DMFC阳极催化剂Fe3O4@Pt的制备及其催化性

doi:10.15541/jim20160683

摘要/Abstract

摘要：

采用水热法制得粒径为150~300 nm、分散性良好的Fe₃O₄磁性内核颗粒, 经APTES对Fe₃O₄进行氨基化修饰后, 用NaBH₄原位还原H₂PtCl₆制得Fe₃O₄@Pt核壳结构的DMFC阳极催化剂, 对其进行TEM、XRD、XPS、EDS和催化活性及稳定性表征, 结果表明: 制得的Fe₃O₄@Pt颗粒表面主要由Pt组成, 形成了完整包覆一层Pt的Fe₃O₄@Pt粒子, 颗粒粒径为200~300 nm, Fe与Pt的原子比近似为3:1; Fe₃O₄@Pt具有良好的稳定性, 在循环100圈后, Fe₃O₄@Pt修饰的玻碳电极在新配制的0.5 mol/L H₂SO₄+1 mol/L CH₃OH溶液中循环第101圈的峰电流密度是第一圈的94.51%; 纯Pt的峰电流密度仅为Fe₃O₄@Pt的90.73%, Fe₃O₄和Pt之间存在电荷传递, 从而提高了Fe₃O₄@Pt的催化活性。因此Fe₃O₄@Pt有望取代Pt作为DMFC的阳极催化剂。

关键词: 四氧化三铁, 铂, 核壳结构, 甲醇催化氧化

Abstract:

Fe₃O₄ magnetic core particles was prepared by hydrothermal method with a particle size of 150-300 nm, which showed good dispersibility. After amination of Fe₃O₄ particles by APTES, combined with in situ reduction of H₂PtCl₆ with NaBH₄, we obtained Fe₃O₄@Pt with core-shell structure, and used it as a DMFC anode catalyst. The composition, morphology and structure of Fe₃O₄@Pt were characterized by transmission electron microscopy (TEM), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), and energy-dispersive X-ray spectroscopy (EDS). The electrocatalytic activities of Fe₃O₄@Pt were also investigated by cyclic voltammetry (CV). As a result, the surface of Fe₃O₄@Pt particles mainly composed of Pt. The particle size of Fe₃O₄@Pt particles is between 200 nm and 300 nm. Atomic ratio between Fe and Pt is about 3:1. The prepared Fe₃O₄@Pt particles have a good stability. After 100 cycles, the cycle peak current density of the 101th’ cyclic voltammetry curve of glassy carbon electrode modified by Fe₃O₄@Pt in fresh 0.5 mol/L H₂SO₄+1 mol/L CH₃OH aqueous solutions is 94.51% of the first cyclic voltammetry curve. The peak current density of pure Pt is only 90.73% compared with that of Fe₃O₄@Pt. The charge transfer between Fe₃O₄ and Pt improves the catalytic activity Fe₃O₄@Pt. As a result, this work demonstrates the potential of Fe₃O₄@Pt catalyst to replace Pt as the anode of DMFC in the future.

Key words: Fe3O4, Pt, core-shell, the catalytic oxidation of methanol

中图分类号:

O643

李敏, 洛园, 许伟佳, 刘家祥. DMFC阳极催化剂Fe₃O₄@Pt的制备及其催化性[J]. 无机材料学报, 2017, 32(9): 916-922.

LI Min, LUO Yuan, XU Wei-Jia, LIU Jia-Xiang. DMFC Anode Catalyst Fe₃O₄@Pt Particles: Synthesis and Catalytic Performanc[J]. Journal of Inorganic Materials, 2017, 32(9): 916-922.

图/表 10

图1 Fe3O4粒子的TEM照片(a)和XRD图谱(b)

Fig. 1 TEM image (a) and XRD pattern (b) of Fe3O4 particles

图2 氨基化修饰Fe3O4颗粒的TEM照片

Fig. 2 TEM image of amino-coated Fe3O4 particles

图3 氨基化修饰Fe3O4的XPS图谱(a)和N1s图谱(b)

Fig. 3 XPS spectrum and N1s XPS spectra of amino-coated Fe3O4

图4 Fe3O4@Pt颗粒的XRD图谱(a)和TEM照片(b)

Fig. 4 XRD pattern (a) and TEM image (b) of Fe3O4@Pt nanoparticles

图5 Fe3O4@Pt颗粒的XPS图谱(a)和Pt4f图谱(b)

Fig. 5 XPS spectrum (a) and Pt4f XPS spectra (b) of Fe3O4@Pt particles

图6 Fe3O4@Pt(a)单个颗粒与(b)多个颗粒的EDS谱图

Fig. 6 EDS patterns of single Fe3O4@Pt nanoparticle (a) and multiple Fe3O4@Pt nanoparticles (b)

图7 样品Fe3O4@Pt的峰电流密度与扫描时间的关系曲线

Fig. 7 Relationship between peak currents and scanning time of the Fe3O4@Pt catalysts

图8 样品Fe3O4@Pt修饰玻碳电极的第101圈及第1圈循环伏安曲线

Fig. 8 The 101th’ and first cyclic voltammetry curves of glassy carbon electrode modified by Fe3O4@Pt (a) After 100 cycles, the 101th’ cyclic voltammetry curve of glassy carbon electrode modified by Fe3O4@Pt in fresh 0.5 mol/L H2SO4+1 mol/L CH3OH aqueous solutions and the first cyclic voltammetry curve; (b) After 100 cycles, the 101th’ cyclic voltammetry curve of glassy carbon electrode modified by new Fe3O4@Pt in 0.5 mol/L H2SO4+1 mol/L CH3OH aqueous solutions and the first cyclic voltammetry curve

图9 样品Fe3O4@Pt在0.5 mol/L H2SO4+1 mol/L CH3OH溶液中的ip与v1/2的关系曲线

Fig. 9 Relationship between peak current ip and v1/2 of Fe3O4@Pt in 0.5 mol/L H2SO4 +1 mol/L methanol aqueous solution

图10 Fe3O4@Pt和Pt在0.5 mol/L H2SO4 + 1 mol/L CH3OH溶液中的线性循环伏安曲线

Fig. 10 Linear cyclic voltammetry curves of Fe3O4@Pt and Pt in 0.5 mol/L H2SO4+1 mol/L methanol aqueous solutions

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DMFC阳极催化剂Fe₃O₄@Pt的制备及其催化性

DMFC Anode Catalyst Fe₃O₄@Pt Particles: Synthesis and Catalytic Performanc

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