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Journal of Materials Chemistry

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One-pot synthesis of functional two-dimensional graphene/SnO2 composite nanosheets as a building block for self-assembly and an enhancing nanomaterial for biosensing
Chengzhou Zhu, Youxing Fang, Dan Wen and Shaojun Dong*
Downloaded by University of Ulsan on 08 October 2011 Published on 15 July 2011 on http://pubs.rsc.org | doi:10.1039/C1JM11612F

Received 15th April 2011, Accepted 2nd June 2011 DOI: 10.1039/c1jm11612f A one-step approach to synthesize functional two-dimensional graphene/SnO2 composite nanosheets (GSCN) is reported. It should be noted that SnCl2 is not only a reducing agent for graphene oxide (GO), but also a precursor of SnO2. On the other hand, polyelectrolyte poly(diallyldimethylammonium chloride) (PDDA) was introduced simultaneously in the preparation, to endow it with an ideal selfassembly building block. Through electrostatic interaction, a general method has been developed for the preparation of ternary GSCN/nanoparticles (GSCN/NPs) hybrid structures with high-density noble metal NPs. Prominent examples including Au, Pt and Au@Pt hybrid NPs could be loaded on the surface of GSCN. Furthermore, we employed high-density Au@Pt NPs supported on GSCN as the electrochemical material for nonenzymatic glucose detection, which exhibited good electrocatalytic activity.

1. Introduction
Graphene (GN), as a two-dimensional nanomaterial, possesses nano-scale dimensions in thickness only and innite length in the plane. It has attracted tremendous attention since the experimental observation of single layers by K. S. Novoselov and A. K. Geim in 2004.1 So far, several methods have been developed to produce graphene.14 Among these methods, chemical conversion from graphene oxide (GO), which can be prepared from natural graphite by the modied Hummers method, is the most suitable method for low-cost and large-scale production of graphene.2,5 Signicantly, its several excellent attributes, such as the large theoretical specic surface area, excellent conductivity and high transparency due to its one-atom thickness, make GN a novel substrate for forming hybrid structures with a variety of nanomaterials.612 With appropriate designs, nanocomposites can exhibit the excellent properties of parent constituents, producing a desired material with improved performance.13,14 To date, much effort has been devoted to incorporate GN into composite materials and explore their applications in various elds such as nanoelectronics,1517 biosensors,1821 nanocomposites,2227 batteries,28,29 supercapacitors,30,31 etc. On the other hand, among diverse metal oxides, intensive attention has been given to SnO2 because of its unique properties such as high optical transparency, electrical conductivity,

State Key Laboratory of Electroanalytical Chemistry, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun, 130022, China. E-mail: dongsj@ciac.jl.cn; Fax: (+86)-431-85689711; Tel: (+86)431-85262101

chemical sensitivity and low cost. To date, there are a few reports about the preparation of SnO2/graphene composites via different synthetic protocols with applications to lithium batteries,3234 gas sensors,35 photocatalytic degradation36 or supercapacitors.37 However, the synthesis of graphene/SnO2 nanocomposites with well-dispersed decorated particles is still a challenge in that the hydrophobic/hydrophilic incompatibility between GN and inorganic compounds (especially metal oxides) makes it difcult to directly deposit metal oxides on GN.38,39 In addition, noble metal nanoparticles (NPs) have been widely used as electrocatalysts.40,41 Meanwhile, the immobilization of NPs on highsurface-area substrates have recently attracted much attention because of their extraordinary and enhanced properties, which are attributed to surface effects, quantum-size effects, and metal support interactions.42,43 However, few works have yet been reported on the synthesis of GN/SnO2/NPs nanocomposite with well dened nanosheet-like morphology and excellent performance. With the demand for uniform distrubution and high loading, facile and effective approaches for the preparation of the above ternary (GN, SnO2 and noble metal NPs) hybrids are highly desirable and remain a great challenge. Herein, we report a convenient method of a one-step synthesis of positive-charged graphene/SnO2 composite nanosheets GSCN which serve as the buiding blocks for self-assembly. The polyelectrolyte PDDA was rst introduced to endow graphene oxide with good solubility and positive electrostatic charge for uniform anchoring of SnO2 onto the surface of graphene. GSCN was directly prepared by reducing GO/PDDA with Sn2+ ions in aqueous solution, which possesses positive charge and provides an ideal self-assembly platform. Through electrostatic
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interaction, the negatively charged metal NPs could be assembled on both sides of the positively charged GSCN. A general method has been developed for the preparation of GSCN/NPs hybrid structures with high-density noble metal NPs by using very homogeneous SnO2 as a linker. Prominent examples include Au, Pt and Au@Pt hybrid NPs which can be loaded onto the surface of GSCN. The whole procedure for self-assembly of GN and metal NPs is shown in Scheme 1. UV-visible (UV-vis) absorption spectroscopy, Fourier transform infrared (FTIR) spectra, atomic force microscopy (AFM), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS) and X-ray diffraction (XRD) spectra were used to characterize the structure and morphology of the obtained GSCN/NPs. Furthermore, we employed the high-density Au@Pt NPs supported on GSCN as the electrochemical enhanced nanomaterial for nonenzymatic glucose detection, which exhibited prominent electrocatalytic activity.

were measured by Autolab with PGSTAT 30 (Eco Chemie B.V., Utrecht, Netherlands) and with the aid of a frequency response analysis system software under an oscillation potential of 5 mV over a frequency range of 100 kHz to 0.01 Hz. Zeta potential measurements were performed using a Zetasizer NanoZS (Malvern Instruments) and all the graphene samples were washed and diluted to 0.05 mg mL1 before measurements. Cyclic voltammetry experiments were performed on a CHI 832 electrochemical analyzer (CH Instruments, Chenhua Co., Shanghai, China). A conventional three electrode cell was used, including an Ag/AgCl (saturated KCl) electrode as reference electrode, a platinum wire as counter electrode, and the bare and modied glassy carbon electrode (GCE, 3 mm in diameter) as working electrode.

2.3.

Preparation of graphene oxide

2. Experimental
2.1. Chemical reagents and materials Graphite was purchased from Alfa Aesar. HAuCl4$4H2O, H2PtCl6$6H2O, trisodium citrate dihydrate were purchased from Shanghai Chemical Factory and used without further purication. SnCl2$2H2O and HCl (3638%) were bought from Beijing Chemical Works (Beijing, China). Poly(diallyldimethylammonium chloride) (PDDA, 35 wt.% in water) was obtained from Aldrich. Unless otherwise stated, other reagents were of analytical grade and were used as received. All aqueous solutions were prepared with ultrapure water (>18 MU) from a Milli-Q Plus system (Millipore). 2.2. Apparatus

The graphite oxide was synthesized from natural graphite powder based on a modied Hummers method.44 Then, exfoliation of graphite oxide to GO was achieved by ultrasonication of the dispersion for 40 min (1000 W, 20% amplitude). Finally, a homogeneous GO aqueous dispersion (0.5 mg mL1) was obtained and used for further characterizations and the chemical reduction.

2.4.

Synthesis of functional GSCN

UV-vis detection was carried out on a Cary 50 UV-vis spectrophotometer (Varian, USA). Infrared spectra were collected on a VERTEX 70 Fourier transform infrared (FTIR) spectrometer (Bruker). AFM was conducted with a SPI3800N microscope (Seiko Instruments, Inc.). TEM and HRTEM images were obtained with a TECNAI G2 high-resolution transmission electron microscope operating at 200 kV. X-ray diffraction (XRD) spectra were obtained using a D8 ADVANCE (Germany) using  Cu K (1.5406 A) radiation. X-ray photoelectron spectroscopy (XPS) analysis was carried on an ESCALAB MK II X-ray photoelectron spectrometer. The electrochemical impedance (EIS) experiments were performed in the presence of 2.5 mM K3[Fe(CN)6]/K4[Fe(CN)6] (1:1) as the redox probe. The spectra

GSCN was prepared according to previous work with minor modication.37 Typically, 20 mL of GO (0.50 mg mL1) and 0.4 mL PDDA were mixed together, followed by stirring for more than 0.5 h. Subsequently, 0.15 ml of HCl, 0.30 g of SnCl2$2H2O were added. The mixture was continually stirred at 90  C for 3 h. Then, the resulting stable black dispersion was centrifuged and washed with water. Finally, the obtained GSCN was dissolved in 20 mL water for further use.

2.5.

Synthesis of noble metal nanoparticles

Scheme 1 Procedure to design GSCN/metal NPs.

(a) Au@Pt NPs were prepared according to our previous work.45 Briey, 1 wt % HAuCl4 solution (1 mL) was added to 100 mL of aqueous solution. Second, 1 wt % sodium citrate (3 mL) was quickly introduced into the above solution, followed by the addition of NaBH4 aqueous solution (excess). After the solution was stirred overnight, 2.5 mL of 1 wt % H2PtCl6 was added into a Au NPs boiling solution, followed by the addition of 2 mL of 0.1 M ascorbic acid (AA) (excess). After this solution was heated for 30 min, Au/Pt hybrid NPs were obtained. (b) Gold nanoparticles of 13 nm diameter were synthesized according to the literature.46 100 mL of 1mM HAuCl4 was brought to reux while stirring and then 10 mL of a 38.8 mM trisodium citrate solution was added quickly, which resulted in a color change of the solution from pale yellow to deep red. After the color change, the solution was reuxed for an additional 15 min. (c) Pt NPs were synthesized according to the literature.45,47 Typically, 5 mL of 1% H2PtCl6 aqueous solution was added to 100 mL of water and then heated to boiling. Then, 3 mL of 5% sodium citrate aqueous solution was added rapidly, and the mixture was kept at boiling temperature for about 30 min.
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2.6. Constructing GSCN/noble metal NPs hybrid nanostructures The GSCN/metal NPs hybrid nanostructures were prepared by mixing 0.1 mL of GSCN aqueous solution with 6 mL of Au, Pt or Au@Pt NPs solution. The resulting products were collected and dissolved in 0.2 mL of water. 2.7. Electrocatalytic experiment

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GCE was polished with 1.0 and 0.3 mm alumina slurry sequentially and then washed ultrasonically in water and ethanol for a few minutes, respectively. The cleaned GCE was dried with a high-purify nitrogen steam for the next modication. A total of 5 mL of GSCN or GSCN/Au@Pt NPs (GN, 0.25 mg mL1) was dropped on the pretreated GCE surface and dried at room temperature. Naon (3 mL, 0.5% in aqueous solution) was then placed on the surface of the above materials modied GCE and dried before electrochemical experiments

3. Results and discussion


High-quality GSCN with designed functionality was rst synthesized. It should be noted that SnCl2 is not only a reducing agent for GO, but also a precursor of SnO2. By incorporation of positive charged PDDA into the resulting GSCN, the aggregation of GN nanosheets could be inhibited due to the strong repulsion between them and GSCN. Thus, the as-prepared aqueous colloidal dispersions were very stable, which was favorable for the subsequent assembly. Firstly, the conversion of GO to GSCN was monitored by UV-vis spectra (Fig. 1a). The UV-vis absorption peak of the GO dispersion at 230 nm disappeared and red shifted to a broad peak located at 255 nm, which suggests that GO is reduced and the electronic conjugation within the GN sheets is restored upon reduction.2,5 Meanwhile, the reduction was also conrmed from the color change of the solution before and after reduction (from brown to dark, as shown in inset of Fig. 1a). These results agree well with previous reports.23,37 Furthermore, FTIR spectroscopy was employed to investigate the functionalized and reduction processes (Fig. 1b). The signicant decrease of the peaks at 1732 cm1 (C]O) and 1365 cm1 (OH) indicated the remove of oxygen-containing groups on GO after reduction.5,48 The absorption bands at 1633 cm1 (C]C) and 1460 cm1 (C]C) corresponded to the characteristic bands of PDDA, indicating the functionalization of GSCN with PDDA.49
Fig. 2 The typical TEM (a, b and c) and HRTEM (d) image of the obtained GSCN.

Fig.2 shows the typical TEM image of the as-made GSCN. It is clear that GSCN has nanosheet morphology with some corrugations. Additionally, the high-resolution TEM (HRTEM) image revealed that the whole surface of the GSCN sheet was decorated with worm-like SnO2 nanoparticles. The distance of the visible lattice fringes over a large area was measured to be 0.33 nm, as shown in Fig. 2d, corresponding to the d-spacing of (110) planes of SnO2. Obviously, introducing PDDA had no effect on the dispersity of SnO2 on the graphene surface.36,37 In addition, we further investigated the morphology by AFM. Fig. 3a shows a typical AFM image of GO. It is found that the substrate mica is covered with a number of nanosheets of high purity. The average thickness of GO, measured from the height prole of the AFM image (Fig. 3b), is about 1.1 nm. Similar to

Fig. 1 UV-vis absorption (a) and FTIR (b) spectra of GO and the obtained GSCN. The inset in (a) shows typical images of aqueous dispersions of GO and GSCN.

Fig. 3 AFM images (a, c) and height proles (b, d) along the lines shown in AFM images of GO (a, b) and as-prepared GSCN (c, d).

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the original GO dispersion, the as-synthesized GSCN is shown in Fig. 3c, both remain separated in the dispersion, which was coincident with the TEM results. The AFM analysis reveals that the average thickness of GSCN obtained in this work was about 20.3 nm (Fig. 3d). When compared with well exfoliated GO sheets, the thickness of GSCN is greater, which suggests that the SnO2 was completely covered on both surfaces of the GSCN. Fig. 4 shows the XRD patterns of samples GO and GSCN. For the sample GO (black line), the sharp (002) diffraction peak at 10.4 illustrated that most of the natural graphite was oxidized into GO by expanding the d-spacing from 0.34 nm to 0.76 nm.5,50 For the resulting GSCN (red line), no diffraction peaks of layered GO can be seen, conrming the great reduction of GO and the formation of the layered GSCN. It is observed that the XRD peaks can be indexed to the diffractions of SnO2 planes (JCPDS, no. 411445). To further illustrate the component of GSCN, XPS was performed. The XPS spectra show the existence of C, N, Sn and O (data not shown) in GSCN. Compared with the C 1s XPS spectrum of GO (Fig. 5a), the intensities of all C 1s peaks were assigned to carbon atoms bound to oxygen, the CO (epoxy and alkoxy) peaks especially decreased signicantly revealing that most oxygen-containing functional groups were removed after reduction (Fig. 5b).5,37 The binding energies centered at 486.3 eV and 494.7 eV are ascribed to Sn4+, suggesting the formation of SnO2 on GN (Fig. 5c). Compared with previous reports, negative shifts of the binding energies were found, which maybe due to the introduction of PDDA. Moreover, it should be noted that the detectable N is ascribed to polyelectrolyte PDDA (Fig. 5d). As is already known, self-assembly is an important and effective way for nanofabrication that involves self-organizing the building blocks into functional structures by different driving forces.51 Among them, the self-assembly of oppositely charged interesting species is one of the most important ways to fabricate multifunctional hybrid nanomaterials.52,53 It should be noted that the main advantage of this strategy stems from the highly desired size- and shape-dependent NPs, free from GN modication. To date, GN and its derivatives, which serve as promising

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Fig. 5 The C 1s XPS spectra of GO (a) and the as-obtained GSCN (b). The Sn 3d (c) and N 1s (d) XPS spectra of the GSCN.

building blocks, can be used in assemblies with NPs,51 metal oxide,54 polymers,55 biomolecules,56,57 and so on. However, the introduction of designed linkers or multistep processes limit the application.51 In this work, one-step approach was developed to synthesize functional GN/metal oxide hybrid, which was directly employed as an effective self-assembly platform. As a result, the immobilization of NPs (Au@Pt, Au and Pt NPs) on GSCN was successfully realized for developing new application systems. To reveal the detailed structure of GSCN/Au@Pt hybrid nanomaterials, the corresponding TEM images are shown in Fig. 6. Here, high-density Au@Pt NPs anchored to the surface GSCN by a simple electrostatic adsorption procedure were observed. The high-density Au@Pt NPs loaded on GSCN is ascribed to the strong interaction between positive charged GSCN and negative charged Au@Pt NPs. We also studied the zeta potential change from synthesis to subsequent assembly. The result is summarized in Table 1. The zeta potential of the synthesized GO was 50.7 mV, showing the good solubility of GO in aqueous media. For the obtained GSCN, the zeta potential dramatically changed from a negative to a positive value (+44.5 mV), owing to the adsorption of PDDA at the GN surface. Then, the value altered again to negative (19.6 mV) after assembly with negative charged Au@Pt NPs. As has been shown in TEM images,

Fig. 4 XRD patterns of GO (black) and GSCN (red). The standard spectra of SnO2 is included in the gure for reference.

Fig. 6 Typical TEM images of the obtained GSCN/Au@Pt NPs at different magnications.

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Table 1 The change of zeta potential from GO to GSCN/Au@Pt NPs at 25  C GO Zeta potential (mV) 50.7 GSCN +44.5 GSCN/Au@Pt NPs 19.6

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the entire GSCN were covered by citrate capped Au@Pt NPs, which possess a negative-charged surface. More importantly, the present functionalization method can be a general and attractive strategy for the decoration of GSCN with size and composition-controlled metal NPs. For example, Au NPs (Fig. 7a and b), and Pt NPs (Fig. 7c and d) can be easily adsorbed on the surface of GSCN. Compared with traditional methods, constructing GSCN/NPs hybrid nanostructures have obvious advantages. First, a simple approach for synthesizing GSCN by direct reduction of GO and crystallization of SnO2 is presented. We aimed at assembling noble metal NPs on this layered GN-based binary hybrid. Second, the homogeneous SnO2 can easily be modied in designed functional groups accompanied by formation of GSCN. Namely, the obtained GSCN was directly utilized as a building block to load NPs on both sides of the GSCN, exploring their important applications in various elds. The electrochemical impedance spectroscopy (EIS) measurements were also performed (Fig. 8) to evaluate the resistance against electron transfer during the electrochemical process. According to the Nyquist plot, the charge-transfer resistances (Rct) of the bare GCE, GSCN/GCE and GSCN/Au@Pt/GCE were 117, 42 and 24 U, respectively. Compared with bare GCE and GSCN/GCE, the Rct at the GSCN/Au@Pt/GCE is small, indicating high electron conduction pathways between the electrode and electrolyte due to the introduction of GN and Au@Pt

Fig. 8 Nyquist plot of [Fe(CN)6]3/4 obtained at GSCN/Au@Pt/GCE (blue line), GSCN/GCE (red line) and bare GCE (black line) in 0.10 M KCl solution containing 2.5 mM K3Fe(CN)6 and 2.5 mM K4Fe(CN)6.

Fig. 7 Typical TEM images of the obtained GSCN/Au NPs (a and b) and GSCN/Pt NPs (c and d) at different magnications.

hybrid NPs. Especially, the excellent conductivity and large specic area of GN contributes largely to the smallest Rct.58,59 Namely, these results imply that introduction of GN and Au@Pt hybrid NPs can dramatically improve the electron transfer ability of the hybrid nanostructure. Considering the particular structure of the as-prepared GSCN/ Au@Pt NPs mentioned above, the potential application based on this novel hybrid nanomaterial mentioned here is an extremely promising prospect. First, the obtained GSCN possesses a large surface area and high-density loading of metal NPs, which results in increased surface reactivity thus improving mass transport. Second, the functionalization of GSCN provides a versatile method to construct GN based hybrid nanomaterials, and diverse metal NPs can be anchored on the surface of the GSCN. At the same time, the GN supported nanomaterial is composed of two components and retains the excellent properties of both Au@Pt NPs and SnO2, such as their electrochemical and photocatalytical properties. Herein, we employ high-density Au@Pt NPs on GSCN as the electrochemical enhanced material for nonenzymatic glucose detection. Glucose is the mostly studied analyte of great biological importance.60 Amperometric glucose biosensors are one of the most promising methodologies with high sensitivity and selectivity. Most previous studies on this subject involved the use of enzymes (glucose oxidase).19,61 However, there are some disadvantages of the enzyme-modied electrodes, such as instability, high cost of enzymes, a complicated immobilization procedure, critical operating situation, etc. Recently, direct electrocatalytic oxidation of glucose at enzyme-free electrodes has exhibited obvious conveniences and advantages to avoid the drawbacks of the enzyme electrode.6264 Researchers in this eld are always enthusiastic towards nding new nanomaterials with good catalytic activities for highly sensitive sensing glucose. The present GSCN/Au@Pt provides a good opportunity to build a highly sensitive glucose electrochemical nonenzymatic sensor. The typical hydrogen adsorption-desorption peaks of GSCN/ Au@Pt determined by cyclic voltammetry measurement performed in 0.5 M H2SO4 electrolyte saturated with nitrogen at
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supported on GSCN could be used as enhanced materials for constructing a promising electrochemical sensor with high sensitivity for nonenzymatic glucose. It is expected that the above ternary hybrid materials will nd applications in other important elds, such as electronics and catalysis.

Acknowledgements
This research was supported by the National Natural Science Foundation of China (Nos. 20935003 and 20820102037) and 973 Project (Nos. 2009CB930100 and 2010CB933600).

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Notes and references


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Fig. 9 (a) CVs obtained at GSCN/Au@Pt/GCE and bare GCE in 0.5 M H2SO4 electrolyte saturated with nitrogen at a scan rate of 50 mV s1. (b) CVs obtained at GSCN/Au@Pt/GCE, GSCN/GCE and bare GCE in 0.1 M NaOH with and without 4 mM glucose at the scan rate of 0.05 V s1. (c) CVs at GSCN/Au@Pt/GCE in various concentrations of glucose: 2, 4, 6, 8, 10, 12, 14, 16, 18 and 20 mM from outer to inner. (d) Plot of electrocatalytic current of glucose vs. concentration.

a scan rate of 50 mV s1 is shown in Fig. 9a. This result further conrmed the successful assembling of Au@Pt NPs on the surface of the GSCN, which is consistent with the morphology analyses mentioned above. Fig. 9b shows the CVs of the GSCN/ Au@Pt NPs modied electrode (GSCN/Au@Pt/GCE) in 0.1 M NaOH with and without 4 mM glucose. Compared with the CV curve in the absence of glucose, anodic peaks located at 0.2 V were attributed to the oxidation of glucose. During the cathodic potential scan, the oxidation of glucose is suppressed in the high potential range because of the presence of surface oxide. With the reduction of Pt oxide, more surface-active sites are available for the oxidation of glucose, resulting in a decrease in the reduction peak of Pt oxide.65 For comparison, there is no signicant reduction behavior observed on bare GCE or GSCN/GCE under the same experimental conditions (inset of Fig. 9b). Fig. 9c shows CVs of the GSCN/Au@Pt/GCE in 0.1 M NaOH solution with different concentrations of glucose. The reduction current originating from the reduction of Pt oxide gradually decreases with increasing glucose concentration because of the oxidation of the analyte. Moreover, the calibration curve corresponding to the amperometric response (Fig. 9d) is linear against the concentrations of glucose ranging from 2 to 20 mM, (R 0.999) with a sensitivity of 20.3 mA mM1, which is superior or comparable to those reported in other literature,62,65,66 meaning that the GSCN/Au@Pt/GCE is promising for analytical applications.

4. Conclusion
In summary, we have developed a facile approach for synthesizing GSCN by direct reduction of GO and crystallization of SnO2 simultaneously. Owing to the introduction of PDDA, the as-prepared GSCN has been directly employed as a twodimensional support for self-assembly metal or hybrid NPs such as Au, Pt and Au@Pt hybrid NPs with high-density and good homogenity. Furthermore, the present high density Au@Pt NPs
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