Facile Electrodeposition of Flower-Like PMo 12-Pt / rGO Composite with Enhanced Electrocatalytic Activity towards Methanol Oxidation

A facile, rapid and green method based on potentiostatic electrodeposition is developed to synthesize a novel H3PMo12O40-Pt/reduced graphene oxide (denoted as PMo12-Pt/rGO) composite. The as-prepared PMo12-Pt/rGO is characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM) and X-ray photoelectron spectroscopy (XPS). The results reveal that graphene oxide (GO) is reduced to the rGO by electrochemical method and POMs clusters are successfully located on the rGO as the modifier. Furthermore, the PMo12-Pt/rGO composite shows higher electrocatalytic activity, better tolerance towards CO and better stability than the conventional pure Pt catalyst.


Introduction
Direct methanol fuel cells (DMFCs) have drawn increasing attention due to their simple operation, high energy density, low pollutant emission, low operating temperature (60-100 °C) and ease of handling liquid fuel [1][2][3].It is widely agreed that, as a single component catalyst, platinum shows OPEN ACCESS significant electrocatalytic activity for methanol oxidation at lower temperatures.However, there are two key problems inhibiting its utilization in DMFCs: (1) high cost of precious platinum and (2) pure Pt electrocatalysts are prone to deactivation/ poisoning by the reaction intermediates (mainly CO), which generate from incomplete oxidation of methanol and chemically adsorb onto the Pt surface and block the active sites [4].
In order to decrease the usage of pure Pt electrocatalysts, various nanostructured carbon materials have been used to effectively disperse metal nanoparticles.In particular, reduced graphene oxide (rGO) has been found as a promising candidate for catalyst support in DMFCs [5].Reduced graphene oxide (rGO) is gradually attracting more scientific and technological research interests due to its unique mechanical and electronic properties and wide applications [6,7].On the other hand, polyoxometalates (POMs) are early-row transition metal oxygen anionic clusters with a remarkable redox and photo-electrochemical properties [8].It was demonstrated [9] that Keggin-type PMo12O40 3−  anions in an aqueous solution could effectively convert carbon monoxide to carbon dioxide over catalysts, as represented by following equation.
[CO(g) + H2O + PMo12O40 3− (aq)→CO2(g) + 2H + (aq) + PMo12O40 5− (aq)] (1) In order to enhance CO tolerance in methanol oxidation and improve the durability of the Pt electrocatalysts, our group have studied the effects of silicotungstic acid (H4SiW12O40) on the electrocatalytic activity of Pt catalysts towards methanol oxidation, and found that silicotungstic acid can promote the further oxidation of intermediates such as CO and supplies enough active sites for methanol oxidation [10].Moreover, H3PMo12O40 can also enhance electrocatalysis of Pd toward formic acid electrooxidation.The addition of H3PMo12O40 contributes to converting CO into CO2, which reduces the poisoning effects of CO over Pd catalyst [11].All of these positive studies provide evidence that POMs could enhance antipoisoning ability of Pt in the methanol electrooxidation process on fuel cell anodes.
Up to now, many electrochemical methods have been used to reduce graphene oxide (GO) into reduced graphene oxide (rGO), such as cyclic voltammograms [12], potentiostatic electro deposition methods [13] and differential pulse voltammetry (DPV) [14].The experiment results reveal that the electrochemical approach is a relatively economic, fast and environmental friendly method to prepare graphene avoiding toxic and hazardous chemicals such as hydrazine or dimethylhydrazine in the reduction process [15].
In this study, we firstly report a facile, fast, scalable, economic and environmentally benign pathway to prepare PMo12-Pt/rGO composites.The electrochemical prepared approach can be undertaken via two steps (Figure 1): the first step involves direct electrochemical reduction of GO in suspension onto the substrate.Then, PMo12-Pt clusters on the substrate surface were also deposited by electrodeposition method in situ.As expected, the as-prepared PMo12-Pt/rGO composite exhibits superior catalytic activity on the electrochemical catalysis of methanol and CO oxidation.

Results and Discussion
Figure 2 displays the X-ray diffraction (XRD) patterns of rGO/indium tin oxide (rGO/ITO), Pt/rGO/ITO and PMo12-Pt/rGO/ITO, respectively.As shown in Figure 2a, the diffraction peaks located at 30.23°, 35.16°, 50.47° and 60.02° can be considered as ( 222), (400), ( 440) and (622) crystal planes of ITO [16].According to the ICDD PDF 04-0802, the diffraction peaks at 40.00°, 46.54°, 67.91° and 81.48° can be indexed to the (111), ( 200), ( 220) and (311) planes for Pt.These diffraction peaks are found in Figure 2b,c, which suggest that the successful formation of Pt on the rGO film by electrodeposition in situ.However, the diffraction peaks of Pt crystal planes (curve c) slightly shift comparing with curve (b).It may be as a result of the interaction among rGO, PMo12 and Pt.There are no distinct diffraction peaks of PMo12, which may be due to the characteristic diffraction pattern of crystalline PMo12 being absent, which further implies that PMo12 clusters do not exist in the crystalline state but in the dispersed state [17].The presence of Pt, P, Mo, C, N, and O elements on the surface of the composite is confirmed in the full-spectra of X-ray photoelectron spectroscopy (XPS) (Figure 3a).As shown in Figure 3b, the C1s XPS spectrum of the prepared composite show that there are four kinds of carbon atoms in different functional groups: C-C/C=C bonds (284.6 eV), C-O bands (286.7 eV), C=O bands (287.5 eV) and O-C=O bands (288.5 eV) [18,19].The C1s spectrum of GO shows the presence of two typical carbon bonds: C-C/C=C (284.6 eV) and C-O (286.7 eV) (Figure 3e).After electrochemical reduction, only the C-C/C=C bands remain dominant, which implies that the functional groups such as carboxyl groups, hydroxyl groups, and epoxy groups are reduced and detached from graphene surface.In Pt (4f) XPS of the composite (Figure 3c), the principle peaks are attributed to Pt° at 71.2 eV (4f7/2) and 74.6 eV (4f5/2) [20], while peaks at 72.1, 75.9 and 74.4,77.5 eV are assigned to Pt in +2 and +4 states [21,22], respectively.The results of different Pt species are calculated based on above data and listed in Table S1.After electrolytic deposition by cyclic voltammetry, the relative intensity of Pt°, Pt 2+ and Pt 4+ are calculated to be 62.92%, 26.57% and 10.51% for prepared composite, respectively.However, in contrast, the proportion of Pt° on the surface is only 36.3% via chemical synchronous reduction [23].Thus, the preparation method we used can effectively improve the content of Pt°.Moreover, the Mo 3d core level spectrum displays two peaks at binding energies of 232.8 eV and 236.0 eV, corresponding to the Mo 3d3/2 and Mo 3d5/2 spin-orbit states of PMo12, respectively (Figure 3d) [24], which indicated the presence of PMo12 in the composite.Raman spectroscopy is a powerful nondestructive technique that is widely used to distinguish order and disorder in the crystal structure of carbon [25].Figure 4 presents the Raman spectra of GO and PMo12-Pt/rGO, respectively.Two groups of typical characteristic peaks of D bands and G bands can be observed at about ~1320 and ~1590 cm −1 , respectively.The D band originates from the disordered structural defects or edge areas, and the G band is associated with the in-plane vibration of sp 2 bonded carbon atoms [26].Meanwhile, the intensity ratio of D and G bands (ID/IG) can be used to evaluate the extent of defects in carbonaceous materials.The ID/IG value of PMo12-Pt/rGO is estimated about 1.80, which is higher than that of GO (1.33).The increase suggests the realization of deoxygenation during the reduction of GO [27].5a, when the deposition potential is −0.2 V, the coral-like clusters shape up on the rGO surface with the 100-800 nm diameters and less aggregation.When the deposition potential is −0.3 V, they are composed of flower-like clusters (Figure 5b) and the diameter is in range from 450 to 900 nm.Each flower-like cluster (Figure 5b inset) is three-dimensional, spear-shaped and multi-faceted.The mean diameter is of ~100 nm.These special structures may provide a larger specific surface area compared with other morphologies.When the deposition potential is decreased to −0.4 V, the PMo12-Pt/rGO/ITO composite is in an irregular shape (Figure 5c).The catalytic activity of the different modified electrodes was studied in a conventional three electrode system in 0.5 M H2SO4 + 1 M CH3OH electrolyte solutions at a scan rate of 100 mV•s −1 .Figure 6 presents the steady state cyclic voltammograms of Pt, Pt/rGO, PMo12-Pt/rGO deposited on glassy carbon electrodes, referring to the Ag/AgCl electrode.The forward scan current density (If) of PMo12-Pt/rGO/glass carbon electrode (PMo12-Pt/rGO/GCE) was 269.1 mA•cm −2 •mg −1 Pt, but it was 176.6 mA•cm −2 mg −1 Pt for Pt/rGO/GCE catalysts and only 147.9 mA•cm −2 mg −1 Pt for Pt/GCE catalysts.It is evident that the forward peak current value of PMo12-Pt/rGO/GCE (about 269.1 mA•cm −2 •mg −1 Pt) is 1.52 times higher than that of Pt/rGO/GCE (about 176.6 mA•cm −2 mg −1 Pt), which indicates that PMo12-Pt clusters have better catalytic activity for methanol electrooxidation.The result may be explained as following: the poisonous intermediates such as CO that are absorbed on the active sites of Pt nanoparticles significantly can be catalytically oxidized by POMs, which results in the increased electrocatalytic activity of PMo12-Pt clusters [28].Therefore, PMo12-Pt/rGO/GCE modified electrode for the oxidation of methanol in acidic medium shows better catalytic activity than Pt/rGO/GCE and Pt/GCE.The short-term stability of the catalysts was investigated by accelerated aging tests, which were performed by running the 1st time and 100 times between −0.20 V and 1.0 V with a scan rate of 0.10 V•s −1 in 0.5 M H2SO4 and 1 M CH3OH aqueous solution for the catalysts are presented in Figure 7a-c.The peak for the Pt/GCE have the same change characteristics as that for the other electrodes with the increasing cycling number, but the electricity density for the Pt/GCE declines faster than the other electrodes (Figure 7a).However, for the Pt/rGO/GCE (Figure 7b) and PMo12-Pt/rGO/GCE composite (Figure 7c), the current densities decline 11.33% and 6.99% (Table S2), respectively.Therefore, the PMo12-Pt/rGO/GCE has better short-term stability than the other two.To evaluate the long-term performance of the three electrodes for methanol oxidation (in 0.5 M H2SO4 + 1 M CH3OH solution), they were polarized at 0.68 V for 7200 s.As shown in Figure 8, a rapid initial current density decay is observed, due to the formation of some intermediate species (mainly COads) during the methanol oxidation reaction [29].Then the currents slowly decrease and reach a quasi-stationary state within 7200 s.As observed from Figure 9, the current densities at 7200 s are 6.18, 4.60, 2.81 mA•cm −2 mg −1 •Pt towards methanol oxidation, respectively.The maximum steady-state oxidation current density for PMo12-Pt/rGO/GCE is the largest compared to those of other electrodes.Thus, it confirms that the combination of PMo12-Pt and rGO enhance electrocatalytic performance of the Pt catalyst.Efficient elimination of the poisoning species such as CO from the catalyst is very important for assessing the catalyst performance in DMFCs.Figure 10 shows the voltammograms of CO oxidation on the different modified electrodes.As seen in Figure 10c, the distinct CO oxidation peak appears during the first forward scan, whereas it disappears in the second forward scan, indicating that the adsorbed CO on the surface of PMo12-Pt/rGO nanoparticles has been oxidized during the first forward scan [31].The PMo12-Pt/rGO/GCE exhibited the more negative peak potential (0.647 V), while the peak potential of Pt/rGO/GCE and Pt/GCE only 0.687 V and 0.729 V, respectively.The negatively shifted peak potentials indicate that CO species on the PMo12-Pt/rGO interfaces are more easily transformed to CO2 due to the oxidation ability of PMo12 [32].Therefore, the active sites on Pt are released for further electrochemical reaction.

Preparation of Reduced Graphene Oxide (rGO) Modified Electrode
Graphite oxide was prepared from graphite powder by a modified Hummers' method [33,34].To obtain a homogeneous suspension, Graphite oxide was mixed with deionized water and ultrasonicated for 2 h.The as-prepared GO suspension was coated onto an indium tin oxide (ITO) glass or glass carbon electrode (GCE) to form GO film.The rGO film was prepared upon electrochemically reduction of GO film in 0.1 M Na2SO4 at a constant potential of −1.5 V for 600 s. (Figure 1).

Synthesis of PMo12-Pt/rGO
PMo12-Pt clusters were deposited in situ on the surface of the rGO film-modified GCE (3 mm in diameter) or ITO electrode (4 mm in width) by potentiostatic electrodeposition in a 0.5 M H2SO4 solution containing 2 mM H2PtCl6 and 0.2 mM PMo12 at −0.3 V for 600 s.After deposition, the working electrode was rinsed with distilled water and dried under an infrared lamp.For comparison, the electrodeposition of platinum on the surface of bare GCE or ITO, and rGO was also performed under the same conditions.

Characterization
XPS was performed at room temperature with monochromatic Al Kα radiation (1486.6 eV) using a Quantum 2000 system (PHI, Chanhassen, MN, USA).XRD patterns were measured on an X'pert Pro diffractometer (Philips, Almelo, The Netherlands), using Cu Kα radiation.Field emission scanning electron microscopy (FE-SEM) images were observed on a JSM-7500F field emission scanning electron microanalyzer (JEOL, Tokyo, Japan).EDS was used to confirm the existence of Pt particles.Ramam spectra was measured using a Renishaw-in-Via Raman (Renishaw, London, UK) micro-spectrometer equipped with 514 nm diode laser excitation on a 300 lines•mm −1 grating.The actual amount of Pt loadings of the catalysts was determined by inductively coupled plasma-mass spectroscopy (ICP-MS, X Series 2, Thermo Scientific, Waltham, MA, USA).

Electrochemical Measurements
Electrochemical measurements were conducted on a CHI660 Electrochemical Workstation (Chenhua, Shanghai, China) using a conventional three-electrode electrochemical system.The working electrode was a glassy carbon electrode (geometric area, 0.07 cm 2 ) modified with the catalysts; Ag/AgCl electrode and Pt wire were used as the counter and reference electrode, respectively.Cyclic voltammetric, EIS and chronoamperometric experiments were carried out in 0.5 M H2SO4 in the absence and presence of 1 M methanol.The electrolyte solution was deaerated with ultrahigh-purity N2 before scanning.The CO stripping voltammograms were measured by oxidation of preadsorbed CO (COad) in the 0.5 M H2SO4 solution at a scan rate of 100 mV•s −1 .CO was bubbled for 30 min to allow the complete adsorption of CO onto the composites when the potential was kept at 0.1 V. Excess CO in the electrolyte was then purged out with N2 for 15 min.
CO-stripping curves of Pt/GCE, Pt/rGO/GCE, and PMo12-Pt/rGO/GCE in 0.5 M H2SO4 solution is collected to evaluate the electrochemical surface areas (ECSA).All the composites show characteristic CO oxidation peak in the first forward scan, suggesting the presence of electrochemically active Pt.The ECSA were calculated by the integrated charge (Q) in the CO oxidation region.According to the equation ECSA = Q/(420 μC•cm −2 × Pt loading), we have added the Pt load for each sample in Table S3.

Conclusions
In this work, a unique flower-like PMo12-Pt/rGO composite has been successfully synthesized by the electrochemical reduction method and used as an electrocatalyst for methanol oxidation.Cyclic voltammetry, chronoamperometry and CO stripping voltammetry were used to study electrocatalytic properties of PMo12-Pt/rGO composite in acidic medium for methanol oxidation.The PMo12-Pt/rGO composite modified electrode shows higher catalytic activity, better electrochemical stability and resistance to CO poisoning, which may be attributed to the synergistic effect of the special morphology of the composite, excellent conductivity of rGO and superior redox properties of PMo12.These findings suggest that the PMo12-Pt/rGO composite can be considered as a good electrocatalyst material for DMFCs.

Figure 5
Figure5displays the SEM images of different composites.Figure5a-c are the surface morphology of PMo12-Pt/ rGO/ITO composite, which are deposited at different electrode potentials.As shown in Figure5a, when the deposition potential is −0.2 V, the coral-like clusters shape up on the rGO surface with the 100-800 nm diameters and less aggregation.When the deposition potential is −0.3 V, they are composed of flower-like clusters (Figure5b) and the diameter is in range from 450 to 900 nm.Each flower-like cluster (Figure5binset) is three-dimensional, spear-shaped and multi-faceted.The mean diameter is of ~100 nm.These special structures may provide a larger specific surface area compared with other morphologies.When the deposition potential is decreased to −0.4 V, the PMo12-Pt/rGO/ITO composite is in an irregular shape (Figure5c).Figure 5b,d and e presents the SEM images of PMo12-Pt/rGO/ITO (b), Pt/rGO/ITO (d) and PMo12-Pt/ITO (e) obtained from deposition potential of −0.3 V, respectively.As shown in Figure 5d, Pt clusters are spherical with diameters in the range of 100-450 nm and less aggregation.By contrast, PMo12-Pt clusters are the same morphology as Pt/rGO with big size distribution (150-900 nm) in Figure 5e.It suggests that the introduction of the PMo12 and rGO may have an impact on the formation of the structure of clusters.Energy dispersive spectroscopy (EDS) analysis in Figure 5f identifies the presence of Pt, P, Mo, C, N and O on the PMo12-Pt/rGO/ITO electrode and further confirms that PMo12, Pt, and rGO are present in the composite.
Figure5displays the SEM images of different composites.Figure5a-c are the surface morphology of PMo12-Pt/ rGO/ITO composite, which are deposited at different electrode potentials.As shown in Figure5a, when the deposition potential is −0.2 V, the coral-like clusters shape up on the rGO surface with the 100-800 nm diameters and less aggregation.When the deposition potential is −0.3 V, they are composed of flower-like clusters (Figure5b) and the diameter is in range from 450 to 900 nm.Each flower-like cluster (Figure5binset) is three-dimensional, spear-shaped and multi-faceted.The mean diameter is of ~100 nm.These special structures may provide a larger specific surface area compared with other morphologies.When the deposition potential is decreased to −0.4 V, the PMo12-Pt/rGO/ITO composite is in an irregular shape (Figure5c).Figure 5b,d and e presents the SEM images of PMo12-Pt/rGO/ITO (b), Pt/rGO/ITO (d) and PMo12-Pt/ITO (e) obtained from deposition potential of −0.3 V, respectively.As shown in Figure 5d, Pt clusters are spherical with diameters in the range of 100-450 nm and less aggregation.By contrast, PMo12-Pt clusters are the same morphology as Pt/rGO with big size distribution (150-900 nm) in Figure 5e.It suggests that the introduction of the PMo12 and rGO may have an impact on the formation of the structure of clusters.Energy dispersive spectroscopy (EDS) analysis in Figure 5f identifies the presence of Pt, P, Mo, C, N and O on the PMo12-Pt/rGO/ITO electrode and further confirms that PMo12, Pt, and rGO are present in the composite.