Pd/PMo12-GN复合膜的制备及其对甲酸氧化的电催化性能

doi:10.3724/SP.J.1077.2014.13541

摘要/Abstract

摘要：

以紫外光还原法将氧化石墨(GO)还原成石墨烯(GN), 同时将磷钼酸(PMo₁₂)修饰到石墨烯上, 形成磷钼酸功能化的石墨烯PMo₁₂-GN, 并以此为基底利用电化学还原法制备了Pd/PMo₁₂-GN复合膜催化剂。运用X射线粉末衍射、X射线光电子能谱、扫描电镜、透射电镜等对复合膜的组成、结构、形态进行表征, 结果表明: 实验成功制备了Pd/PMo₁₂-GN复合膜催化剂, 且Pd颗粒均匀分散在PMo₁₂-GN基底上。采用CV、计时电流法、CO溶出伏安法、交流阻抗法等电化学方法研究了Pd/PMo₁₂-GN复合膜的电催化性能。研究结果表明: 制备的复合膜催化剂对甲酸氧化反应的催化活性、催化稳定性、抗CO毒化能力和电子传递能力显著优于商品化的Pd/C催化剂。Pd/PMo₁₂-GN复合膜电催化性能的提高主要是由于Pd纳米颗粒在PMo₁₂-GN基底上均匀分散, 以及PMo₁₂的强氧化能力从而使钯表面一氧化碳等中间产物能迅速氧化去除。

关键词: 石墨烯, 多金属氧酸盐, 甲酸, 催化氧化

Abstract:

The Pd/PMo₁₂-GN composite film was prepared by electrochemical reduction, in which GN prepared from GO reduction under UV irradiation and simultaneously functional embellished by PMo₁₂. The as-prepared composite was characterized by X-ray diffraction, X-ray photoelectron spectroscope, scanning electron microscope and transmission electron microscope. It was shown that Pd/PMo₁₂-GN composite was successfully prepared and Pd particles were uniformly-dispersed with a small particle size on the PMo₁₂-GN substrate. Cyclic voltammetry, chronoamperometric curves, CO-stripping curves and EIS were used to discuss the electrocatalytic activities of the Pd/PMo₁₂-GN composite film. The results indicated that the as-prepared composite film presented better electrocatalytic activity, stability, CO tolerance ability, and electric conductivity towards formic acid oxidation as compared with commercial Pd/C catalyst. The enhancement in electrochemical performance of the Pd/PMo₁₂-GN composite film can be attributed to the synergistic effect of highly dispersed Pd nanoparticles on the PMo₁₂-GN substrate and higher oxidation power of PMo₁₂ which promotes the removal of the poisonous species on the Pd surface.

Key words: graphene, polyoxometalates, formic acid, catalytic oxidation

中图分类号:

O646

黄晓灵, 林舟, 练昕怡, 张晓凤, 林深. Pd/PMo₁₂-GN复合膜的制备及其对甲酸氧化的电催化性能[J]. 无机材料学报, 2014, 29(7): 722-728.

HUANG Xiao-Ling, LIN Zhou, LIAN Xing-Yi, ZHANG Xiao-Feng, LIN Shen. Preparation and Electrocatalytic Properties of Pd/PMo₁₂-GN Composite towards Formic Acid Oxidation[J]. Journal of Inorganic Materials, 2014, 29(7): 722-728.

图/表 10

图1 Pd/PMo12-GN(a)和Pd/C(b)的XRD图谱

Fig. 1 XRD patterns of Pd/PMo12-GN (a) and Pd/C (b)

图2 Pd/PMo12-GN的XPS光谱图

Fig. 2 XPS spectra of Pd/PMo12-GN (a) Full-spectra; (b) Pd3d spectra

图3 Pd/PMo12-GN(a)和GO(b)的C1s XPS谱图

Fig. 3 C1s XPS spectra of Pd/PMo12-GN (a) and GO (b)

图 4 不同放大倍数下Pd/PMo12-GN的SEM照片

Fig. 4 Different magnification SEM images of Pd/PMo12-GN

图 5 Pd/PMo12-GN的TEM(a)和HRTEM(b)照片

Fig. 5 TEM (a) and HRTEM (b) images of Pd/PMo12-GN

图6 Pd/PMo12-GN/GCE(a)和Pd/C/GCE(b)在0.5 mol/L H2SO4溶液中的循环伏安曲线

Fig. 6 Cyclic voltammograms of Pd/PMo12-GN/GCE (a) and Pd/C/GCE (b) in 0.5 mol/L H2SO4 solution

图7 Pd/PMo12-GN/GCE(a)和Pd/C/GCE(b)在0.5 mol/L H2SO4+ 1.0 mol/L HCOOH溶液中的循环伏安曲线

Fig.7 Cyclic voltammograms of Pd/PMo12-GN/GCE (a) and Pd/C/GCE (b) in 0.5 mol/L H2SO4+1.0 mol/L HCOOH solution

图8 Pd/PMo12-GN/GCE(a)和Pd/C/GCE(b)在0.5 mol/L H2SO4+ 1.0 mol/L HCOOH溶液中的电流-时间曲线

Fig.8 I-t curves of Pd/PMo12-GN/GCE (a) and Pd/C/GCE (b) in 0.5 mol/L H2SO4+1.0 mol/L HCOOH solution

图 9 Pd/PMo12-GN/GCE(a)和Pd/C/GCE(b)在 0.5 mol/L H2SO4溶液中的CO溶出伏安曲线

Fig.9 CO-stripping curves of Pd/PMo12-GN/GCE (a) and Pd/ C/GCE (b) in 0.5 mol/L H2SO4 solution

图10 Pd/PMo12-GN/GCE(a)和Pd/C/GCE(b)在0.5 mol/L H2SO4+ 1.0 mol/L HCOOH溶液中的交流阻抗图

Fig.10 Nyquist plots of EIS of Pd/PMo12-GN/GCE (a) and Pd/C/GCE (b) in 0.5 mol/L H2SO4+1.0 mol/L HCOOH solution

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Pd/PMo₁₂-GN复合膜的制备及其对甲酸氧化的电催化性能

Preparation and Electrocatalytic Properties of Pd/PMo₁₂-GN Composite towards Formic Acid Oxidation

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