Pt/{GN/CuPW11}n复合膜的制备及其对甲醇氧化电催化性能

doi:10.15541//jim20160684

摘要/Abstract

摘要：

利用层接层自组装法(Layer-by-Layer assembly, LBL)制备过渡金属取代多金属氧酸盐CuPW₁₁与石墨烯的复合膜{GN/CuPW₁₁}_n, 再通过恒电位法将Pt纳米粒子电沉积到复合膜上得到Pt/{GN/CuPW₁₁}_n复合膜催化剂。用AFM、SEM、XRD和XPS对Pt/{GN/CuPW₁₁}₄复合多层膜的组分和表面形貌进行了表征, 结果表明: 载体多层膜{GN/CuPW₁₁}₄表面较为平整均匀, 在选定恒电位下沉积在载体表面的Pt纳米粒子呈现花簇状且分布均匀。Pt/{GN/CuPW₁₁}₄复合多层膜中Pt 主要以Pt(0)形式存在, 还含有少量Pt (Ⅱ)和Pt(Ⅳ)。电催化实验研究结果显示:引入CuPW₁₁有效增强了Pt/GN复合膜催化剂的催化活性、电化学稳定性和抗CO毒化性能。

关键词: 直接甲醇燃料电池, 石墨烯, 多金属氧酸盐, 电沉积技术, 电催化氧化

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

中图分类号:

张艺, 张晓凤, 何晓蕾, 黄火娣, 乐丽娟, 林深. Pt/{GN/CuPW₁₁}_n复合膜的制备及其对甲醇氧化电催化性能[J]. 无机材料学报, 2017, 32(10): 1075-1082.

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.

图/表 11

图1 不同层数的 Pt/{GN/CuPW11}n修饰电极在 0.5 mol/L H2SO4 + 1.0 mol/L CH3OH 溶液中的循环伏安曲线

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

图2 (A)不同扫速下Pt/{GN/CuPW11}4在0.5 mol/L H2SO4 + 1.0 mol/L CH3OH 溶液中的循环伏安曲线; (B)不同扫速下Pt/{GN/CuPW11}4峰电流与扫速平方根的线性关系曲线

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

图3 不同修饰电极在0.5 mol/L H2SO4 + 1.0 mol/L CH3OH溶液中的循环伏安曲线

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

图4 不同修饰电极的循环伏安曲线对比图

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

图5 不同修饰电极的电流-时间(I-T)曲线

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.

图6 不同修饰电极的CO溶出伏安曲线

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

图7 不同修饰电极在 0.5 mol/L H2SO4 + 1.0 mol/L CH3OH 溶液中的交流阻抗图

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

图8 {GN/CuPW11}4多层复合膜的AFM形貌

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

图9 {GN/CuPW11}4和Pt/{GN/CuPW11}4的XRD图谱

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

图10 Pt/{GN/CuPW11}4沉积在ITO电极上的XPS图谱

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

图11 不同循环电位范围下Pt/{GN/CuPW11}4的SEM照片

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

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Pt/{GN/CuPW₁₁}_n复合膜的制备及其对甲醇氧化电催化性能

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

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