碳纳米管复合二维碳化钛负载钯粒子电催化性能研究

doi:10.15541/jim20170365

摘要/Abstract

摘要：

为提高Ti₃C₂的层间距及电催化性能, 利用碳纳米管(CNT)进行层间微结构调控。Ti₃AlC₂经HF化学刻蚀法获得层状Ti₃C₂, 再以羟基化碳纳米管(CNT)以及次氯钯酸钾(K₂PdCl₄)为原料, 通过超声分散和溶剂热法将贵金属Pd粒子负载到Ti₃C₂-CNT上, 制得直接甲醇电池阳极催化剂材料Pd/Ti₃C₂-CNT。采用X射线衍射、扫描电镜以及光电子衍射对样品的形貌和结构进行表征, 考察了CNT对Ti₃C₂层间微结构的调整效果; 采用循环伏安法、计时电流法以及交流阻抗图谱研究了Pd/Ti₃C₂-CNT复合催化剂在酸性、碱性溶液中对甲酸、甲醇的电催化性能。结果表明, 复合材料中CNT对Ti₃C₂有插层作用, 建立了“桥联”效果, 有利于催化剂载体电子传输, 进而提高了Pd/Ti₃C₂-CNT的电催化性能。

关键词: 直接甲醇燃料电池, 钯, 碳纳米管, 碳化钛

Abstract:

To improve the layer spacing and the electrocatalytic performance of Ti₃C₂, the carbon nanotubes (CNTs) was utilized to tailor the microstructure. Layered Ti₃C₂, obtained by etching Ti₃AlC₂ with HF, hydroxylated carbon nanotubes (CNTs) and potassium tetrachloropalladate (K₂PdCl₄) were used to synthesize Pd naoparticles supported on Ti₃C₂-CNT (Pd/Ti₃C₂-CNT) catalyst through ultrasonic dispersion and solvothermal method. XRD, FE-SEM and XPS were adopted to investigate the effect of CNT on the microstructural tailoring of Ti₃C₂ interlayers. The electrocatalytic performance of Pd/ Ti₃C₂-CNT catalysts for both formic acid and methanol in acidic and alkaline solutions, were investigated by cyclic voltammetry, chronoamperometry, and AC impedance spectroscopy, respectively. The results validated that the intercalation of CNTs into Ti₃C₂ interlayers, whose “bridge” effects benefit the electron transportation in the catalysts, and thus the electrocatalytic performance of Pd/Ti₃C₂-CNT was elevated.

Key words: direct methanol fuel cell, palladium, CNTs, Ti3C2

中图分类号:

TQ174

张欣, 张建峰, 杨水仙, 曹惠杨, 黄华杰, 江莞. 碳纳米管复合二维碳化钛负载钯粒子电催化性能研究[J]. 无机材料学报, 2018, 33(2): 206-212.

ZHANG Xin, ZHANG Jian-Feng, YANG Shui-Xian, CAO Hui-Yang, HUANG Hua-Jie, JIANG Wan. Electrocatalytic Performance of Palladium Nanoparticle Supported by Two-dimensional Titanium Carbide-CNT Composites[J]. Journal of Inorganic Materials, 2018, 33(2): 206-212.

图/表 8

图1 (a) Ti3C2和 (b) Pd/(Ti3C2)5-(CNT)5的SEM照片

Fig. 1 SEM images of (a) Ti3C2 and (b) Pd/(Ti3C2)5-(CNT)5 electrocatalysts

图2 Ti3C2、Pd/Ti3C2、Pd/Ti3C2-CNT和Pd/CNT的XRD图谱

Fig. 2 XRD patterns of Ti3C2, Pd/Ti3C2, Pd/Ti3C2-CNT, and Pd/CNT electrocatalysts

图3 Pd/Ti3C2、Pd/Ti3C2-CNT和Pd/CNT的(a~c) C1s; (d~f) Pd3d XPS图谱

Fig. 3 High-resolution (a-c) C1s and (d-f) Pd3d core-level XPS spectra of Pd/CNT, Pd/Ti3C2-CNT and Pd/Ti3C2 electrocatalysts

图4 (a) Pd/Ti3C2、(b) Pd/Ti3C2-CNT的Ti2p XPS图谱

Fig. 4 High-resolution Ti2p core-level XPS spectra of (a) Pd/Ti3C2-CNT and (b) Pd/Ti3C2 electrocatalysts

图5 Pd/Ti3C2-CNT分别在(a) 0.5 mol/L H2SO4和(c) 0.5 mol/L NaOH的电解液中50 mV/s扫速下的循环伏安曲线。图(b), (d)分别是对应的ECSA值

Fig. 5 Cyclic voltammetry curves of Pd/Ti3C2-CNT electrocatalysts in (a) 0.5 mol/L H2SO4 and (c) 0.5 mol/L NaOH at 50 mV/s. The corresponding ECSA values were shown in (c) and (d)

图6 Pd/Ti3C2-CNT分别在(a) 0.5 mol/L H2SO4+0.5 mol/L HCOOH和(c) 0.5 mol/L NaOH+1 mol/L CH3OH的电解液中50 mV/s扫速下的循环伏安曲线。图(b), (d)分别是对应的正向峰值电流密度值(IF)

Fig. 6 Cyclic voltammetry curves of Pd/Ti3C2-CNT electrocatalysts in (a) 0.5 mol/L H2SO4+0.5 mol/L HCOOH and (c) 0.5 mol/L NaOH+1 mol/L CH3OH at 50 mV/s. The corresponding forward peak current densities were shown in (c) and (d)

图7 (a) Pd/CNT和(b) Pd/(Ti3C2)5-(CNT)5的EIS曲线

Fig. 7 Nyquist plots of EIS for (a) Pd/CNT and (b) Pd/(Ti3C2)5-(CNT)5 electrocatalysts

图8 Pd/Ti3C2-CNT分别在(a) 0.5 mol/L H2SO4+0.5 mol/L HCOOH和(b) 0.5 mol/L NaOH+1 mol/L CH3OH电解液中的计时电流曲线

Fig. 8 Chronoamperometric curves of Pd/Ti3C2-CNT electrocatalysts recorded in (a) 0.5 mol/L H2SO4+0.5 mol/L HCOOH and (b) 0.5 mol/L NaOH+1 mol/L CH3OH solutions

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