Pd-Sb/C复合纳米催化剂对甲酸电催化氧化的性能研究

doi:10.13208/j.electrochem.141124

电化学（中英文） ›› 2015, Vol. 21 ›› Issue (4): 368-374. doi: 10.13208/j.electrochem.141124

Pd-Sb/C复合纳米催化剂对甲酸电催化氧化的性能研究

王龙龙，曹晓璐，王亚骏，平金豪，李巧霞^*

上海电力学院，上海高校电力腐蚀控制与应用电化学重点实验室，上海 200090

收稿日期:2014-11-24 修回日期:2015-03-06 出版日期:2015-08-28 发布日期:2015-08-28
通讯作者: 李巧霞 E-mail:liqiaoxia@shiep.edu.cn
基金资助:
国家自然科学基金项目（No. 21103107）、上海市科委重点项目（No. 10160502300）资助

Preparation and Characterization of Carbon Supported Pd-Sb Composite Nanocatalysts for Formic Acid Electrooxidation

WANG Long-long, CAO Xiao-lu, WANG Ya-jun, PING Jin-hao, LI Qiao-xia^*

Key Laboratory of Shanghai Colleges and Universities for Corrosion Control in Electric Power System and Applied Electrochemistry, Shanghai University of Electric Power, Shanghai 200090, China

Received:2014-11-24 Revised:2015-03-06 Published:2015-08-28 Online:2015-08-28
Contact: LI Qiao-xia E-mail:liqiaoxia@shiep.edu.cn

摘要/Abstract

摘要： 以柠檬酸三钠为稳定剂，硼氢化钠为还原剂，制备了碳载型的Pd-Sb复合纳米催化剂（Pd-Sb/C），通过调制不同Pd:Sb摩尔比研究了其对甲酸电催化性能的影响. TEM结果表明，合成的纳米颗粒粒径较小且均匀分散在碳载体表面. XRD和XPS测试表明，Pd-Sb/C中少量的单质态Sb(0)高度分散在Pd颗粒中或表面，形成合金化程度较低的PdSb合金. 电化学测试表明，当Pd:Sb = 20:1时，合成的催化剂对甲酸的催化效能最佳. 与合成的Pd/C和商业Pd/C相比，Pd-Sb/C(20:1)的电流密度分别是Pd/C的2.6倍、商业Pd/C的4.2倍. Pd-Sb/C的整体催化性能得到改善主要归因于适量的单质态Sb(0)引入到Pd中，诱导产生电子效应和“双功能”效应，一方面减小Pd与CO毒性物种之间的吸附作用，另一方面促使Pd表面吸附的CO快速氧化，提高了Pd-Sb/C催化剂的抗CO中毒能力，使得Pd-Sb/C催化剂的整体催化性能得到改善.

关键词: Pd基催化剂, Sb修饰, 甲酸电氧化, 浸渍还原法

Abstract: Palladium is considered as an efficient anode catalyst with high catalytic activity for electrooxidation of formic acid. To further improve the catalytic activity and stability, alloying or surface modification with Sb is an effective way. In this work, the well dispersed carbon supported Pd-Sb composite nanocatalysts (Pd-Sb/C) were synthesized by traditional impregnation reduction method with trisodium citrate as the complexing agent, sodium borohydride as the reducing agent. The morphologies of Pd-Sb/C and the effects of molar ratio of Pd to Sb on the electrocatalytic properties of Pd-Sb/C for HCOOH electrooxidation were studied. The XRD and XPS analyses on the as-prepared Pd-Sb/C catalyst revealed that Sb (0) was presented on the Pd surface, and the immature alloying of Pd with Sb was achieved. Cyclic voltammetryic and chronoamperometric studies indicated a volcano-shaped relationship between Sb content and electrocatalytic activity with an optimum molar ratio of Pd:Sb=20:1. Compared with the commercial Pd/C catalyst, the Pd-Sb/C (20:1) presented the highest electrocatalytic activity and best stability. This enhancement may be attributed to the electronic effect and bi-functional effect induced by addition of Sb onto Pd surface, resulting in a weaker adsorption and accelerated oxidative removal of CO poison formed during HCOOH electrooxidation.

Key words: palladium-based catalyst, antimony decoration, formic acid electrooxidation, impregnation reduction

中图分类号:

O646

王龙龙, 曹晓璐, 王亚骏, 平金豪, 李巧霞. Pd-Sb/C复合纳米催化剂对甲酸电催化氧化的性能研究[J]. 电化学（中英文）, 2015, 21(4): 368-374.

WANG Long-long, CAO Xiao-lu, WANG Ya-jun, PING Jin-hao, LI Qiao-xia. Preparation and Characterization of Carbon Supported Pd-Sb Composite Nanocatalysts for Formic Acid Electrooxidation[J]. Journal of Electrochemistry, 2015, 21(4): 368-374.

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https://electrochem.xmu.edu.cn/CN/Y2015/V21/I4/368

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Pd-Sb/C复合纳米催化剂对甲酸电催化氧化的性能研究

Preparation and Characterization of Carbon Supported Pd-Sb Composite Nanocatalysts for Formic Acid Electrooxidation

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