Beruflich Dokumente
Kultur Dokumente
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
194
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
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).
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-
196
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.
197
Fig. 5. Stacked UVvis absorbance spectra of (a) 2-CP system, (b) DCP system, (c) 4-CP system and (d) phenol system.
198
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.
Fig.
8. DMPO
spin-trapping
ESR
spectra
obtained
Fe3 O4 @C@TNCuPc BuOOH system at different incubation time.
from
the
199
Scheme 2. Proposed mechanisms of the generation of copper-oxygen active species and the formation process of dye products.
200
Fig. 9. The magnetization curves of Fe3 O4 , Fe3 O4 @C@ and Fe3 O4 @C@TNCuPc measured at room temperature.
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 ).
201
References
[1] K. Ariga, K. Kawakami, M. Ebara, Y. Kotsuchibashi, Q.M. Ji, J.P. Hill, New J.
Chem. 38 (2014) 51495163.
[2] T.R. Simmons, G. Berggren, M. Bacchi, M. Fontecave, V. Artero, Coord. Chem.
Rev. 270271 (2014) 127150.
[3] K. Ariga, Q.M. Ji, T. Mori, M. Naito, Y. Yamauchi, H. Abe, J.P. Hill, Chem. Soc.
Rev. 42 (2013) 63226345.
[4] J.P. Layeld, S. Hammes-Schiffer, Chem. Rev. 114 (2014) 34663494.
[5] A. Sorokin, J.L. Sris, B. Meunier, Science 268 (1995) 11631166.
[6] B. Meunier, A. Sorokin, Acc. Chem. Res. 30 (1997) 470476.
[7] X. Tao, W.H. Ma, T.Y. Zhang, J.C. Zhao, Angew. Chem. Int. Ed. 40 (2001)
30143016.
[8] A. Rezaeifard, M. Jafarpour, A. Naeimi, R. Haddad, Green Chem. 14 (2012)
33863394.
[9] N. Li, W.Y. Lu, K.M. Pei, Y.Y. Yao, W.X. Chen, Appl. Catal. B: Environ. 163 (2015)
105112.
[10] A.B. Sorokin, E.V. Kudrik, Catal. Today 159 (2011) 3746.
[11] A.B. Sorokin, Chem. Rev. 113 (2013) 81528191.
[12] K. Kumar, P. Adhikary, S. Krishnamoorthi, Polym. Int. 63 (2014) 18421849.
[13] M.Y. Ghaly, G. Htel, R. Mayer, R. Haseneder, Waste Manage. 21 (2001) 4147.
[14] F.A. Banat, B. Al-Bashir, S. Al-Asheh, O. Hayajneh, Environ. Pollut. 107 (2000)
391398.
[15] E. Emerson, J. Org. Chem. 8 (1943) 417428.
[16] E. Emerson, K. Kelly, J. Org. Chem. 13 (1948) 532534.
[17] M. Ettinger, C. Ruchhoft, R. Lishka, Anal. Chem. 23 (1951) 17831788.
[18] Lenore S. Clesceri, Arnold E. Greenberg, R. Rhodes Trussell, Standard Methods
for the Examination of Water and Wastewater, 17th ed., American Public
Health Association, New York, 1989, pp. 551.
[19] Y.C. Fiamegos, C.D. Stalikas, G.A. Pilidis, M.I. Karayannis, Anal. Chim. Acta 403
(2000) 315323.
[20] Y. Fiamegos, C. Stalikas, G. Pilidis, Anal. Chim. Acta 467 (2002) 105114.
[21] N. Rajendiran, J. Santhanalakshmi, J. Mol. Catal. A: Chem. 245 (2006) 185191.
[22] D.P. Li, Y.L. Tong, J. Huang, L.Y. Ding, Y.M. Zhong, D. Zeng, P. Yan, J. Mol. Catal.
A: Chem. 345 (2011) 108116.
[23] D.P. Li, S.X. Ge, J. Huang, J.J. Gong, T.X. Wang, P. Yan, G.B. Li, L.Y. Ding, Sep.
Purif. Technol. 125 (2014) 216222.
[24] D.P. Li, S.X. Ge, J. Huang, J.J. Gong, P. Yan, W.Y. Lu, G.Z. Tian, L.Y. Ding, Catal.
Commun. 45 (2014) 9599.
[25] J.J. Gong, D.P. Li, J. Huang, L.Y. Ding, Y.L. Tong, K. Li, C. Zhang, Catal. Lett. 144
(2014) 487497.
[26] Z.C. Guo, C.L. Shao, M.Y. Zhang, J.B. Mu, Z.Y. Zhang, P. Zhang, B. Chen, Y.C. Liu, J.
Mater. Chem. 21 (2011) 1208312088.
[27] M.Y. Zhang, C.L. Shao, Z.C. Guo, Z.Y. Zhang, J.B. Mu, P. Zhang, T.P. Cao, Y.C. Liu,
ACS Appl. Mater. Interfaces 3 (2011) 25732578.
[28] M.Y. Zhang, C.L. Shao, Z.C. Guo, Z.Y. Zhang, J.B. Mu, T.P. Cao, Y.C. Liu, ACS Appl.
Mater. Interfaces 3 (2011) 369377.
[29] H. Deng, X.L. Li, Q. Peng, X. Wang, J.P. Chen, Y.D. Li, Angew. Chem. Int. Ed. 44
(2005) 27822785.
[30] X.X. Yu, S.W. Liu, J.G. Yu, Appl. Catal. B: Environ. 104 (2011) 1220.
[31] P. Hu, L. Yu, A. Zuo, C. Guo, F. Yuan, J. Phys. Chem. C 113 (2008) 900906.
[32] P. Zhang, C.L. Shao, Z.Y. Zhang, M.Y. Zhang, J.B. Mu, Z.C. Guo, Y.C. Liu,
Nanoscale 3 (2011) 29432949.
[33] J.N. Gao, X.Z. Ran, C.M. Shi, H.M. Cheng, T.M. Cheng, Y.P. Su, Nanoscale 5
(2013) 70267033.
[34] T. Yamashita, P. Hayes, Appl. Surf. Sci. 254 (2008) 24412449.
[35] Z.C. Guo, B. Chen, J.B. Mu, M.Y. Zhang, P. Zhang, Z.Y. Zhang, J.F. Wang, X.
Zhang, Y.Y. Sun, C.L. Shao, Y.C. Liu, J. Hazard. Mater. 219220 (2012) 156163.
[36] R.L. Arechederra, K. Artyushkova, P. Atanassov, S.D. Minteer, ACS Appl. Mater.
Interfaces 2 (2010) 32953302.
[37] F. Jaouen, J. Herranz, M. Lefvre, J.P. Dodelet, U.I. Kramm, I. Herrmann, P.
Bogdanoff, J. Maruyama, T. Nagaoka, A. Garsuch, J.R. Dahn, T. Olson, S.
Pylypenko, P. Atanassov, E.A. Ustinov, ACS Appl. Mater. Interfaces 1 (2009)
16231639.
[38] R.R. Carballo, V. Campodall Orto, I.N. Rezzano, J. Mol. Catal. A: Chem. 280
(2008) 156163.
[39] Q. Guo, S.Y. Qian, R.P. Mason, J. Am. Soc. Mass Spectrom. 14 (2003) 862871.
[40] A.H. Lu, E.L. Salabas, F. Schth, Angew. Chem. Int. Ed. 46 (2007) 12221244.