物理化学学报 >> 2019, Vol. 35 >> Issue (7): 749-754.doi: 10.3866/PKU.WHXB201810051

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Ru修饰Pd二十四面体纳米晶的合成及其甲醇电催化氧化性能

郭锦成,林燕芬,田娜*(),孙世刚*()   

  • 收稿日期:2018-10-23 发布日期:2018-12-21
  • 通讯作者: 田娜,孙世刚 E-mail:tnsd@xmu.edu.cn;sgsun@xmu.edu.cn
  • 基金资助:
    国家自然科学基金(21573183);中央高校基本科研业务费(20720160045)

Modification of Tetrahexahedral Pd Nanocrystals with Ru and Their Performance for Methanol Electro-oxidation

Jincheng GUO,Yanfen LIN,Na TIAN*(),Shigang SUN*()   

  • Received:2018-10-23 Published:2018-12-21
  • Contact: Na TIAN,Shigang SUN E-mail:tnsd@xmu.edu.cn;sgsun@xmu.edu.cn
  • Supported by:
    the National Natural Science Foundation of China(21573183);the Fundamental Research Funds for the Central Universities, China(20720160045)

摘要:

表面结构控制和表面异种金属修饰是调控催化剂反应性的重要方法。因此,我们结合高指数晶面结构的高反应性与表面修饰异种金属,合成具有{730}高指数晶面的钯二十四面体纳米晶,并通过循环伏安扫描电沉积法得到Ru修饰的钯二十四面体纳米晶。电化学测试结果表明,低的Ru覆盖度(θRu = 0.08)可显著提高对碱性介质中甲醇电氧化的催化性能。电化学原位红外光谱结果表明,少量Ru的修饰没有减少CO的生成,而是促进了低电位下甲醇氧化成甲酸根。

关键词: 高指数晶面, Pd二十四面体, 表面修饰, 甲醇

Abstract:

Direct methanol fuel cell (DMFC) is a potential clean energy facility because of abundant resources, easy storage, and high safety of methanol. However, the low activity, poor durability, and high price of the catalysts hamper the development of DMFC. High-index faceted nanocrystals usually show high catalytic activity for the electro-oxidation of small organic molecules due to high densities of low-coordinated surface sites. Surface modification is an alternative approach for improving catalyst performance via ligand effect or electronic effect. Herein, we prepared tetrahexahedral Pd nanocrystals (THH Pd NCs) enclosed by {730} high-index facets via electrochemical square-wave potential deposition, and modified the THH Pd NCs with Ru using cyclic voltammetry (CV). The coverages of Ru (θRu) were controlled by limiting the CV cycles. The electrocatalytic performance of the Ru-modified THH Pd NCs for methanol oxidation was studied using CV in an alkaline methanol solution. We found that Ru modification can greatly reduce the onset and peak potentials of methanol electro-oxidation from -0.33 to -0.39 V and from -0.16 to -0.26 V, respectively. The current densities at -0.3 V during methanol electro-oxidation increased with increasing θRu from 0 to 0.08, and decreased with increasing θRu from 0.08 to 0.27. When θRu was 0.08, the current density on the Ru-modified THH Pd NCs reached 1.5 mA∙cm-2, which was 10 times higher than that achieved for the THH Pd NCs. To detect the products at molecular level during methanol electro-oxidation, in-situ electrochemical Fourier-transform infrared (FTIR) spectroscopy was applied. The spectra of both THH Pd NCs and Ru-modified THH Pd NCs (θRu = 0.08) showed that both CO2 and formate were produced. The band intensities of CO2 and formate on Ru-modified THH Pd NCs (θRu = 0.08) were 1.6- and 1.2-times larger than those of THH Pd NCs, respectively. However, the band intensity of COad during methanol electro-oxidation was almost equal on the two catalysts, implying that the "CO poison path" is not suppressed by Ru modification. These results indicate that a small amount of Ru (θRu = 0.08) modification is beneficial for the electrocatalytic oxidation of methanol by enhancing the "formate path" at low potential. Overall, this study illustrates the influence of Ru modification of THH Pd NCs on its catalytic performance in methanol electro-oxidation, which throws light on the synthesis and application of catalysts with high activities.

Key words: High-index facet, Tetrahexahedral Pd nanocrystal, Surface modification, Methanol

MSC2000: 

  • O647