benzyl
alcohol, also the conversion rate of toluene.
4
| CONCLUSIONS
Single metal porphyrins are prone to loss of activity in
homogeneous catalytic oxidation due to gradual oxidization
and resulting in their single use. A metalloporphyrin
conjugated polymer with [p‐Br]4PMn and [p‐ethynyl]4PMn
as building blocks was synthesized in this work. With a
porous structure and large BET surface area, MnE‐TPP was
highly catalytically active in toluene oxidation and could be
reusable. Under MnE‐TPP catalysis, the total selectivity of
benzaldehyde and benzyl alcohol was 70.0% at 10.2%
conversion of toluene, with a turnover numbers of about 13
653 mol at 160°C, 0.6 MPa and 1000 ml min−1 airflow rate,
combining the advantages of the two during catalytic toluene
oxidation, elevating the conversion rate of toluene and the
total selectivity of benzaldehyde and benzyl alcohol. In addi-
tion, the porphyrin polymer had a recovery rate of over 90%,
thus meeting the requirements of modern green chemistry to
replace porphyrins for catalytic oxidation of hydrocarbons,
being potentially applicable to the industrial production of
benzaldehyde and benzyl alcohol.
ACKNOWLEDGMENTS
The financial support of the National Natural Science
Foundation of China (grant no. 21576074) is gratefully
acknowledged. We are also grateful for the financial support
of Hunan University.
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How to cite this article: Li, Y., Sun, B., Zhou, Y.,
and Yang, W. (2016), Novel conjugated nanoporous
alkynyl metalloporphyrin framework as effective cata-
lyst for oxidation of toluene with molecular oxygen,
Appl. Organometal. Chem., doi: 10.1002/aoc.3578
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