Preparation of Pt Ag alloy nanoisland/graphene hybrid composites and its high stability and catalytic activity in methanol electro-oxidation
© Feng et al; licensee Springer. 2011
Received: 20 June 2011
Accepted: 7 October 2011
Published: 7 October 2011
In this article, PtAg alloy nanoislands/graphene hybrid composites were prepared based on the self-organization of Au@PtAg nanorods on graphene sheets. Graphite oxides (GO) were prepared and separated to individual sheets using Hummer's method. Graphene nano-sheets were prepared by chemical reduction with hydrazine. The prepared PtAg alloy nanomaterial and the hybrid composites with graphene were characterized by SEM, TEM, and zeta potential measurements. It is confirmed that the prepared Au@PtAg alloy nanorods/graphene hybrid composites own good catalytic function for methanol electro-oxidation by cyclic voltammograms measurements, and exhibited higher catalytic activity and more stability than pure Au@Pt nanorods and Au@AgPt alloy nanorods. In conclusion, the prepared PtAg alloy nanoislands/graphene hybrid composites own high stability and catalytic activity in methanol electro-oxidation, so that it is one kind of high-performance catalyst, and has great potential in applications such as methanol fuel cells in near future.
Graphene, a single-atom-thick sheet of hexagonally arrayed sp 2-bonded carbon atoms, has attracted intensive interests in recent years , owing to its large specific surface area, high thermal and electrical conductivities [2–6], great mechanical strength . The unique properties of graphene sheets provide applications in synthesis of nanocomposites [8–10], fabrication of field-effect transistors [11–13], dye-sensitized solar cells , lithium ion batteries [15, 16], and electrochemical sensors . Up to date, many methods such as a scotch tape (peel off) method , epitaxial growth [19, 20], chemical vapor deposition , and reduction of graphene oxide [22–26] have been used to prepare individual graphene sheets and to improve the properties of graphene. Among these methods, chemical reduction method of graphene oxide is with lowest cost and large scale to prepare graphene, which attract scientists' intensive attention, and exhibit great application prospect.
In the field of electrochemistry, graphene is an excellent substrate to load active nanomaterials for energy applications due to its high conductivity, large surface area, flexibility, and chemical stability. For example, Dai and colleagues  made high-capacity anode material for lithium ion batteries by growing Mn3O4 nanoparticles (NPs) on graphene sheets. Zhang et al.  prepared mono-dispersed SnO2 NPs on both sides of single layer graphene sheets as anode materials in Li-ion batteries. They found much higher retention of SnO2-graphene composite than commercial SnO2 powder after 50 cycles. Apart from these studies, a lot of efforts had been paid on metal oxide/graphene hybrid composites . However, so far, few reports are closely associated with the use of graphene-based metal materials as heterogeneous catalysts [28–30]. Therefore, to prepare and study graphene/noble metal, heterogeneous materials become more and more important.
In the field of catalysis, Pt (and Pd) is intensively applied in direct methanol fuel cells (DMFCs) [31, 32], because of their high-efficient catalysis function for methanol dehydrogenation. To improve catalytic properties of the metal materials, the size and structure of NPs become more and more important. Pt NPs with several nanometers in diameter and porous structures own high catalytic activity because of their enlarged surface area. In addition, the composition of the catalyst is another important factor for catalytic activity. For instance, pure Pt nanostructures are easily poisoned by chemisorbed CO-like intermediates generated in the course of methanol oxidation, which makes their catalytic performance decreased quickly. To solve this problem, it is feasible to prepare bimetallic nanocomposites composed of Pt and those metals such as Ru, Rh, Pd, and Au [33–37]. Other metal materials are proposed to provide oxygen-containing species at relative negative potential, which can oxidize CO at Pt sites. Therefore, to prepare alloyed Pt NPs are very necessary. Wu and colleagues had proved that PtAg alloy nanoislands on gold nanorods had good optical responses and electrochemical catalytic activity [38, 39]. However, up to date, graphene-based PtAg alloy nanoislands as heterogeneous catalysts are not still investigated well.
In this study, we reported to prepare PtAg alloy nanoislands/graphene hybrid composites based on the self-assembly of positively charged gold nanorods and Au@AgPt alloy nanorods on negatively charged graphene sheets. (Here "@" was defined as a core/shell structure. Au@AgPt alloy nanorod is a core/shell structure for Au nanorod as the core and AgPt alloy as the shell. We use Au@Pt m Ag n to represent the samples, and m and n are percentage determined by EDX.) The self-assembly technology enables loading a lot of Au NRs and Au@AgPt alloy nanorods on individual graphene sheets with uniform morphology. It was investigated that the prepared Au@AgPt alloy nanorods/graphene hybrid composites were used as a fuel cell electrocatalyst for methanol electro-oxidation. The utilization ratio of Pt was 23.4%, but its catalytic activity was 124 mA mg Pt-1, which was close to 162.5 mA mg Pt-1 (99.2% utilization ratio of Pt) reported previously . In addition, Pt material has also good catalytic stabilization, which shows that catalytic activity may increase with the utilization ratio of Pt increase, further investigation will be helpful to clarify its potential mechanism.
10000 mesh (dimension: 1.5µm) graphite, etyltrimethylammonium bromide (CTAB), PVP (K30, Mw = 30000-40000) were obtained from Alfa Company and used as-received. Sodium borohydride (NaBH4), chlorauric acid (HAuCl4·3H2O), silver nitrate (AgNO3), and potassium tetrachloroplatinate(II) (K2PtCl4), L-ascorbic acid (AA), methanol, sulfuric acid, potassium permanganate (KMnO4), hydrogenperoxide (H2O2), sodium nitrate (NaNO3), were purchased from Shanghai Sigma Company and used as-received. Milli-Q water (18 MΩ cm) was used for all solution preparations. All glassware used in the following procedures were cleaned in a bath of a piranha solution (H2SO4/30%H2O2 = 7:3 v/v) and boiling for 30 min.
Synthesis of graphene nanosheets
Graphene oxides (GO) were synthesized from flake graphite (1.5 µm graphite) using modified Hummer's method [41, 42]. Then graphite oxides were exfoliated by ultrasonication for more than 5 h. Well-dispersed homogeneous graphene oxide solution (0.5 mg mL-1) was obtained. PVP was used to prevent flocculation when reduced graphene oxide to graphene sheets. In a typical procedure for chemical conversion of graphene oxide to graphene (GN), 100 mL 8 mg mL-1 PVP solution was added to 50 mL 0.5 mg mL-1 GO solution, then stirred vigorously for more than 12 h. Afterward, 1.75 mL 0.5% hydrazine solution and 2 mL 2.5% ammonia solution were added. The mixture was stirred for 1 h at 95°C. After that, graphene was cooled at room temperature. The whole reduction process was repeated once more to reduce GO further. The stable black dispersion of GN was filtered under the condition of vacuum with 200 nm membrane as filter paper to collect it, at the same time it was washed with Milli-Q water (18 MΩ cm). Finally, the prepared GNs were dissolved in 50 mL water (0.5 mg mL-1).
Growth of Au@AgPt nanorods
Au@AgPt nanorods were prepared using an etching method described by Wu . The specific process is consisted of four steps: (1) Au nanorods synthesis; (2) precoat a thin Pt layer on Au nanorod ; (3) grow Ag shell on Au@Pt NRs; and (4) etch Ag shell with Pt (II) ions.
Hybrid of graphene and Au nanorods
A certain volume of 0.5 mg mL-1 GNs was added to 1 mL of the gold nanorods solution (0.5 mmol L-1) or Au@AgPt nanorods solution. The mixture solution was then shaken vigorously and sonicated for 30 s. Afterward, the mixture was left undisturbed and aged at room temperature for more than 24 h. The color of the solution changed from red (Au nanorods) or dark gray (Au@AgPt nanorods) to colorless, and the hybrid composites precipitated at the bottom of the vessel. Afterward, the precipitate was collected by centrifugation (12000 rpm for 5 min). Finally, the precipitate was redispersed in 100 µL water for electrochemical testing.
UV-Vis-NIR absorption spectra were obtained from a Varian Cary 50 spectrophotometer. Scanning electron microscopy (SEM) images and energy dispersive X-ray (EDX) analysis were taken on a field emission scanning electron microscope (FESEM, Zeiss Ultra). Transmission electron microscopy (TEM) images were captured on a JEM-2010/INCA OXFORD at an accelerating voltage of 200 kV. Zeta potential results were carried out on zeta potential/particle sizer (Nicom 380ZLS). CHI660C electrochemical workstation (Chenhua, Shanghai) was carried out for the electrochemical measurement. Cyclic voltammetry was performed in a three-electrode glass cell at room temperature. Glassy carbon (GC) electrode was used as working electrode. Before testing, the electrode was rejuvenated by polished with 0.3 and 0.05 µm alumina powders, respectively, then sonicated sequentially in alcohol, pure water in each for about 20 min. 5 μL as-prepared samples were drop-casted onto GC electrodes, and dried overnight in vacuum conditions. A platinum wire and an Ag/AgCl (saturated KCl) electrode were used as counter electrode and reference electrode, respectively. The electrolyte solution was purged with high-purity nitrogen for 30 min and protected under nitrogen during the measurements. Methanol was electro-oxidized in an electrolyte containing 0.5 mol L-1 H2SO4 and 2 mol L-1 CH3OH in the potential range of -0.25 to 1.0 V at a sweep rate of 50 mV s-1.
Results and discussion
Characterization of Pt Ag alloy nanoisland/graphene hybrid composites
Average zeta potential measured at 25°C
Zeta potential (mV)
TEM was also carried out for the sample of weight ratio 2:1 and 5:1 (see "Figure S2 in Additional file 1"). In the case of weight ratio 2:1, graphene could easily be recognized from the fringe and some pleats of graphene sheets (marked by red arrows). When weight ratio was 5:1, apart from uniformly distributed Au NRs, graphene sheets could not be seen clearly, which is because it was quite hard to make a distinction between them and the carbon-supported films on the copper grid due to the thin thickness of graphene sheets. SEM and TEM images both showed that self-assembly method was effective in producing homogeneous high-loading nanorods on the surface of graphene. The procedure of preparing graphene/Au@PtAg NRs hybrids was similar to that of graphene/Au NRs hybrids except for using Au@PtAg NRs as precursor for self-assembly. In the following experiment, we used the hybrid composition of weight ratio 5:1 for methanol electro-oxidation.
Catalytic activity for methanol electro-oxidation
Utilization of Pt and the electrochemical properties of the Pt electrocatalysts
Another important parameter to value catalytic activity of the samples is onset potential in electrical oxidation process. In forward sweep, all the samples had the same onset potentials (0.216 V). Otherwise, in backward sweep, sample b had frontier onset potentials (up to 124 mV) than sample a (without graphene). As mentioned above, the oxidation current of methanol oxidation in backward sweep represented the removal activity of the incompletely oxidized carbonaceous species (usually CO adsorbed on sample surface) generated in the forward sweep. The frontier onset potentials of graphene/Au@PtAg alloy NRs hybrid compositions indicated easier remove of the incompletely oxidized carbonaceous species. This phenomenon was very similar to that discovered by Yoo et al. before. In their research, Yoo et al. had done COad stripping voltammograms to explain the role graphene played in this reaction. The different state of CO adsorption on Pt/graphene was inferred to traditional Pt catalysts supported on carbon black . In our study, the values of I f /I b were 1.46 and 1.24, respectively, for graphene/Au@PtAg alloy NRs hybrid compositions (the first sweep) and Au@PtAg alloy NRs (the 25th sweep) without graphene. The different onset potential and I f /I b value in backward sweep could be attributed to different CO adsorption state. The different CO adsorption state on graphene/Au@PtAg alloy NRs hybrid compositions and ordinary PtAg alloy NRs materials influenced the catalytic activity for methanol electrooxidation. Graphene in hybrid compositions could enhance anti-poisoning effect in the backward sweep. Graphene in the hybrid composition could change adsorption state of reactant, so the electrochemical process was affected. The higher oxidation peak in the first cycle of graphene/Au@PtAg alloy NRs hybrid compositions might result from the different interaction between graphene and methanol. Therefore, graphene in the hybrid compositions could improve the catalytic activity for methanol electrooxidation.
In addition, graphene had the advantages of good dispersion, high conductivity, large surface area, flexibility, and chemical stability. The higher catalytic activity of graphene architecture was attributed to the larger surface area which led to large currents and good dispersion of Au@PtAg NRs on the surface. The good dispersion of Au@PtAg NRs on graphene would give reactants easy access to the catalytic active sites, which would help to improve proton diffusion and mass transport.
In this study, PtAg alloy nanoislands/graphene hybrid composites based on self-assembling of Au@PtAg NRs on graphene sheets were successfully prepared. The high-loading Au@PtAg NRs distributed uniformly on the surface of graphene sheets. It is confirmed that PtAg alloy nanoislands/graphene hybrid composites own better catalytic activity and longer stabilization for methanol oxidation compared with traditional method. Because large-scale graphene can be prepared by chemical reduction of graphene oxide; therefore, the PtAg alloy nanoislands/graphene hybrid composites can be obtained by large scale with low cost; therefore, as-prepared PtAg alloy nanoislands/graphene hybrid composite has great potential in applications such as electro-catalyst for DMFCs in near future.
This study was supported by the National Key Basic Research Program (973 Project) (2010CB933901), the Important National Science & Technology Specific Project (2009ZX10004-311), the National Natural Scientific Fund (No. 20803040), the Special project for nano-technology from Shanghai (No. 1052nm04100), the New Century Excellent Talent of Ministry of Education of China (NCET-08-0350), and the Shanghai Science and Technology Fund (10XD1406100).
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