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Catalytic Activity of Styrene-divinyl Benzene Supporting Metallophthalocyanine 1

HUANG Xian-wen, YAO Yu-yuan, LV Wang-yang, WANG Xiu-hua, CHEN Wen-xing* Key Laboratory of Advanced Textile Materials and Manufacturing Technology, Ministry of Education, Zhejiang Sci-Tech University, Zhejiang Hangzhou, 310018 *E-mail: chenwxg@yahoo.com.cn

Abstract
Binuclear cobalt phthalocyanine (Co2Pc2) was supported on styrene-divinyl benzene resin by covalent bond to obtain a novel catalytic functional material, Resin-Co2Pc2. The effects of pH, the quantity of Resin-Co2Pc2 and temperature on the catalytic activity of Resin-Co2Pc2 on 2-mercaptoethanol were investigated. The results showed that Resin-Co2Pc2 had high catalytic activity on 2-mercaptoethanol, and even the catalytic activity was the best at pH11. The reaction can further be enhanced with the quantity of Resin-Co2Pc2 and temperature increasing, due to its endothermic characteristics. There was no decrease in the catalytic activity of Resin-Co2Pc2 after five repetitive experiments, which indicated that Resin-Co2Pc2 could be recycled. Keywords: binuclear cobalt phthalocyanine; catalytic oxidation; functional materials; 2-mercaptoethanol

Introduction
Metallophthalocyanines (MtPc) have attracted considerable attention as good catalysts because of

their structural similarity to the P450 prosthetic group porphyrin in the biological system.[1]-[3] The extensive studies on catalytic activity of metallophthalocyanines have been carried out in homogeneous catalytic system.[4]-[5] However, there are some problems in homogeneous system: difficultly separating from reaction system, bringing the second pollution to the surrounding environment and so on. Therefore, metallophthalocyanines has been tried to be supported on the polymer and inorganic materials, such as molecular sieve, zeolite, etc. All of these researches have obtained some achievements.[6]-[9] Among those supports, resin is cheap and has some special properties, such as excellent thermal stability and easily separating from the reaction system. Our group had reported that, relative to mononuclear metallophthalocyanine, binuclear metallophthalocyanine showed more effective catalytic activity on mercaptoethanol (MEA) because of its plane rigid structures and expanding electron conjugation system. In this paper, binuclear cobalt phthalocyanine (Co2Pc2) was

Support by the National natural science foundation of China (No. 20574061, 50872124),

Specialized Research Fund for the Doctoral Program of Higher Education ( 20060338002)and Zhejiang Provincial Natural Science Foundation of China (Y4080341) -1-

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prepared and supported on styrene-divinyl benzene resin by covalent bond to obtain a novel catalytic functional material, styrene-divinyl benzene supporting metallophthalocyanine (Resin-Co2Pc2). This catalytic functional material possessed excellent catalytic performances on mercaptoethanol at normal temperature, and facilitated catalyst separating from reaction system and was even recycled, avoiding the second pollution from molecular metallophthalocyanines. This kind of catalytic functional materials has wide application prospect in degrading organic pollutant.

2
2.1

Experiment
Materials and instrument

Binuclear cobalt phthalocyanine (Co2Pc2, synthesized in our laboratory according to the reference[10]). Styrene-divinyl benzene resin was obtained from Zhengguang Resin Factory (Hangzhou, China). Thionyl chloride was purchased from Shanghai Meixing Chemical Co., Ltd. (Shanghai, China). N,N-dimethylformamide(DMF) was obtained from Hangzhou Huipu Chemical Co., Ltd. (Hangzhou,China). Sodium Hydroxide was purchased from Zhejiang Hangzhou Xiaoshan Chemical Reagent Factory (Hangzhou,China). Pyridine was obtained from Wuxi Hongsheng Chemical Factory (Wuxi,China). Benzene was purchased from Hangzhou Chemical Reagent Factory (Hangzhou,China). Anhydrous aluminum chloride was obtained from Shanghai Meixing Chemical Co., Ltd. (Shanghai, China). 2-mercaptoethanol was purchased from Shanghai Reagent Sihewei Chemical Co., Ltd. (Shanghai, China). The instruments and apparatus: FAS2004 Electronic Balance, 78HW-1 Constant temperature Magnrtic Stirring, Hitachi 170-70 Atomic Absorption Spectrophotometer (Japan Hitachi Co.), Perkin Elmer Pyris 7 Thermogravimetric Analyzer (American Perkin Elmer Co.).
2.2 Synthesis of resin catalyst

The preparation route of Co2Pc2-Resin was shown in Figure 1. 2.00g Co2Pc2 was placed in a 250ml three-necked flask, and then 3ml thionyl chloride, 10ml mixture solvent of DMF and benzene were added. The reaction temperature was controlled at 80 C and held reaction for 12 h under stirring and refluxing. 150ml pyridine was poured into reaction solution, fully dissolved, and 4g AlCl3 and 60g treated Styrene-divinyl benzene resin were added. The reaction mixture was heated to 80 C and reacted
for some time. After filtration, the product was washed with water twice, 0.1 molL-1 sodium hydroxide solution, water, methanol, acetone. Upon drying at 80 C, the Co2Pc2-Resin was obtained.

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HOOC

COOH

HOOC

COOH

N HOOC HOOC

N N N

N N N COOH COOH

SOCl2 , 80 C6H6 , DMF

N Co N N

N Co N N

HOOC ClOC

COOH COCl

HOOC ClOC

COOH COCl

N ClOC ClOC

N N N

N N N COCl COCl

N Co N N

N Co N N

Co2Pc2

COCl

ClOC

COCl

ClOC

COCl

Co2Pc2

COCl C Co2Pc2 O

AlCl3 80 N

Resin

O C Co2Pc2

C O Co2Pc2

Co2Pc2

Resin

Figure 1: The process for preparation of Co2Pc2-Resin 2.3 The measurement of Co2Pc2 in Co2Pc2-Resin 10ml HNO3 (68, w/w) and 2ml H2O2 (30, w/w)) were added in Co2Pc2-Resin (1.00g), microwave digesting for 5min, cooling and determining volume. The concentration of metal ion was determined by Atom Absorbed Spectrometer, and the calculated amount of Co2Pc2 in Co2Pc2-Resin was 0.8 % (wt %). 2.4 The catalytic activity of Co2Pc2-Resin The catalytic activity measurement was carried out by self-made instrument. In the closed system with constant temperature, some resin catalyst was added into 200 ml water whose pH value had been adjusted, and then some 2-mercaptoethanol was added under a fixed stirring speed. The quantity of oxygen consumption was used to characterize the catalytic activity of Co2Pc2-Resin.

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3
3.1

Results and discussion

Thermogravimetric analysis. The thermal stability of Co2Pc2-Resin was verified by Perkin Elemer TGA 7 thermogravimetric

analyzer. The temperature increased to 700 C at a rate of 20C/min and the nitrogen flow rate was 100 ml/min. Figure 2 presents the recorded curves of weight loss for resin and Co2Pc2-Resin. The first weight loss of resin took place at 300 C. When heated to 500 C, the residual weight rate was 2.01%. Co2Pc2-Resin started from 356 C, which indicated that the initial decomposition temperature was higher than resin. When heated to 500 C, the weight residual rate was 3.2%. It suggests that the thermal stability of Co2Pc2-Resin is better than resin.

125 100
Co2Pc2-Resin

weight (%)

75 50 25 0 0 150 300 450 600 o Temperature ( C) 750

Resin

Figure 2: Thermogravimetric analytical curves of Resin and Co2Pc2-Resin

3.2

Phthalocyanines catalyst 2-mercaptoethanol In alkaline medium, the reaction mechanism of metallophthalocyanine derivative and

2-mercaptoethanol [11] was shown as follows (metallophthalocyanine used as a catalyst):

HSCH2CH2OH + OH

catalyst

HOCH2CH2S + H2O

4 HOCH2CH2S + O2 + 2H2O

catalyst

2HOCH2CH2SSCH2CH2OH + 4OH

The whole reaction4HSCH2CH2OH +O2

catalyst

2HOCH2CH2SSCH2CH2OH + 2H2O

From equations above, the catalyzed reaction of 2-mercaptoethanol by metallophthalocyanine was a consumedoxygen reaction. Therefore, the catalytic activity of metallophthalocyanine was determined by measuring the amount of O2 consumed.

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3.3 3.3.1

Catalytic activity of Co2Pc2-Resin on 2-mercaptoethanol Effect of pH on the catalytic activity 10g Co2Pc2-Resin and 200ml water were added at different pH value (5, 7, 9, 11, and 12)

separately at 20 C. Then the catalytic activity was tested after 1.4ml MEA was added. Figure 3 shows that, the oxygen consumption increased as pH rose from 6 to 11 and reached the maximum at pH11 , but decreased above pH 11. This is mainly because the dissociation of 2-mercaptoethanol directly affected the oxidation of thiols and more thiolate anions were formed by the dissociation of 2-mercaptoethanol under high pH conditions, which produced -SCH2CH2OH afterward. However, the

excessive hydroxyl above pH 11 would hinder the combination between -SCH2CH2OH and phthalocyanine, leading to the decrease of the catalytic activity. Therefore, the catalytic activity is highest on pH 11.

Figure 3: Effect of pH on the catalytic activity of Resin-Co2Pc2 (T=20 oC, [RSH]0 =0.1molL, [O2]0=8.5910-3 molL)

3.3.2

Effect of concentration of catalyst on catalytic activity 200ml water (pH=11) and Co2Pc2-Resin was added at different weight(5g, 10g, 15g, 20g, 25g)

separately at 20 C. Then the catalytic activity was tested after adding 1.4ml MEA. Figure 4 shows the oxygen consumption increased with the concentration of Co2Pc2-Resin up. It indicates that the catalytic activity increased with the concentration of catalyst increasing.

Figure 4: Effect of catalyst concentration on the catalytic activity of Co2Pc2-Resin (T=20 C, pH=11, [RSH]0 =0. 1 molL-1, t=60min, [O2]0=8.5910-3 molL-1) -5-

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3.3.3

Effect of temperature on catalytic activity Water bath was at different temperature (10 C, 20 C, 30 C, 40 C). Then 10g Co2Pc2-Resin,

200ml water (pH=11) and 1.4ml MEA were added separately. Figure 5 indicates the oxygen consumption increased with temperature up in the same testing period. It illuminates that the catalytic activity increases with the water bath temperature. Figure 6 shows the dependence of lnV0 (V0, the initial reaction rate) on the T-1, a linear relationship between lnV0 and T-1. Therefore, the relationship between reaction rate and temperature of this reaction satisfies Arrhenius formula. According to Arrhenius formula: ln V =

Ea + B , the slope is Ea and the intercept is B. The activation RT R

energy (Ea), 38.18 kJ/mol, obtained by fitting the slope, indicates that this catalytic oxidation is an endothermic reaction

Figure 5: Effect of temperature on the oxidation rate of 2-mercaptoethanol by Co2Pc2-Resin (a: 10C; b: 20 C; c: 30 C; d: 40 C, pH=11, [RSH]0 =0. 1 molL-1, t=60min, [O2]0=8.5910-3 molL-1)

Figure 6: Plots of lnV0 vs. T-1 for oxidation of 2-mercaptoethanol by Co2Pc2-Resin

3.3.4

Cyclic utilization of Co2Pc2-Resin Water bath temperature was at 20 C, 10g Co2Pc2-Resin was placed in 500ml three-necked flask

on pH 11, and then some MEA was added. As shown in Figure 7(1), Co2Pc2-Resin has excellent catalytic oxidation performance on MEA. In order to investigate the cyclic utilization of Co2Pc2-Resin, we repeated the test four times under the same experimental condition after separating Co2Pc2-Resin from solution and treating, as shown in Figure 7(2-5). The results indicate that, after 5 times cyclic utilization, the catalytic activity of Co2Pc2-Resin on MEA has no remarkable decrease. Therefore, Co2Pc2-Resin has great reusability.

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12

Consumed oxidation (ml)

10 8 6 4 2 0 0 50 100 150 200 250 Reaction time (min) 300

1 2 3 4 5

Figure 7: The rate of oxidation of mercaptoethanol by Co2Pc2-Resin in five runs.

Conclusions

(1) Binuclear cobalt phthalocyanine (Co2Pc2) was immobilized styrene-divinyl benzene resin by covalent bond to obtain a novel polymer catalyst. (2) Co2Pc2-Resin has high catalytic activity on MEA and even the catalytic activity is best at pH 11. The catalytic activity increases with temperature up and the activation energy Ea is 38.18 kJ/mol,

so the catalytic reaction is endothermic. (3) Co2Pc2-Resin shows excellent catalytic oxidation performance on MEA for 5 times cyclic utilization without catalytic activity decreasing significantly

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