Pd/Fe3O4-C催化剂对甲醇、乙醇和丙醇氧化的电催化活性

邹涛,易清风,张媛媛,刘小平,徐国荣,聂会东,周秀林

doi:10.13208/j.electrochem.161104

电化学 >

2017 , Vol. 23 >Issue 6: 708 - 717

DOI: https://doi.org/10.13208/j.electrochem.161104

研究论文

Pd/Fe₃O₄-C催化剂对甲醇、乙醇和丙醇氧化的电催化活性

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1.湖南科技大学，化学化工学院，中国,湘潭，411201；2.理论有机化学与功能分子教育部重点实验室，中国湖南，湘潭，411201

收稿日期: 2016-11-04

修回日期: 2017-03-15

网络出版日期: 2017-03-16

基金资助

国家自然科学基金项目(21376070)，湖南省研究生科研创新项目(CX2016B567)资助

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Electroactivities of Pd/Fe₃O₄-C catalysts for electro-oxidation of methanol, ethanol and propanol

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1.School of Chemistry and Chemical Engineering, Hunan University of Science and Technology, Xiangtan 411201, China; 2.Key Laboratory of Theoretical Organic Chemistry and Functional Molecule, Ministry of Education, Xiangtan 411201, Hunan, China

Received date: 2016-11-04

Revised date: 2017-03-15

Online published: 2017-03-16

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摘要

制备对醇氧化反应具有优异电活性的钯催化剂是醇燃料电池研究的重要内容。本文用硼氢化钠还原法制备了钯纳米颗粒, 然后沉积在Fe3O4/C复合物表面, 得到了不同Fe₃O₄负载量的Pd/Fe₃O₄-C催化剂. 透射电镜（TEM）图显示钯纳米颗粒均匀地分散在Fe₃O₄/C表面. 对制备好的Pd/Fe₃O₄-C催化剂进行了循环伏安法（CV）、计时电流（CA）和电化学阻抗谱（EIS）的测试, 研究了其在碱性介质中对C1-C3醇类（甲醇、乙醇和丙醇）氧化的电催化活性. 结果表明, 所制备的不同Fe₃O₄负载量的Pd/Fe₃O₄(2%)-C,Pd/Fe₃O₄(5%)-C, Pd/Fe₃O₄(10%)-C和Pd/C催化剂中, Pd/Fe₃O₄(5%)-C催化剂表现出最高的醇氧化电流密度. 依据循环伏安（CV）数据，Pd/Fe₃O₄(5%)-C催化剂对甲醇、乙醇、正丙醇和异丙醇氧化的阳极峰电流密度分别是Pd/C催化剂的1.7、1.4、1.7和1.3倍. Pd/Fe₃O₄(5%)-C催化剂对乙醇氧化的电荷传递电阻也远低于Pd/C催化剂. 制备的所有催化剂对C1-C3醇类电氧化的电流密度大小排序如下: 正丙醇﹥乙醇﹥甲醇﹥异丙醇. 此外, 碳粉中Fe₃O₄纳米颗粒的存在提高了钯纳米颗粒的电化学稳定性.

关键词： 钯催化剂; Fe₃O₄; 醇氧化; 电催化

本文引用格式

邹涛,易清风,张媛媛,刘小平,徐国荣,聂会东,周秀林 . Pd/Fe₃O₄-C催化剂对甲醇、乙醇和丙醇氧化的电催化活性[J]. 电化学, 2017 , 23(6) : 708 -717 . DOI: 10.13208/j.electrochem.161104

Abstract

Development of palladium (Pd) catalysts with high electroactivity for alcohol oxidation is significant for alcohol fuel cells. In this work, Pd nanoparticles were formed by sodium borohydride (NaBH₄) reduction method and subsequently deposited on the surface of carbon supported ferriferrous oxide (Fe₃O₄/C) composites to obtain the Pd/Fe₃O₄-C catalysts with different Fe₃O₄loadings. Their transmission electron microscopic (TEM) images show that the Pd nanoparticles were uniformly dispersed on the Fe₃O₄/C. Electroactivities of the prepared Pd/Fe₃O₄-C catalysts toward oxidations of C1-C3 alcohols (methanol, ethanol, n-propanol and iso-propanol) in alkaline media were investigated by cyclic voltammetry (CV), chronoamperometry and electrochemical impedance spectroscopy. Among the prepared catalysts (Pd/Fe₃O₄(2%)-C, Pd/Fe₃O₄(5%)-C, Pd/Fe₃O₄(10%)-C and Pd/C), the Pd/Fe₃O₄(5%)-C catalyst presented the highest electro-oxidation current density for oxidations of C1-C3 alcohols. According to the CV data, the anodic peak current densities for oxidations of methanol, ethanol, n-propanol and iso-propanol on the Pd/Fe₃O₄(5%)-C catalyst were over 1.7, 1.4, 1.7 and 1.3 times larger than that on the Pd/C catalyst, respectively. Furthermore, the charge transfer resistance of ethanol oxidation on the Pd/Fe₃O₄(5%)-C catalyst was much lower than that on the Pd/C catalyst. For all of the prepared catalysts, the decreases in electro-oxidation current density of the tested C1-C3 alcohols followed the order of n-propanol >ethanol > methanol >iso-propanol. In addition, the presence of Fe₃O₄ nanoparticles in the carbon powder improved the electrochemical stability of the Pd nanoparticles.

Key words： Pd catalyst; Fe₃O₄; Alcohol oxidation; Electrocatalyst

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