Preparation and Electrocatalytic Property of Pt/{GN/CuPW11}n Composite Films toward Methanol Oxidation

doi:10.15541//jim20160684

Abstract

Abstract:

Composite films consisting of graphene and CuPW₁₁ polyoxometalates {GN/CuPW₁₁}_n, were prepared by layer-by-layer (LBL) assembly and used as a support for electro-deposition of Pt nanoparticles by cyclic voltammetry. The component and surface morphology of the multilayer composite films were characterized by AFM, SEM, XRD and XPS. The results indicate that {GN/CuPW₁₁}₄ composite multilayer films exhibit even and uniform distribution and Pt nanoparticles on the surface of {GN/CuPW₁₁}₄ composite multilayer films display flower-like cluster shape. Pt in the Pt/{GN/CuPW₁₁}₄composite multilayer films mainly exists in the form of Pt(0) but some exists in the form of Pt(Ⅱ) and Pt(Ⅳ). The electrocatalysis experiment results show that introduction of CuPW₁₁ evidently improves electrocatalytic activity, stability and CO tolerance ability of Pt/graphene composite catalysts toward methanol oxidation.

Key words: direct methanol fuel cell, graphene, polyoxometalates, electrodeposition technique, electrocatalytic oxidation

CLC Number:

ZHANG Yi, ZHANG Xiao-Feng, He Xiao-Lei, HUANG Huo-Di, LE Li-Juan, LIN Shen. Preparation and Electrocatalytic Property of Pt/{GN/CuPW₁₁}_n Composite Films toward Methanol Oxidation[J]. Journal of Inorganic Materials, 2017, 32(10): 1075-1082.

Figures/Tables 11

Fig. 1 Cyclic voltammograms of Pt/{GN/CuPW11}n multilayer nanocomposites with different layers in 0.5 mol/L H2SO4 + 1 mol/L CH3OH solution

Fig. 2 (A) Cyclic voltammograms of Pt/{GN/CuPW11}4 in 0.5 mol/L H2SO4 + 1.0 mol/L CH3OH solution at different scan rates and (B) relationship between the current peaks and the square root of scan ratesThe scan rates from a to g in Fig. 2(A) were 10, 22.5, 40, 62.5, 90, 122.5, 160 mV/s, respectively

Fig. 3 Cyclic voltammograms of different modified electrodes(a) {GN/CuPW11}4, (b) Pt, (c) Pt/{GN/PW12}4, (d) Pt/{GN/ CuPW11}4 in 0.5 mol/L H2SO4 + 1.0 mol/L CH3OH solution. Scan rate: 100 mV/s

Fig. 4 Comparative cyclic voltammograms of the different modified GCE electrodes(a) Pt, (b) Pt/{GN/PW12}4, (c) Pt/{GN/CuPW11}4 at 1st time and 100th times in 0.5 mol/L H2SO4 + 1.0 mol/L/CH3OH solution. Scan rate: 100 mV/s

Fig. 5 Chronoamperometric curves of different modified electrodes(a) Pt, (b) Pt/{GN/PW12}4, (c) Pt/{GN/CuPW11}4 in 0.5 mol/L H2SO4 + 1.0 mol/L CH3OH solution at a fixed potential of 0.68 V for 2 h.

Fig. 6 CO-stripping curves of different modified electrodes(a) Pt, (b) Pt/{GN/PW12}4, (c) Pt/{GN/CuPW11}4 in 0.5 mol/L H2SO4 solution. Scan rate: 100 mV/s

Fig. 7 Nyquist plots of EIS with different films modified electrodes in 0.5 mol/L H2SO4 + 1.0 mol/L CH3OH solution(a) Pt; (b) Pt/{GN/PW12}4; (c) Pt/{GN/CuPW11}4

Fig. 8 AFM images of {GN/CuPW11}4 multilayer films(a) Height profile; (b) 3D image; (c) 2D image

Fig. 9 XRD patterns of the {GN/CuPW11}4 (curve a), Pt/{GN/CuPW11}4 (curve b)

Fig. 10 XPS spectra of Pt/{GN/CuPW11}4 multilayer films(a) Full spectra; (b) C1s spectra; (c) Pt4f spectra; (d) W4f spectra

Fig. 11 SEM images of Pt/{GN/CuPW11}4 composites at different cycling potentials(a,b) 0-0.6 V; (c,d) -0.15-0.6 V; (e,f) -0.3-0.6 V. Scan rate: 100 mV/s

References 19

[1]	WANG H, TUMER J A.Austenitic stainless steels in high temperature phosphoric acid.Journal of Power Sources, 2008, 180(2): 803-807.
[2]	LI C, YANG X, ZHANG G.Mesopore-dominant activated carbon aerogels with high surface area for electric double-layer capacitor application.Materials Letters, 2015, 161: 538-541.
[3]	GEIM A K.Graphene: status and prospects.Science, 2009, 324(5934): 1530-1534.
[4]	CHEN D, TANG L, LI J.Graphene-based materials in electrochemistry.Chemical Society Reviews, 2010, 39(8): 3157-3180.
[5]	POPE M T, MUILER A.Polyoxometalates: from Platonic Solids to Snti-retroviral activity. Springer Science & Business Media, 1994, 10.
[6]	LEE J, KIM J, CHOI W.Oxidation on zerovalent iron promoted by polyoxometalate as an electron shuttle.Environmental Science & Technology, 2007, 41(9): 3335-3340.
[7]	HE X, CHEN L, LI Z, et al.Enhanced electrocatalysis for methanol oxidation on ordered {[PdPW11O39]5-/Pt/PAMAM}n multilayer composites.Fuel Cells, 2015, 15(1): 221-229.
[8]	LE L, ZHANG X, MA A, et al.Facile synthesis of Pd/PDDA- GN/PMo11Co composite and its enhanced catalytic performance for formic acid oxidation.RSC Advances, 2016, 6(109): 107370-107378.
[9]	贺鹤鸣, 孙铁. P-Cu-Mo 杂多阴离子柱撑水滑石的制备. 高等学校化学学报, 1993, 14(10): 1349-1350.
[10]	YU F, WANG R.Deep oxidative desulfurization of dibenzothiophene in simulated oil and real diesel using heteropolyanion- substituted hydrotalcite-like compounds as catalysts.Molecules, 2013, 18(11): 13691-13704.
[11]	SHAHRIARY L, ATHAWALE A A.Graphene oxide synthesized by using modified hummers approach.Int. J. Renew. Energy Environ. Eng., 2014, 2: 58-63.
[12]	ZHU H, GUO Z, ZHANG X, et al.Methanol-tolerant carbon aerogel-supported Pt-Au catalysts for direct methanol fuel cell.International Journal of Hydrogen Energy, 2012, 37(1): 873-876.
[13]	HERRANZ T, GARCIA S, MARTINEZ-HUERTA M V, et al. Electrooxidation of CO and methanol on well-characterized carbon supported PtxSn electrodes. Effect of crystal structure.International Journal of Hydrogen Energy, 2012, 37(8): 7109-7118.
[14]	LI Z S, LIN S, CHEN Z, et al.In situ electro-deposition of Pt micro- nano clusters on the surface of {[PMo12O40]3-/PAMAM}n multilayer composite films and their electrocatalytic activities regarding methanol oxidation.Journal of Colloid and Interface Science, 2012, 368(1): 413-419.
[15]	SALGADO J R C, ALCAIDE F, ÁLVAREZ G, et al. Pt-Ru electrocatalysts supported on ordered mesoporous carbon for direct methanol fuel cell.Journal of Power Sources, 2010, 195(13): 4022-4029.
[16]	NASEER R, MAL S S, IBRAHIM M, et al.Redox, surface and electrocatalytic properties of layer-by-layer films based upon Fe (III)- substituted crown polyoxometalate [P8W48O184Fe16(OH)28(H2O)4]20.Electrochimica Acta, 2014, 134: 450-458.
[17]	SUN Z, HE J, KUMBHAR A, et al.Nonaqueous synthesis and photoluminescence of ITO nanoparticles.Langmuir, 2010, 26(6): 4246-4250.
[18]	LIU R, LI S, YU X, et al.A general green strategy for fabricating metal nanoparticles/polyoxometalate/graphene tri-component nanohybrids: enhanced electrocatalytic properties.Journal of Materials Chemistry, 2012, 22(8): 3319-3322.
[19]	ZHANG X, HUANG Q, LI Z, et al.Effects of silicotungstic acid on the physical stability and electrocatalytic activity of platinum nanoparticles assembled on graphene.Materials Research Bulletin, 2014, 60: 57-63.

Preparation and Electrocatalytic Property of Pt/{GN/CuPW₁₁}_n Composite Films toward Methanol Oxidation

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