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Synthesis of Polymeric Ionic Liquid Microsphere/Pt Nanoparticle Hybrids for Electrocatalytic Oxidation of Methanol and Catalytic Oxidation of Benzyl Alcohol
Jianhu Yang,1 Lihua Qiu,1 Baoqiang Liu,1 Yingjing Peng,1 Feng Yan,1 Songmin Shang2
1

Jiangsu Key Laboratory of Advanced Functional Polymer Design and Application, Department of Polymer Science and Engineering, College of Chemistry, Chemical Engineering and Materials Science, Soochow University, Suzhou, 215123, China 2 Institute of Textiles and Clothing, The Hong Kong Polytechnic University, Hong Kong, China Correspondence to: F. Yan (E-mail: fyan@suda.edu.cn) Received 23 April 2011; accepted 18 July 2011; published online in Wiley Online Library DOI: 10.1002/pola.24895

ABSTRACT: Herein, we present a facile approach for the synthesis of polymeric ionic liquids (PILs) microspheres for metal scavenging and catalysis. Crosslinked poly(1-butyl-3-vinylimidazolium bromide) microspheres with the diameter of about 200 nm were synthesized via miniemulsion polymerization, in which 1,4di(vinylimidazolium) butane bisbromide was added as the crosslinker. Anion exchange of PIL microspheres with Pt precursor and followed by the reduction of Pt ions produced PIL microsphere supported Pt nanoparticle hybrids. The synthesized Pt nanoparticles with a diameter of about 2 nm are uniformly dispersed and strongly bound to the surface of PIL microspheres. The catalytic performances of PIL/Pt nanoparticle hybrids were

evaluated for both the electrocatalytic oxidation of methanol and oxidation of benzyl alcohol. The PIL/Pt nanoparticle hybrids show better electrocatalytic activity towards the electrooxidation of methanol than pure Pt nanoparticles. Furthermore, they are effective and easily reusable catalysts for the selective oxidation of benzyl alcohol in aqueous reaction media, demonstrating that the synthesized PIL microspheres are suitable scaffolds for hetC 2011 Wiley Periodicals, Inc. J Polym erogeneous catalysts Pt. V Sci Part A: Polym Chem 000: 000000, 2011
KEYWORDS: electrocatalysis;

heterogeneous liquids; miniemulsion polymerization

catalysis;

ionic

INTRODUCTION Metal nanoparticles are attracting a great deal of attention because of their potential applications in electronic, photonic, and magnetic devices.1 However, direct application of metal nanoparticles is usually difficult because of their ultrasmall size and high tendency of agglomeration into large clusters due to the van der Waals interactions.2 It has demonstrated that such drawbacks could be partially overcome by use of suitable carriers or supporting materials, such as dendrimers,3 polymers,4 polymeric microgels,5 and polymeric or inorganic spheres.6 Among the various carriers, polymeric microspheres have received particular attention because the loading of metal nanoparticles onto the polymeric microsphere surface facilitates the high amount of accessible surface active sites of metal nanoparticles, and thereby raises the activity of the catalysts. Furthermore, polymeric microspheres can be easily synthesized, purified, and surface modified with functional groups.

A variety of polymeric microspheres with or without surface modification have been synthesized and used as templates for the immobilization of metal nanoparticles.711 For instance, Thompson and coworkers7 loaded Pt and Au nanoparticles onto the amino-functionalized polystyrene microsphere surface.

The deposited metal nanoparticles were strongly bound to the microsphere surface and could not be removed by either vigorous stirring or ultrasonication. Akashi and coworkers8 deposited well-dispersed Pd nanoparticles on the surface of polystyrene-co-poly(N-isopropylacrylamide) microspheres, and the catalytic properties of the resulting hybrids were investigated. Zhang and coworkers9(a) reported the synthesis of noble metal nanoparticles embedded in the shell layer of core-shell poly (styrene-co-4-vinylpyridine) microspheres. The resultant shellembedded Pd nanoparticle hybrids are an efficient and easily reusable catalyst for Suzuki reactions. Recently, ionic liquidgrafted rigid poly(p-phenylene) microspheres have been developed for metal scavenging and deemed to be an effective heterogeneous catalyst.9(b) Moreover, polyelectrolyte-coated polymeric microspheres prepared by surface grafting10 or layer-by-layer deposition11 have also been used as scaffolds for the immobilizing of metal nanoparticles. However, preparation of the polymeric sphere templates mentioned above generally needs a multistep synthesis, which is relatively time-consuming. Ionic liquids are organic salts being liquid below 100  C. They are attracting wide attentions because of their negligible vapor pressure, high ionic conductivity, and wide electrochemical

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SCHEME 1 Reaction Scheme for the Preparation of PIL/Pt Hybrids.

window. More recently, growing attention has been paid to polymeric ionic liquids [(PILs), polymers formed from IL monomers], because they are a new class of polymers that combine both the novel properties of ILs and improved mechanical durability and dimensional control. Most studies on PILs are related to the development of advanced polymer gels or electrolytes for electrochemical devices.12 Furthermore, the excellent ion-exchange capability of PILs enables the preparation of PIL microspheres with a variety of counter anions by polymerization of only one IL monomer and followed by anion-exchange reactions.13,14 Herein, we propose a facile strategy for the synthesis of PIL microspheres and their application as potential scaffolds for the immobilizing of metal nanoparticles for electrocatalysis and heterogeneous catalysis. The approach involves the synthesis of PIL microspheres via miniemulsion polymerization, the anion-exchange of PIL microspheres with metal precursor and followed by the reduction of metal ions to zerovalent metal nanoparticles. Taking the advantage of the high ionic conductivity of PILs, the electrocatalytic activities of produced PIL microsphere/Pt nanoparticle (denoted as PIL/Pt) hybrids toward the methanol oxidation reaction were evaluated. The catalytic performances of the resultant PIL/Pt hybrids were evaluated using the oxidation of aerobic benzyl alcohol as the model reaction. The activity and durability of the heterogeneous catalysts were systematically investigated as well.
RESULTS AND DISCUSSION

steps: the synthesis of PIL microspheres via miniemulsion polymerization, and the Br ions of ILs moiety were then exchanged with PtCl2 and followed by the reduction of 4 metal ions with NaBH4 to zerovalent metal nanoparticles to produce the PIL/Pt nanoparticle hybrids. In the first stage, copolymerization of [Bvim][Br] and [C4(vim)2][Br]2 in a water/oil miniemulsion stabilized with Span-80 produced highly cross-linked PIL microspheres with a diameter of about 200 nm although some smaller spheres are observed as well (Fig. 1). Thermogravimetric analysis (TGA) revealed that the produced PIL microspheres decomposed at about 250  C. Such a thermal stability of PIL microspheres makes it possible to be used for medium temperature catalytic reactions. The PIL microspheres bearing Br counter anions were anion exchanged with PtCl2 anions and subsequently 4 reduced by NaBH4 to produce PIL/Pt nanoparticle hybrids. Figure 2 shows the representative transmission electron microscopy (TEM) images of the synthesized PIL/Pt nanoparticle hybrids. It can be clearly seen that high-density Pt nanoparticles were well dispersed on the surface of PIL microspheres. The inset of Figure 2(B) shows the size distribution of Pt nanoparticles deposited on PIL microspheres. It is observed that the Pt nanoparticles show a relatively narrow size distribution and have a size of about 2.1 nm with the deviation of 0.2 nm. The formation of high-density and well-dispersed Pt nanoparticles on the surface of PIL microspheres is probably due to the excellent anion exchange abil ity of PILs that enables PtCl2 4 anions to be enriched on the surface of PIL microspheres, which therefore facilitates the

Synthesis of PIL-Metal Nanoparticle Hybrids Scheme 1 shows the reaction route for the preparation of PIL/Pt hybrids. The synthesis procedure involves following

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FIGURE 3 XRD patterns of (A) PIL microspheres and (B) PIL/Pt nanoparticle hybrids. [Color figure can be viewed in the online issue, which is available at wileyonlinelibrary.com.] FIGURE 1 TEM image of the PIL microspheres synthesized via miniemulsion polymerization.

preparation of high-density Pt nanoparticles.15 Moreover, the low interfacial tensions of the imidazolium groups on the surface of PILs microspheres promote the nucleation rate of Pt nanoparticles, and thus allowing the formation of small nanoparticles because of the low rates of Ostwald ripening.16 TEM images also demonstrate that the Pt nanoparticles are strongly bound to the surface of PIL microspheres and could not be removed by either vigorous stirring or even ultrasonication. The strong interaction between PIL microsphere and metal nanoparticles is probably due to the electrostatic interaction between imidazolium cations and metal nanoparticles.15,16 These results suggest that the PIL microspheres are one of the suitable scaffolds for the metal nanoparticle synthesis. Figure 3 shows the X-ray diffraction (XRD) spectra of PIL/Pt nanoparticle hybrids. Figure 3(A) shows a broad peak at

23.4 corresponding to the diffraction of amorphous nature of PIL microspheres. Such a weak peak at the same location can be also observed in Figure 3(B). The XRD pattern of PIL/Pt nanoparticle hybrids is shown in Figure 3(B). Typical peaks at 39.6 , 46.3 , 67.4 and 81.4 can be assigned to (111), (200), (220), and (311) crystalline plane diffraction peaks of Pt nanoparticles, respectively. The broad peaks in the XRD pattern indicate that the synthesized Pt nanoparticles are small. Here, the peak width of the (111) Bragg reflection was chosen to calculate the mean size of the Pt nanoparticles by using the Debye-Scherrer equation,13 which gives a mean size of 2.4 nm. This value agrees well with the TEM images (Fig. 2). Catalysts for Electrocatalytic Oxidation of Methanol Direct methanol fuel cells (DMFCs) are promising energy conversion devices that convert the chemical energy stored in the fuel directly into electricity. However, high cost and

FIGURE 2 TEM images of PIL/Pt nanoparticle hybrids (insets of B show the corresponding Pt particle size distribution).

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modified glassy carbon (GC) electrode (denoted as Pt/GC) was applied for the electrooxidation of methanol under the same experimental condition for comparison. The performance of the PIL/Pt nanoparticle hybrids toward the electrocatalytic activity was firstly evaluated by cyclic voltammetry (CV). Figure 4 shows the CVs for PIL/Pt/GC and Pt/GC in 0.5 M H2SO4 solution. The preoxidation/reduction peaks of Pt indicate that Pt nanoparticles have a very clean active surface on the electrode. A pair of current peaks between 0.20 and 0.10 V are attributed to the hydrogen adsorption and desorption at Pt nanoparticles. The electrochemical surface areas (ECSA) was measured from the area of the hydrogen adsorptiondesorption peaks after correcting for the double layer charging current from the CV.18 The ECSA value of the PIL/Pt/GC is calculated to be 27.04 m2 g1 of Pt, which is higher than that of Pt/GC (4.29 m2 g1 of Pt). It has demonstrated that the higher ECSA value of a catalyst, the higher the electrocatalytic activity. Therefore, it is expected that the PIL/Pt nanoparticle hybrids will have a higher electrocatalytic activity than pure Pt catalyst deposited on the GC electrode. Figure 5(A) shows the CVs of PIL/Pt/GC and Pt/GC in a 0.5 M H2SO4 solution containing 0.5 M methanol in a potential window of 01.0 V at a scan rate of 50 mV s1. It can be clearly seen that the voltammogram of methanol oxidation at PIL/Pt/GC and Pt/GC was very similar. In the forward scan, the onset potential and the prominent anodic peak were observed at about 0.18 and 0.65 V, respectively. An anodic peak appeared at around 0.46 V which was assigned to the removal of incompletely oxidized carbonaceous species generated in the forward scan is observed in the reverse scan. As can be seen from Figure 5(A) that the peak current of PIL/Pt/GC for the electrooxidation of methanol is 120 mA per mg Pt, which is about 1.45 times higher than that of Pt/ GC (83 mA per mg Pt). The results indicate that the PIL/Pt nanoparticle hybrids have much better electrocatalytic activity toward the electrooxidation of methanol than pure Pt nanoparticles. The high efficiency of PIL/Pt nanoparticle

FIGURE 4 CVs of PIL/Pt/GC and Pt/GC in N2 saturated 0.5 M H2SO4 solution at a scan rate of 50 mV s1. [Color figure can be viewed in the online issue, which is available at wileyonlinelibrary.com.]

carbon monoxide poisoning of Pt catalysts are still the barriers that impede widescale commercialization of DMFCs technologies.17 Recently, Pt and Pt-based alloys deposited on the supporting materials have been investigated as the catalyst for electrooxidation of methanol. To overcome this obstacle and lower the cost of DMFCs, lots of supporting materials for Pt nanoparticles have been tested. It has already demonstrated that a suitable supporting material for dispersing metallic nanoparticles for electrocatalysis should have a high conductivity to provide a facile flow of electronic charges through the supporting material in electrochemical processes and reduce the inner electrical resistance of the catalytic layer. Conductive supporting materials such as carbon nanotubes,18 graphene sheets,19 and conducting polymers20 have been extensively investigated as catalyst support materials for electrooxidation of methanol. As the PIL microspheres prepared in this work are high ionic conducting polymers, they are first used as the nanoelectrocatalysts for the electrooxidation of methanol. Pure Pt nanoparticles (4 nm)

FIGURE 5 (A) CVs of PIL/Pt/GC and Pt/GC at a scan rate of 50 mV s1; and (B) effect of forward CV scan rate on PIL/Pt/GC in N2 saturated 0.5 M H2SO4 0.5 M CH3OH electrolyte. Inset of Figure 5(B) shows the anodic peak currents versus square root of the scan rates (v1/2). [Color figure can be viewed in the online issue, which is available at wileyonlinelibrary.com.]

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FIGURE 6 (A) Potential-dependent steady-state current of PIL/Pt/GC and Pt/GC (recorded at 120 s), and (B) long-term stability of PIL/Pt/GC and Pt/GC in N2 saturated 0.5 M H2SO4 0.5 M CH3OH electrolyte at a scan rate of 50 mV s1.

hybrids on electrocatalytic oxidation methanol could be due to the small size and highly distributed Pt nanoparticles on the PIL microsphere surface, as well as high electron transfer at the electrochemical interface. During the methanol oxidation process, the adsorption of intermediate carbonaceous species on the catalysts surface would lead to catalyst poisoning. The ratio of the forward oxidation current peak (If) to the reverse current peak (Ib), If/Ib, is an important index of the catalyst tolerance to the carbonaceous species accumulation. A higher ratio indicates that methanol is efficiently oxidized to CO2 and a little accumulation of carbonaceous residues at the catalyst surface.21 Here, the If/Ib value is calculated to be 1.94 for PIL/Pt and 1.78 for pure Pt nanoparticles, respectively. The high If/Ib value of PIL/Pt catalyst indicates more effective oxidation of methanol occurs and most of the intermediate carbonaceous species have been oxidized to CO2 during the forward potential scan. The enhanced stability for methanol oxidation of PIL/Pt hybrids is probably due to the strong interactions between the PIL microsphere surface and Pt nanoparticles which inhibit the formation of strongly bond chemisorbed carbonaceous species.20(a) To further evaluate the transport characteristics of methanol in the PIL/Pt hybrids-modified GC electrode, the effect of different scan rate on CVs of PIL/Pt/GC has also been investigated [Fig. 5(B)]. The anodic peak currents are linearly proportional to the square root of the scan rates [inset of Figure 5(B)], suggesting that the electrocatalytic oxidation of methanol at PIL/Pt nanoparticle hybrids is a diffusion-controlled surface process.22 Figure 6(A) shows that the steady-state polarization curve for PIL/Pt hybrids is about 25 times as high as that for Pt nanoparticles during the whole testing process, indicating that the PIL/Pt nanoparticle hybrids have excellent electrocatalytic activity toward the electrooxidation of methanol. From the viewpoint of practical applications, the long-term stability of the catalyst modified electrode is very important. The stability of the PIL/Pt/GC was characterized by multi-

cycle CVs in 0.5 M H2SO4 solution containing 0.5 M methanol, which shows the variation of peak current density with respect to cycle number. It can be seen that the peak current density decreases gradually with the successive scans and about 63% of the catalytic activity is kept after 200 successive scans. However, the catalytic activity of Pt/GC decreased rapidly and about 10% was retained after 200 cycles. The loss of catalytic activity is probably due to the consumption of methanol during the CV scans or catalyst poisoning by adsorbing of CO produced in methanol electrooxidation process.20(a),22 The results demonstrate that the activity and stability of PIL/Pt hybrids are higher than pure Pt deposited on GC electrode. Catalysts for Oxidation of Benzyl Alcohol The polymeric microsphere-supported catalysts have attracted much attention because they facilitate the separation process by precipitation, ultracentrifugation, and ultrafiltration.23 Furthermore, the high dispersion of the polymeric microspheres in the reaction medium allows the reactant molecules to easily access to the active site of nanoparticle catalysts. The development of oxidation process is a topic of current interests. The selective oxidation of alcohols into carbonyl compounds is one of the most important fundamental reactions both at the laboratory and industrial level. Most researches are commonly referred to the selectivity for aldehydes,6(f),24 while the direct conversion of primary alcohols to the corresponding carboxylic acids is still a challenge.21 Here, we expand the use of the produced PIL/Pt nanoparticle hybrids as heterogeneous catalysts for the oxidation of benzyl alcohol to carboxylic acid using oxygen as the oxidant. Considering of the green-chemistry processes and low cost for the clean catalytic synthesis under mild conditions water was chosen as the reaction media instead of organic solvent in this work.25 The effect of catalyst amount on the alcohol conversion was first investigated and the data were summarized in Table 1. Under the same experimental conditions, the blank

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TABLE 1 Benzyl Alcohol Oxidation Catalyzed by PIL/Pt Nanoparticle Hybrids with Different Amounts of Catalystsa Selectivity (%) Entries 1 2 3 4 5
a

PIL/Pt Hybrids (g) 0 0.002 0.005 0.01 0.02

Benzyl Alcohol Conversion (%) 55 61 92 92

Benzaldehyde 87 71 0 0

Benzoic Acid 13 29 100 100

Benzyl alcohol (0.432 g, 4 mmol), K2CO3 (0.552 g, 4 mmol), PIL/Pt hybrids (containing 19.5 wt % of Pt), H2O (50 mL), 90  C, O2, 24 h.

experiment in the absence of catalyst did not show any catalytic activity even after 24 h reaction (Table 1, entry 1). At low catalyst amount, a low alcohol conversion was achieved, and the products were mainly benzaldehyde plus small amount of benzoic acid. The increasing catalyst amount improved the alcohol conversion and so does the selectivity of benzoic acid. Under the catalyst of 0.01 g, the highest alcohol conversion (92%) and acid selectivity (100%) can be acquired. However, a further increase of catalyst amount will not lead to higher alcohol conversion. One of the advantages of PIL/Pt nanoparticle hybrids is that the catalysts can be easily separated from the product and recycled. After the reaction was quenched, the product was extracted from the reaction mixture with ethyl acetate and the hybrid catalysts remaining in the water phase were collected by using centrifugation, washed with water and methanol, and dried before further using in the next run. As can be seen from Table 2 that the catalytic activity of preformed PIL/Pt catalysts was almost constant, and only a slight decrease in conversion were found after six consecutive runs. The decrease may be caused by the slight leaching of hybrid catalysts on recycling, and the diminishing activity of catalysts during catalytic oxidation. These results indicate that PIL/Pt hybrids can be used as efficient and durable catalysts for direct conversion of benzyl alcohol to the corresponding carboxylic acid under relatively mild conditions, which suggests their potential applications in other alcohol catalytic reactions.
EXPERIMENTAL

vinyl-2-pyrrolidone) (PVP, Mn 55,000), diethyl ether, and ethyl acetate were used as purchased. 1-Vinylimidazole was made inhibitor-free by passing the liquid through a column filled with base Al2O3. Deionized water was used for all experiments. Characterization The 1H NMR measurement was carried out on a Varian 400 MHz spectrometer. The particle size of the PIL microspheres was determined by TecnaiG 220 TEM. The powder XRD pattern was recorded on a Rigaku D/max 2500 X-ray diffractometer with parallel Cu Ka radiation (k 1.54178 ). The samples were dried under vacuum at 50  C and then be placed on a glass slide. The weight percentage of metal nanoparticles on the surface of PIL microspheres was determined using a TGA at an increasing temperature rate of 15  C min1 from 50 to 900  C under a continuous nitrogen gas flow. The composition of the samples was determined by inductively coupled plasma-mass spectroscopy (ICP-MS, Varian 710-ES). Synthesis of 1-Butyl-3-vinylimidazolium Bromide Under a nitrogen atmosphere, 1-butyl-3-vinylimidazolium bromide ([Bvim][Br]) was synthesized by stirring the mixture containing 1-vinylimidazole (9.4 g, 100 mmol) and equivalent molar amount of 1-bromobutane (13.7 g, 100 mmol) at room temperature for 24 h. The product was washed three times with diethyl ether and ethyl acetate and dried in vacuum. Colorless liquid. Yield: 95%.
1

Materials 1-Vinylimidazole, 1-bromobutane, 1,4-dibromobutane, 2,20 azobis(2-methylpropionami-dine)-dihydrochloride (V-50), cyclohexane, Span80, K2PtCl4, sodium borohydride, poly(N-

H NMR (400 MHz, CDCl3):10.89 (s, 1H, NCHN), 7.86 (s, 1H, NCHC), 7.58 (s, 1H, CCHN), 7.527.44 (dd, 1H, CH2CHN), 6.015.95 (dd, 1H, HCHCHN), 5.405.36 (dd, 1H, HCHCHN), 4.434.38 (t, 2H, NCH2C), 1.971.87 (quintet, 2H, CH2CH2CH2), 1.441.32 (sextet, 2H, CH2CH2CH3), 0.970.92 (t, 3H,CH2CH3).

TABLE 2 Recovery and Reuse of PIL/Pt Hybrids for Benzyl Alcohol Oxidationa Runs Conversion (%) [selectivity(%)]b First 92 (100) Second 92 (100) Third 90 (98) Fourth 90 (98) Fifth 88 (97) Sixth 87 (99)

a Benzyl alcohol (0.432 g, 4 mmol), K2CO3 (0.552 g, 4 mmol), PIL/Pt hybrids (0.01 g, containing 0.002 g Pt ), H2O (50 mL), 90  C, O2, 24 h. b Refers to the main product of benzoic acid.

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Synthesis of 1,4-Di(vinylimidazolium)butane Bisbromide Under a nitrogen atmosphere, 1,4-di(vinylimidazolium)butane bisbromide [C4(vim)2][Br]226 was synthesized by stirring a mixture containing 1-vinylimidazole (10.4 g, 110 mmol) and 1,4-dibromobutane (10.8 g, 50 mmol) at room temperature for 24 h. The resultant white solids were eluted three times with ether and then dried in vacuo. Yield: 87%.
1

H NMR (400 MHz, DCCl3): 7.587.57 (d, 2H, NCHC), 7.37 7.36 (d, 2H, CCHN), 6.966.88 (dd, 2H, CH2CHN), 5.625.55 (dd, 2H, HCHCHN), 5.235.19 (dd, 2H, HCHCHN), 4.09 (s, 4H, NCH2CH2), 1.75 (s, 4H, NCH2CH2CH2).

GC electrode was coated with 5 lL of PIL/Pt hybrid solution and then dried in air. The surface of modified GC electrode was further coated with 5 lL of Nafion ethanol solution (0.2 wt %) and then dried in air before the electrochemical experiments. A solution containing 0.5 M CH3OH and 0.5 M H2SO4 was used as an electrolyte solution and degassed by high purity nitrogen gas before the measurement. The current (mA mg1) per unit of the loading mass of Pt nanoparticles was used throughout. All the electrochemical characterizations were performed at room temperature. Procedure for Alcohol Catalytic Oxidation Oxygen gas was bubbled into the reaction mixture containing benzyl alcohol (0.432 g, 4 mmol), K2CO3 (0.552 g, 4 mmol), 50 mL H2O and various amount of PIL/Pt hybrids (containing 19.5 wt % of Pt nanoparticles). The reaction mixture was stirred vigorously at 90  C for 24 h. Then the reaction was cooled to room temperature and quenched with 1.0 M HCl. The organic product was extracted with ethyl acetate three times and dried over anhydrous MgSO4. The substrate conversion and product yield were determined by 1H NMR and gas chromatography. The PIL/Pt hybrids were separated by centrifugation and washed thoroughly with ethanol and distilled water, and then dried at 80  C under vacuum before the next recycle run.

Synthesis of PIL Microspheres via Inverse Miniemulsion Polymerization A typical procedure for the synthesis of PIL microspheres is described as below: a mixture containing [Bvim][Br] (1.0 g, 4.3 mmol), [C4(vim)2][Br]2 (0.2 g, 0.5 mmol) and V50 (0.01 g, 0.037 mmol) in water (1.4 mL) was stirred at room temperature under a nitrogen atmosphere. The resultant clear solution was mixed with Span 80 (1.0 g) and cyclohexane (20 g). Then the mixture was ultrasonicated for 10 min in an ice bath to obtain a stable inverse miniemulsion. The miniemulsion was degassed via nitrogen gas bubbling and then kept at 60  C for 6 h. The reaction was cooled to room temperature and poured into acetone. The precipitated PIL microspheres were isolated by decantation, and then separated by centrifugation. The remaining residues were washed with acetone three times to remove unreacted materials and then dried in vacuum at 50  C. Synthesis of Metal Nanoparticles Immobilized on the Surface of PIL Microspheres In a typical experiment, 6 mL of K2PtCl4 solution (7.5 mmol/ L) was added into 4 mL of water in which PIL nanoparticles (0.01 g) and PVP (0.26 g) were dispersed. The mixture was stirred at room temperature for 1 h under a nitrogen atmos phere to convert Br anions to PtCl2 4 . The anion-exchanged PIL microspheres were separated by centrifugation and washed thoroughly with distilled water to remove the excess PVP and K2PtCl4. A sixfold excess of NaBH4 (0.017 g) solution was added dropwise to the suspension with vigorous stirring, then the mixture was kept at room temperature for 1 h. The resultant PIL/Pt hybrids was separated by centrifugation and washed with water to remove the excess salts and free metal nanoparticles not firmly bound to PIL microsphere surface. The produced hybrids were washed with acetone and then vacuum dried. The amount of Pt nanoparticles calculated by ICP is about 19.5 wt %. Electrocatalysis of Methanol Electrochemical performance of PIL/Pt nanoparticle hybrids was evaluated by CV and chronoamperometry and recorded on a CHI660 electrochemical workstation with a conventional three-electrode electrochemical cell. A modified GC electrode with a diameter of 3 mm and platinum foil were used as working and counter electrode, respectively. A saturated calomel electrode was used as the reference electrode. The PIL/Pt hybrids were ultrasonically dispersed in water to form a homogeneous dispersion (1 mg/mL). The surface of

CONCLUSIONS

In summary, we have developed a facile strategy for the synthesis of PIL microspheres supported Pt nanoparticle hybrids. Crosslinked PIL microspheres with the diameter of about 200 nm were synthesized via miniemulsion polymerization. Anion exchange of PIL microspheres with metal precursor and followed by the reduction of metal ions produced PIL/Pt nanocatalysts. The resultant Pt nanoparticles are uniformly dispersed and strongly bound to the surface of PIL microspheres. The catalytic performances of the produced PIL/Pt hybrids were evaluated for the electrocatalytic oxidation of methanol and oxidation of benzyl alcohol. The results revealed that PIL/Pt nanoparticle hybrids show better electrocatalytic activity toward the electrooxidation of methanol than pure Pt nanoparticles. They are effective and easily reusable catalysts for the selective oxidation of benzyl alcohol in aqueous reaction media, demonstrating that the synthesized PIL microspheres are suitable scaffolds for heterogeneous catalysts. Further investigations to develop other noble metals or their alloys nanoparticles decorated on the surface of PIL microspheres for heterogeneous catalysis as well as for electrocatalysis and electrochemical sensors are currently underway. This work was supported by Natural Science Foundation of China (No. 20874071, 20974072), Research Fund for the Dectoral Program of Higher Education (20103201110003), The Program for New Century Excellent Talents in University (Grant NCET-07-0593), Fok Ying Tung Education Foundation (114022) and a Project Funded by the Priority Academic Program Development of Jiangsu Higher Education Institutions.

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