Journal of Molecular Catalysis A: Chemical 410 (2015) 193201

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Journal of Molecular Catalysis A: Chemical

journal homepage: www.elsevier.com/locate/molcata

A magnetically recyclable Fe3 O4 @C@TNCuPc composite catalyst for

chromogenic identication of phenolic pollutants
Suxiang Ge a , Dapeng Li a, , Shuiping Huang b , Weizhe Chen b , Guangliang Tu a ,
Shanwu Yu a , Qin He a , Jingjing Gong c , Yue Li a , Chuang Hong a ,
Changzeng Wu a , Zhi Zheng a,
a
Key Laboratory of Micro-Nano Materials for Energy Storage and Conversion of Henan Province, Institute of Surface Micro and Nano Materials, And School
of Chemistry and Chemical Engineering, Xuchang University, Henan 461000, PR China
b
Quality and Technique Supervision, Inspection and Testing Center of Xuchang City, Henan 461000, PR China
c
National Engineering Laboratory for Fiber Optic Sensing Technology, Wuhan University of Technology, Wuhan 430070, PR China

a r t i c l e

i n f o

Article history:
Received 29 July 2015
Received in revised form
24 September 2015
Accepted 27 September 2015
Available online 8 October 2015
Keywords:
Tetranitro copper phthalocyanine
tert-Butyl hydroperoxide
Chromogenic reaction
Composite catalyst

a b s t r a c t
Metal phthalocyanine (MPc) complexes can accelerate the catalytic oxidation of phenol and chlorophenol
pollutants and therefore attract great attention. Although many efforts have been made on improving the catalytic performance of MPc, most of them are difcult to be recycled and cause secondary
pollution. In this work, for the rst time we report a novel biomimetic phthalocyanine catalyst of
Fe3 O4 @Carbon@Tetranitro copper phthalocyanine (Fe3 O4 @C@TNCuPc) could catalyze the chromogenic
identication of phenol and chlorophenol compounds in the presence of 4-aminoantipyrine and BuOOH
without light irradiation or heating. Signicantly, the Fe3 O4 @C@TNCuPc catalyst could be magnetically
recycled and show high activity after four successive cycles of catalysis. On the basis of the electron paramagnetic resonance (EPR) test and active species trapping experiments, we propose that the oxidation
of substrates was mediated by TNPcCuIII O active species generated from the homolytic cleavage of the
O O bond in TNPcCuII OOBu.
2015 Elsevier B.V. All rights reserved.

1. Introduction
During the past years, biomimetic catalysts have received
increasing intention because they can mimic active sites of natural enzymes and reproduce their catalytic activity in a facile
manner [14]. Among them, metal phthalocyanine (MPc) complexes with advantages of excellent catalytic capability, low cost,
and availability at a large scale are important representatives.
In 1995, Meuniers group rstly reported that metal complex
of 2,9,16,23-tetrasulfophthalocyanine (FePcS and MnPcS) could
perform the bioinspired oxidation process similar to that of
cytochrome P-450 enzyme in chlorinated phenols degradation,
and the catalytic efciency was ultrahigh just with adding H2 O2
at room temperature [5,6]. Also, Zhaos group found that FePcS
could remarkably accelerate the degradation of several organic
pollutants in aqueous solution with H2 O2 as oxidant [7]. In contrast to the well-documented FePcS in catalytic chemistry for long
time, other nonferrous biomimetic phthalocyanine complexes has

Corresponding author. Fax: +86 3744369257.

Corresponding author.
E-mail addresses: lidapengabc@126.com (D. Li), zzheng@xcu.edu.cn (Z. Zheng).
http://dx.doi.org/10.1016/j.molcata.2015.09.022
1381-1169/ 2015 Elsevier B.V. All rights reserved.

not obtained intensive investigation. Until recent years, copper

and cobalt phthalocyanine complex-dependent bioinspired catalysis have been reported [8,9]. The covalently immobilized Cu(II)
phthalocyanine-tetrasulfonic acid tetrasodium (CuPcS) and cobalt
tetra(2,4-dichloro-1,3,5-triazine) aminophthalocyanine have been
utilized to oxidation of organic suldes and elimination of recalcitrant dyes, respectively. In fact, the MPc complexes exhibit
substrate-specic activity in biomimetic catalysis, and the catalytic
activity of MPc complexes was closely related to the centered metal
ion, oxidant, and the substituents on Pc ring [10,11]. Different oxidant could assist MPc complexes in forming different high-valent
metal-oxo phthalocyanine species, which are crucial entities for
oxidation reactions [6,10]. Besides, the substituents on Pc ring as
a cofactor could regulate the electron structure of MPc complexes
for improving their catalytic activity [10]. Therefore, it is thought
that exploring novel MPc-based catalyst with biomimetic features
is reasonable and feasible.
Phenol and chlorophenol compounds are important raw materials for producing various pharmaceuticals, chemical dyes, polymer,
and other valuable chemical products [1214]. The abuse of phenolic compounds has led to their widespread contamination in
our living environment. Therefore, the development of low cost,
easy-operation, and environment-friendly method to identify these

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Scheme 1. The synthesis route of TNCuPc via the solvothermal reaction.

phenolic pollutants is desirable. Since 1965, the 4-aminoantipyrine

(4-AAP) assisted chromogenic reaction driven by K3 Fe(CN)6 has
became a standard method [1520] for phenolic compounds detection [19,20]. Though the K3 Fe(CN)6 based chromogenic reaction is
fast and has high conversion efciency under mild conditions, the
necessary oxidant K3 Fe(CN)6 is toxic and unstable when exposed
to sunlight or mixed with acid/alkali substance. Fortunately, MPc
complexes as biomimetic catalysts has shown promising potential for chromogenic reaction. In 2007, Santhanalakshmi reported
that soluble metal tetrasulfophthalocyanine (metal, such as Mn,
Fe) complexes could catalyze the oxidation of phenol to pink dyes
in the presence of 4-AAP and H2 O2 , this is the rst literature
on the MPc-catalyzed chromogenic identication of phenol [21].
Later, our group presented that the chormogenic identication of
phenol and chlorophenol could be accelerated in TNFe(II) Pc O2
heterogeneous catalytic system [22], MnPc O2 heterogeneous
photocatalytic system [23], Fe(III)OCPc BuOOH homogeneous system [24], and water-soluble FePc BuOOH homogeneous system
[25]. Although the chromogenic reactions catalyzed by abovementioned MPc have been proved to be successful, the used soluble
MPc complexes or tiny MPc particles were difcult to be recycled, which could lead to the secondary pollution. Therefore, the
development of recoverable MPc catalysts is desirable.
Recently, the investigations on preparation and photocatalytic
performance of TNCuPc have been reported [2628], however,
its biomimetic catalysis property has not been found yet. In this
paper, for the rst time we fabricated Fe3 O4 @C@TNCuPc catalyst by using a successive solvothermal method and presented
its oxygenase-like catalytic activity in chromogenic identication
of phenols/chrolophenols assisted with 4-aminoantipyrine and
BuOOH (the chemical structure of TNCuPc is shown in Scheme 1).
Signicantly, the Fe3 O4 @C@TNCuPc catalysts could be easily separated and reused after a simple post-treatment process, and the
catalytic activity only decline a little even after four cycles. Moreover, a possible mechanism was proposed to explain the intrinsic
roles of Fe3 O4 @C@TNCuPc, BuOOH, and 4-aminoantipyrine in chromogenic identication.
2. Experimental

Fig. 1. XRD patterns of (a) TNCuPc, (b) Fe3 O4 , (c) Fe3 O4 @C and (d) Fe3 O4 @C@TNCuPc.

used as the spin-trapping reagent for probable radicals in electron spin-resonance spectroscopy (ESR) experiment and purchased
from Sigma Chemical Co. Deionized water was used in all the experiments.
2.2. Characterization
Powder X-ray diffraction (XRD) patterns were recorded on
a Bruker D8 Advance X-ray powder diffractometer with CuKa
radiation. Scanning electron microscopy (SEM) and Transmission
electron microscopy (TEM) were performed by an S-4800 Field
Emission SEM (FESEM, Hitachi, Japan) and JEM-2010 microscope.
Nitrogen adsorptiondesorption isotherms were collected on a
Micromeritics ASAP 2020 gas adsorption apparatus (USA) after the
sample had been degassed in the ow of N2 at 150 C. Fourier
Transform-Infrared (FT-IR) spectra were recorded on a Thermo
Nicolet Nexus FT-IR spectrometer with the standard KBr pellet
method. The magnetization curve of the magnetic samples was
characterized with a MPMS-XL-7 magnetometer (Quantum Design,
USA) at room temperature. X-ray photoelectron spectroscopy (XPS)
was performed on a Thermo ESCALAB 250XI instrument with Al
K (h = 1486.6 eV) source. UVvis spectra of catalytic reactions
were recorded on a Cary 500 UVvis-NIR Spectrophotometer. The
catalytic reaction of 2-chlorophenol was monitored by high performance liquid chromatography (HPLC, Agilent-1200 instrument)
equipped with a C18 reverse phase column (250 mm 4.6 mm).
The mobile phase consisted of acetonitrilemethanolwater mixture (32%:8%:60%, v/v) with a ow rate of 1.0 mL/min. The column
temperature was set at 25 C. The ESR experiment was conducted at
room temperature on an ER200-SRC instrument (Bruker) to determine the generated active species in the catalytic system composed
of Fe3 O4 @C@TNCuPc and BuOOH. The detailed parameters for ESR
measurement were set as following: center eld, 3233 G; sweep
width, 50 G; sweep time, 1.0 min; modulation frequency, 100 kHz;
microwave frequency, 9055.2 MHz; power, 0.998 mW.

2.1. Chemicals
2.3. Synthesis of Fe3 O4 microsphere
Ferric chloride hexahydrate (FeCl3 6H2 O), sodium dodecylbenzenesulphonate (SDBS), sodium acetate (NaAc), ethylene glycol,
glucose, copper (II) acetate dehydrate (Cu(Ac)2 2H2 O), ammonium molybdate tetrahydrate were AR grade and purchased from
Shanghai Chemical Reagent Co., China. 4-nitrophthalonitrile (>99
%) was purchased form Shanghai D&B Chemicals Technology
Co., Ltd. Phenol, 2-chlorophenol (2-CP), 4-chlorophenol (4-CP),
2,4-dichlorophenol (DCP), and 4-aminoantipyrine were used in
chromogenic reaction and purchased from Sinopharm Chemical
Reagent Co., Ltd. 5,5-dimethyl-1-pyrroline-N-oxide (DMPO) was

The synthesis of Fe3 O4 microsphere was referred to the reported

methods [2931], but with some modications. FeCl3 6H2 O (1.35 g)
and SDBS (0.40 g) were dissolved in ethylene glycol (75 mL) with
magnetic stirring to form a clear solution. Then, NaAc (4.10 g) was
added into above solution and the mixture was transferred into a
Telfon-lined stainless-steel autoclave (100 mL capacity). The autoclave was placed in a programmed oven at 190 C for 8 h. After
the natural cooling to room temperature, the black products were
washed for ve times with ethanol and dried at 60 C overnight.

S. Ge et al. / Journal of Molecular Catalysis A: Chemical 410 (2015) 193201

195

Fig. 2. (a) Large-eld view of SEM morphologies of Fe3 O4 microspheres; (b) and (c) SEM images of Fe3 O4 microspheres at higher magnication; (d) and (e) SEM images of
Fe3 O4 @C microspheres at low and high magnication, respectively; (f) and (g) SEM images of Fe3 O4 @C@TNCuPc microspheres at low and high magnication, respectively;
(h) TEM image of Fe3 O4 @C@TNCuPc microspheres; (i) HRTEM of Fe3 O4 @C@TNCuPc recorded from parts of catalyst in (h).

2.4. Synthesis of Fe3 O4 @C

The coating of carbon onto the as-synthesized Fe3 O4 microspheres to Fe3 O4 @C was according to a reported literature [32].
The as-prepared Fe3 O4 microspheres (30 mg) and glucose powder (100 mg) were put into a Telfon-lined stainless-steel autoclave
(28 mL capacity) containing 20 mL of deionized water. After vigorous stirring for 10 min, the mixture turned into a suspension, sealed
and hydrothermally treated at 180 C for 4 h. After natural cooling
to room temperature, the suspension was separated by centrifugation and washed with water several times and dried in oven at
100 C for 2 h.

(1.0 103 mol/L) and 5 mL of phenolic aqueous solution (phenol

or chlorophenol, 1.0 103 mol/L) were added into a 50 mL glass
beaker. Then a 15 mg of Fe3 O4 @C@TNCuPc powder was dispersed
into the above solution assisted with the ultrasonic treatment for
15 s. The catalytic reaction (chromogenic reaction) was initiated by
addition of 15 L of t-BuOOH aqueous solution. At regular intervals,
catalysts were separated using a magnet and about 3 mL of reaction solution was collected for UVvis absorbance measurement.
All the reactions were performed at room temperature (20 C) and
a glass rod was used to stir the reaction solution during the catalytic
process.
2.7. The recycling experiment

2.5. Synthesis of Fe3 O4 @C@TNCuPc

The synthesis procedure of Fe3 O4 @C@TNCuPc was presented as
following. Fe3 O4 @C powder (100 mg), 4-nitrophthalonitrile (0.200
mmol), Cu(Ac)2 2H2 O (0.05 mmol) and ammonium molybdate
(5 mg) were put into a 28 mL Telfon-lined stainless-steel autoclave. The absolute ethanol was used as medium and added into
the autoclave up to 75% of the total volume. Next, the autoclave
was heated and maintained at 160 C for 10 h. The obtained samples were washed with deionized water assisted with ultrasound
treatment and dried at 100 C for 2 h.
2.6. Typical chromogenic reaction of phenolic compounds
catalyzed by Fe3 O4 @C@TNCuPc
The typical chromogenic reaction of four phenolic compounds
with 4-APP in the presence of Fe3 O4 @C@TNCuPc and t-BuOOH
was performed under the following experimental procedure. A
35 mL of deionized water, 10 mL of 4-AAP aqueous solution

The recycling experiment of Fe3 O4 @C@TNCuPc catalysis reaction was carried out under the typical conditions. After the
chromogenic reactions, the catalysts were recycled with a magnet
and washed with deionized water until the pink color was disappeared. Then the resulting catalysts were dispersed into boiled
water for 30 min to undergo desorption from the residual reactants
and products. Finally, the catalysts were dried at 100 C in vacuum
for next recycling chromogenic experiments.
3. Results and discussion
3.1. Preparation and characterization of Fe3 O4 @C@TNCuPc
XRD method is used to investigate the phase structures of the
as-prepared materials. As shown in Fig. 1, the XRD patterns of pure
TNCuPc, Fe3 O4 , Fe3 O4 @C, and Fe3 O4 @C@TNCuPc are recorded in
traces from a to d, respectively. Thereinto, the characteristic peaks
in trace (b) can be well indexed to the orthorhombic Fe3 O4 with lat-

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tice parameters of a = 8.394 (JCPDS card le, 75-1610, Fd-3m: (No.

227)). From detailed observations, we nd that the XRD patterns of
trace c and d show no obvious difference with trace b, which indicated that the phase structures of Fe3 O4 core were well maintained
after the treatments of coating and loading. Therefore, two deductions can be obtained. (i) The amorphous carbon could probably be
formed on surface of Fe3 O4 cores after the carbonization of glucose
in solvothermal process, and the shell of carbon should not be too
thick. (ii) The loaded TNCuPc on surfaces of Fe3 O4 @C was very small
according to the comparison of trace a and d. To verify the reasonableness of above estimation, SEM, TEM, and HRTEM analysis were
performed on the as-prepared series samples.
Fig. 2 shows SEM, TEM, and HRTEM images of the various samples synthesized on the basis of magnetic Fe3 O4 core. In Fig. 2a, it
is clear that the as-prepared Fe3 O4 cores exhibit the spherical morphologies and the diameter distribution of these microspheres is
very narrow. From detailed observations of Fig. 2b and c, we nd
that the representative Fe3 O4 microspheres have a mean diameter
of about 800 nm and relatively smooth surfaces, which indicate that
Fe3 O4 microspheres undergo homogeneous growth. After coating
with carbon layer on Fe3 O4 microspheres, there is no signicant
variation on the average diameter (Fig. 2b versus Fig. 2d), but
the overall surface of Fe3 O4 @C microspheres become much rough
and a large number of nanoparticles exposed on them (Fig. 2e),
which indicates a thin layer of carbon deposited homogeneously
on Fe3 O4 microsphere surfaces. These rough surfaces are thought
to be benecial for providing available sites for further deposition of TNCuPc. Fig. 2f and g present the SEM morphologies of
nal Fe3 O4 @C@TNCuPc composite with different magnications.
Compared Fig. 2d with Fig. 2f, it seems that the average diameter of Fe3 O4 @C@TNCuPc dose not substantially increase any more,
but small amounts of island-like structures can be found on the
surfaces of Fe3 O4 @C microspheres. Therefore, it can be conrmed
that the TNCuPc deposits uniformly through the heterogeneous
growth process (Fig. 2g). To get more detailed structure information of Fe3 O4 @C@TNCuPc, TEM and HRTEM analysis is performed.

Fig. 3. FT-IR spectra of (a) TNCuPc, (b) Fe3 O4 , (c) Fe3 O4 @C and (d) Fe3 O4 @C@TNCuPc.

As shown in Fig. 2h, the composite catalysts show the island-onmicrosphere morphologies with low magnication, and the poor
crystallinity of TNCuPc on Fe3 O4 @C surface can be clearly determined in Fig. 2i. Thus, our estimation of small amount of TNCuPc on
Fe3 O4 @C surface is reasonable. In addition, the estimation is also in
agreement with the comparison results according to TG measurement of these Fe3 O4 -based samples. (see Fig. S1 of Supplementary
information)
To further testify the existence of TNCuPc complexes in
Fe3 O4 @C@TNCuPc, various spectral techniques are performed.
Fig. 3 records the FT-IR spectra of pure TNCuPc, Fe3 O4 cores,
Fe3 O4 @C, and Fe3 O4 @C@TNCuPc in curve a-d, respectively. The
FT-IR spectrum of Fe3 O4 cores exhibits a broad absorption peak
centered at 607 cm1 , which can be assigned to the Fe O stretching mode of the tetrahedral and octahedral sites [33]. Besides, the
peaks at 1640 cm1 , 1088 cm1 and 1048 cm1 can be assigned
to vibration of acetas, O H bending and C O stretching of ethylene glycol. Interestingly, the FT-IR spectrum of Fe3 O4 @C is very
similar to that of Fe3 O4 cores (curve b versus curve c), which also

Fig. 4. (a) XPS fully scanned spectra of Fe3 O4 @C@TNCuPc; (b) region XPS spectra of Cu; (c) region XPS spectra of Fe; (d) region XPS spectra of N.

S. Ge et al. / Journal of Molecular Catalysis A: Chemical 410 (2015) 193201

197

Fig. 5. Stacked UVvis absorbance spectra of (a) 2-CP system, (b) DCP system, (c) 4-CP system and (d) phenol system.

testies the thin layer of carbon deposited on Fe3 O4 microsphere

surface. It is noted that there are almost no strong absorption
peaks belonged to TNCuPc in the FT-IR spectra of Fe3 O4 @C@TNCuPc
(curve a versus curve d), for example, 1334 and 1525 cm1 , which
are the characterized and strongest peaks of NO2 group on Pc ring
[26], become the very weak peaks of composite catalyst. Besides,
several characterized absorption peaks of Pc skeletal and metalligand vibrations at 1613, 1143, 1086, 760, and 730 cm1 [27], can
be found still as the weak peaks. (Herein, the detailed FT-IR peaks
from TNCuPc can be assigned as following: 1613 cm1 (C C stretching vibration in pyrrole), 1525 cm1 (asymmetric N O stretching),
1334 cm1 (symmetric N O stretching), 1143 cm1 (C N in plane
band vibration), 1086 cm1 (C H bending in plane deformations),
847 cm1 (C NO2 stretching), 760 cm1 (C N stretching vibration), 730 cm1 (C H bending out of plane deformations))
Moreover, the chemical composition of Fe3 O4 @C@TNCuPc is
further studied by XPS analysis. As shown in Fig. 4a, the fully
scanned spectrum demonstrates that Fe, O, C, N and Cu elements
can be found in Fe3 O4 @C@TNCuPc catalyst. The high-resolution
XPS spectrum (Fig. 4b), in which the peak located at 933.2 eV
and another one located at 953.0 eV can be assigned to Cu
2p3/2 and Cu 2p1/2, respectively [26]. These two characteristic
peaks conrm convincingly the Cu element exists in as-prepared
Fe3 O4 @C@TNCuPc catalyst. Also, the two peaks at 710.8 and
724.0 eV correspond to Fe 2p3/2 and Fe 2p1/2 in Fe3 O4 cores,
respectively (Fig. 4c). Besides, it is noted that no obvious shakeup
satellite peaks at the higher binding energy side (about 718.8

and 729.5 eV) can be found, which is the characteristic of Fe3 O4

[33,34]. For high-resolution XPS spectrum of N 1s (Fig. 4d), which
is the combination derived from various electronic structures in
Pc ring and NO2 groups, was resolved using the XPS peak tting
program (version 4.1). Particularly, the lower binding energy component at 398.7 eV is attributed to the pyridyl N, the peak located
at 399.0 eV resulted from pyridyl N associated with metal Cu, and
the peaks at 400.2 and 405.4 eV were assigned to pyrrolic N and
NO2 , respectively [3537]. In brief, the above results indicate that
TNCuPc complexes have been successfully coated on the surface of
Fe3O4@C.
3.2. Catalytic oxidation of several phenolic pollutants
To evaluate the catalytic performance of Fe3 O4 @C@TNCuPc,
phenols and chlorophenols were selected as substrates in chromognic experiments. Additionally, BuOOH was used as the oxidant
for constituting catalytic oxidation system with Fe3 O4 @C@TNCuPc.
Fig. 5 demonstrate that four kinds of phenolic compounds (2CP, DCP, 4-CP and phenol) can be oxidized and transformed
into quinone-imine dyes assisted with 4-AAP in the presence of
Fe3 O4 @C@TNCuPc and BuOOH. The gradually increased absorption
peaks at 510 nm mean the continual generation of dye products [2125]. To illuminate the kinetic of dye formation, the
pseudo-rst-order model was introduced. The reaction rate constants for 2-CP, DCP, 4-CP, and phenol system were calculated as
6.709 102 , 9.188 102 , 1.803 101 , and 9.063 101 min2 ,

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S. Ge et al. / Journal of Molecular Catalysis A: Chemical 410 (2015) 193201

Fig. 7. Comparison of dye formation process under different conditions.

(abs = 510 nm).

Fig. 6. (a) HPLC chromatogram of 2-CP system detected after regular intervals of catalytic reaction. (b) Percentage of 2-CP, 4-AAP and dye according to their respective
peak areas in HPLC chromatogram.

respectively. Interestingly, we found that the initial and middle

stage of chromogenic reaction was found to follow the pseudo-rstorder kinetics model (see Fig. S3 of Supplementary information),
while the reaction behavior at later stage deviated from this model.
For example, for 2-CP and DCP system, the reaction within 60 min
followed the kinetic equation. For 4-CP and Phenol system, after
reacted for 30 min the reaction become deviating from this model.
Therefore, the concentration of substrates is a factor determining
the chromogenic reaction rate.
To demonstrate chromogenic reaction kinetics and ascertain
the possible intermediates, HPLC analysis was performed. Fig. 6a
records the temporal HPLC spectra proles during the chromogenic
reaction of 2-CP in the presence of Fe3 O4 @C@TNCuPc and BuOOH.
The chromatogram peaks of 2-CP, 4-AAP, and BuOOH could be
determined by comparison of their retention time with respective
standards, and the peak of dyes in proles could be identied by
tuning the wavelength of UVvis detector to 510 nm for only one
chromatogram peak observed. Obviously, after 15 min of reaction
time, the peak of 2-CP, and 4-AAP gradually declined, while a new
peak of dyes could be found since 5 min of catalytic reaction. After
reaction interval of 90 min, the peak of 2-CP almost disappeared
and the 4-AAP maintained about 36 % of its initial concentration,
accompanied by the further increase of dyes. Signicantly, none of
intermediates were observed under current conditions. (The existence of two weak peaks at 6.59 and 7.27 min in HPLC proles
resulted from reagent raws, and the peaks with their retention
time before 4 min could be attributed to deionized water solvent.)
The time-dependent curves of contents of substrates and dyes in
chromogenic reaction were described in Fig. 6b according to their
respective area of HPLC peaks. Since the high conversion efciency
of 2-CP to the corresponding dyes, the catalytic oxidation system

consisting of Fe3 O4 @C@TNCuPc and BuOOH shows the potential in

the application of phenol pollutant assay.
Since the composite catalyst of Fe3 O4 @C@TNCuPc consisted
of three kinds of component, it is necessary to illustrate their
respective roles in catalytic reaction. For this purpose, the control experiments were designed and performed. Fig. 7 shows the
comparison of chromogenic reaction process in 2-CP system under
different experimental conditions. First, it is interesting that the
catalytic process of dyes with pure TNCuPc catalysts (15 mg) is
almost similar to that in the presence of Fe3 O4 @C@TNCuPc (15 mg),
which implied that the composite catalysts show the satised activity under current synthesis conditions (curve a versus curve b).
From the detailed comparison, it is clear that the dyes were difcult to be produced without either Fe3 O4 @C@TNCuPc or BuOOH
(curve c and curve d). This is because that some organic hydroperoxides are not able to oxidize organic compounds by themselves,
therefore, the introduction of catalysts for active oxygen transfer
is necessary in the oxidation system [38]. Obviously, none of dyes
could be obtained just with Fe3 O4 microspheres (curve f). When
BuOOH was added in Fe3 O4 system, only less dye could be formed
(curve e). Signicantly, we found that the formation of dyes was
inhibited obviously in the presence of Fe3 O4 @C and BuOOH (curve
e versus curve g), indicating the structure of carbon layer can inhibit
the Fe3 O4 catalysis. After loading TNCuPc on Fe3 O4 @C, the production of dyes was largely enhanced (curve b versus curve g). Thus,
the conclusion could be drawn that the TNCuPc nanostructures
were the real catalytic entities in the hierarchical aggregates of
Fe3 O4 @C@TNCuPc, which greatly contributed to the chromogenic
reaction. Besides, the carbon layer in Fe3 O4 @C@TNCuPc could not
only protect the Fe3 O4 core from acid-base corrosion and Fenton
reaction between Fe3 O4 and BuOOH but also support the TNCuPc
catalyst.
3.3. Proposed mechanism for catalytic system of
Fe3 O4 @C@TNCuPcBuOOH
For general mechanism of bioinspired oxidation catalyzed by
MPc, the well-known theory of active metal-oxygen species had
been proposed by Meunier and Sorokin based on their pioneering
studies on several chemical systems of FePcS/H2 O2 , FePcS/BuOOH,
FePcS-SiO2 /BuOOH, and so on. Thereinto, the homolytic/heterolytic
cleavage of the iron-oxygen bond is the key step that determines
which of the active species of PcSFeIV O and PcSFeV O could be
generated and the practical pathway of catalytic oxidation [6].

S. Ge et al. / Journal of Molecular Catalysis A: Chemical 410 (2015) 193201

Fig.
8. DMPO
spin-trapping
ESR
spectra
obtained
Fe3 O4 @C@TNCuPc BuOOH system at different incubation time.

from

the

Besides, some important intermediates, such as oxygen-centered

radicals in homolytic process and oxygen negative ions in heterolytic process would inevitably be formed as corresponding
paralleled products [6].
To ascertain the catalytic pathway and important active species
in Fe3 O4 @C@TNCuPcBuOOH system, ESR technique was appropriate to detect radical intermediates for our system. Fig. 8 shows the
temporal DMPO spin-trapping ESR spectra in aqueous solution con-

199

taining Fe3 O4 @C@TNCuPc (0.30 mg/mL) and BuOOH (0.30 L/mL).

Interestingly, we found that the resulting ESR spectra from 1 to
6 min were very similar to that of DMPO/ OH adduct. While, the
control experiments have proved that oxidation of substrates was
not mediated by OH radicals for the chromogenic process before
and after adding iso-propanol do not show the distinct difference
(results not shown). Moreover, many research groups had proposed
that the ESR spectra of organic hydroperoxide was complicated
and could be assigned to the DMPO adducts with peroxyl, alkoxyl
and alkyl radicals [39]. The similarity of ESR spectra to that of
known DMPO/radical adducts could not be utilized as the only
criteria. Despite the pure ESR spectra of DMPO/ OC(CH3 )3 adduct
is difcult to obtain, the current results indicated that homolytic
cleavage other than heterolytic cleavage of copper-oxygen bond
took place, and TNPcCuIII O cooperating with BuO radicals are
initial intermediates (Scheme 2, step I). Subsequently, the resulting TNPcCuIII O could coordinate with (chloro) phenol and 4-AAP
along with the axis of Pc ring (Scheme 2, step II). In this step, the
electron from hydroxyl on phenol or amino on 4-AAP was drawn to
CuIII ion and facilitated to the formation of low active TNPcCuII O
or TNPcCuII OH species, and the corresponding radical products
formed (p-quinoid for (chloro) phenol and antipyrine-NH for 4AAP). These active radicals would undergo the oxidative coupling
reaction and resulted in the formation of dyes (Scheme 2, step III).
For recycling catalysis of Fe3 O4 @C@TNCuPc, the BuOO ion dissociated from the secondary added BuOOH could be exchanged with O
in TNPcCuII O species to generate high active TNPcCuIII O species
again for the next cycle of catalytic oxidation (Scheme 2, step IV).

Scheme 2. Proposed mechanisms of the generation of copper-oxygen active species and the formation process of dye products.

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S. Ge et al. / Journal of Molecular Catalysis A: Chemical 410 (2015) 193201

Fig. 9. The magnetization curves of Fe3 O4 , Fe3 O4 @C@ and Fe3 O4 @C@TNCuPc measured at room temperature.

3.4. Recycling experiments of Fe3 O4 @C@TNCuPc catalyst

The magnetic performance of these Fe3 O4 -based products was
investigated by a vibrating sample magnetometer. Fig. 9 shows the
magnetization curves of Fe3 O4 , Fe3 O4 @C and Fe3 O4 @C@TNCuPc
samples with magnetic saturation (Ms) values measured at 66.3,
66.2, and 65.6 emug1 , respectively. The insignicant decrease of

Fig. 10. Recycling of Fe3 O4 @C@TNCuPc catalysts employed in 2-CP system.

Ms for these products indicates that high content of Fe3 O4 occupied

in unit weight samples of Fe3 O4 @C and Fe3 O4 @C@TNCuPc. Moreover, the low value of remanent magnetization (Mr) and coercivity
(Hc) demonstrate that these products exhibit superparamagnetic
properties at room temperature.n applied magnetic eld. Fig. 10
Herein, Mr indicates the residual magnetization of magnetic materials when the applied magnetic eld intensity is zero and Hc refers
to the eld required to bring the magnetization to zero [40]. There-

Fig. 11. The comparison of chromogenic reaction process in (a) 2-CP system, (b) DCP system, (c) 4-CP system and (d) phenol system. The dosage of Fe3 O4 @C@TNCuPc, TNCuPc
and TNFe(II) Pc is 15 mg, and the volume of BuOOH is 15 L. The Abs refers to the absorbance of 510 nm. ( Fe3 O4 @C@TNCuPc;  TNCuPc + BuOOH;  TNFe(II) Pc + O2 ).

S. Ge et al. / Journal of Molecular Catalysis A: Chemical 410 (2015) 193201

fore, the as prepared Fe3 O4 @C@TNCuPc could be easily separated

from reaction solution by a magnet or a shows the chromogenic
efciency of recycled Fe3 O4 @C@TNCuPc under the typical catalytic
conditions. It is obvious that the catalytic activity only decline a
little after four cycles. Though the insignicant decrease of TNCuPc
from surface of composite catalysts was found via SEM and Raman
measurement (see Figs. S3 and S4), the Fe3 O4 @C@TNCuPc still
show the good stability after four cycles. The slight decrease of
the catalytic activity could be attributed to the adsorption of some
species on catalyst surface, which should block its combination
with BuOOH in some extent.
Finally, the chromogenic reaction processes were compared
in three catalytic oxidation systems of Fe3 O4 @C@TNCuPc and
BuOOH; TNCuPc and BuOOH; TNFe(II) Pc and O2 (Fig. 11). It is
obvious that the Fe3 O4 @C@TNCuPc shows the best catalytic performance for its high adsorption capacity (the adsorption-desorption
isotherm curves of Fe3 O4 @C@TNCuPc is recorded in Fig. S5).
Although the initial chromogenic reaction rate (less than 20 min)
in Fe3 O4 @C@TNCuPc system is a little slower than that of TNCuPc
system, its ultimate dyes production is obvious higher, indicating
the active sites on the surface of Fe3 O4 @C@TNCuPc are well dispersed and more adequate than that of pure TNCuPc. Moreover,
Fe3 O4 @C@TNCuPc catalysts can be easily magnetically recycled,
benecial for its application in detecting phenol/chlorophenol pollutants.
4. Conclusions
In summary, we for the rst time demonstrate a novel magnetically recoverable biomimetic catalyst of Fe3 O4 @C@TNCuPc
exhibited satised catalytic performance in chromogenic identication of several phenolic pollutants assisted with 4-AAP. All the
chromogenic reactions could be carried out in a facile manner
at room temperature without light irradiation or heating. Importantly, the Fe3 O4 @C@TNCuPc catalysts could be easily recycled
and exhibited stable catalytic activity even after four successive
cycles. On the basis of the electron paramagnetic resonance (EPR)
test and active species trapping experiments, we proposed that
TNPcCuIII O formed via the homolytic cleavage of the O O bond
in TNPcCuII OOBu is the main active species in oxidization reaction. This found would open a new frontier for preparing recyclable
biomimetic catalysts for chromogenic identication of phenolic
pollutants.
Acknowledgement
This work was nancially supported by the National Natural
Science Foundation of China (Grant No. 51302241, 21507107).
Appendix A. Supplementary data
Supplementary data associated with this article can be found, in
the online version, at http://dx.doi.org/10.1016/j.molcata.2015.09.
022.

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