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电化学近期研究专辑(厦门大学 姜艳霞教授主编)

Pd-Cu/C上甲酸根电催化氧化及其去合金化效应

  • 蒋昆 ,
  • 王晔 ,
  • 林涛 ,
  • 蔡文斌
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  • 复旦大学 化学系,能源材料协同创新中心,上海市分子催化和功能材料表面重点实验室,上海 200433

收稿日期: 2014-01-24

  修回日期: 2014-04-01

  网络出版日期: 2014-04-10

基金资助

国家自然科学基金项目(No. 21073045,No. 21273046)和上海市重点项目(No. 11JC140200,No. 08DZ2270500)资助

Electrocatalytic Oxidation of Formate on Pd-Cu/C - Effect of Dealloying Pretreatment

  • JIANG Kun ,
  • WANG Ye ,
  • LIN Tao ,
  • CAI Wen-Bin
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  • Shanghai Key Laboratory of Molecular Catalysis and Innovative Materials, Collaborative Innovation Center of Chemistry for Energy Materials, Department of Chemistry, Fudan University, Shanghai 200433, China

Received date: 2014-01-24

  Revised date: 2014-04-01

  Online published: 2014-04-10

摘要

以柠檬酸钠为稳定剂,通过一锅法在乙二醇体系中制得高分散的Pd-Cu/C二元合金催化剂. 用高分辨透射电镜和XRD观察、表征其形貌和结构,经重复循环扫描对Pd-Cu/C催化剂进行去合金化处理,研究了去合金效应对甲酸根电催化氧化性能的影响. 通过吸附CO的原位ATR-IR光谱测量,初步探讨了去合金前后催化剂表面结构的改变. 研究表明,Cu的去合金化可提高Pd-Cu/C电极初始的电催化氧化活性,但不利于其长时间的活性保持;合金化Pd-Cu/C电极电催化稳定性有显著的优势.

本文引用格式

蒋昆 , 王晔 , 林涛 , 蔡文斌 . Pd-Cu/C上甲酸根电催化氧化及其去合金化效应[J]. 电化学, 2014 , 20(4) : 343 -348 . DOI: 10.13208/j.electrochem.131173

Abstract

Carbon supported highly dispersed Pd-Cu nanoalloy catalyst toward formate electrooxidation is prepared via one-pot synthesis by using ethylene glycol as the reducing agent and sodium citrate as the stabilizer. The as-prepared catalyst is structurally characterized by TEM and XRD. The Cu dealloyment is carried out through repetitive potential cycling of the Pd-Cu/C catalyst in an acidic solution. The dealloying effect on the performance of the Pd-Cu/C is investigated by using cyclic voltammetry and chronoamperometry, and the surface structural change of Pd-Cu/C is probed by in situ ATR-IR measurement. The results show that the as-prepared Pd-Cu/C processes a better long-term stability than the dealloyed one in electrocatalytic oxidation of formate, while the dealloyed Pd-Cu/C exhibits a higher initial electrocatalytic activity.

参考文献

[1] Bartrom A M, Haan J L. The direct formate fuel cell with an alkaline anion exchange membrane[J]. Journal of Power Sources, 2012, 214: 68-74.
[2] Takamura T, Mochimar F. Adsorption and oxidation of formate on palladium in alkaline solution[J]. Electrochimica Acta, 1969, 14(1): 111-119.
[3] Nishimura K, Machida K I, Enyo M. Electrooxidation of formate and formaldehyde on electrodes of alloys between Pd and group-Ib metals in alkaline media 1. Electrocatalytic properties of component metals[J]. Journal of Electroanalytical Chemistry, 1988, 251(1): 103-116.
[4] Bianchini C, Shen P K. Palladium-based electrocatalysts for alcohol oxidation in half cells and in direct alcohol fuel cells[J]. Chemical Reviews, 2009, 109(9): 4183-4206.
[5] Antolini E. Palladium in fuel cell catalysis[J]. Energy & Environmental Science, 2009, 2(9): 915-931.
[6] Yu X W, Pickup P G. Screening of PdM and PtM catalysts in a multi-anode direct formic acid fuel cell[J]. Journal of Applied Electrochemistry, 2011, 41(5): 589-597.
[7] Yang Y Y(阳耀月), Zhang H X(张涵轩), Cai W B(蔡文斌). Recent experimental progresses on electrochemical ATR-SEIRAS[J]. Journal of Electrochemistry(电化学), 2013, 19(1): 6-16.
[8] Cochell T, Manthiram A. Pt@PdxCuy/C core-shell electrocatalysts for oxygen reduction reaction in fuel cells[J]. Langmuir, 2012, 28(2): 1579-1587.
[9] Jiang K, Cai W B. Carbon supported Pd-Pt-Cu nanocatalysts for formic acid electrooxidation: Synthetic screening and componential functions[J]. Applied Catalysis B: Environmental, 2014, 147: 185-192.
[10] Kariuki N N, Wang X P, Mawdsley J R, et al. Colloidal synthesis and characterization of carbon-supported Pd-Cu nanoparticle oxygen reduction electrocatalysts[J]. Chemistry of Materials, 2010, 22(14): 4144-4152.
[11] Lu L, Shen L P, Shi Y, et al. New insights into enhanced electrocatalytic performance of carbon supported Pd-Cu catalyst for formic acid oxidation[J]. Electrochimica Acta, 2012, 85: 187-194.
[12] Wu H B(武海滨), Zhang R Z(张瑞中), Chen W(陈卫). Synthesis and electrocatalysis of PdCu alloy nanocrystals[J]. Journal of Electrochemistry(电化学), 2013, 19(2): 115-119.
[13] Koh S, Strasser P. Electrocatalysis on bimetallic surfaces: Modifying catalytic reactivity for oxygen reduction by voltammetric surface dealloying[J]. Journal of the American Chemical Society, 2007, 129(42): 12624-12625.
[14] Dai L, Zou S Z. Enhanced formic acid oxidation on Cu-Pd nanoparticles[J]. Journal of Power Sources, 2011, 196(22): 9369-9372.
[15] Bradley J S, Hill E W, Chaudret B, et al. Surface-chemistry on colloidal metals - reversible adsorbate - induced surface-composition changes in colloidal palladium-copper alloys[J]. Langmuir, 1995, 11(3): 693-695.
[16] Bradley J S, Via G H, Bonneviot L, et al. Infrared and EXAFS study of compositional effects in nanoscale colloidal palladium-copper alloys[J]. Chemistry of Materials, 1996, 8(8): 1895-1903.
[17] Liu P, Norskov J K. Ligand and ensemble effects in adsorption on alloy surfaces[J]. Physical Chemistry Chemical Physics, 2001, 3(17): 3814-3818.
[18] Miyake H, Okada T, Samjeske G, et al. Formic acid electrooxidation on Pd in acidic solutions studied by surface-enhanced infrared absorption spectroscopy[J]. Physical Chemistry Chemical Physics, 2008, 10(25): 3662-3669.
[19] Cuesta A, Cabello G, Osawa M, et al. Mechanism of the electrocatalytic oxidation of formic acid on metals[J]. ACS Catalysis, 2012, 2(5): 728-738.
[20] Wang J Y, Zhang H X, Jiang K, et al. From HCOOH to CO at Pd Electrodes: A surface-enhanced infrared spectroscopy study[J]. Journal of the American Chemical Society, 2011, 133(38): 14876-14879.
[21] Zhang H X, Wang S H, Jiang K, et al. In situ spectroscopic investigation of CO accumulation and poisoning on Pd black surfaces in concentrated HCOOH[J]. Journal of Power Sources, 2012, 199: 165-169.
[22] Jiang K, Xu K, Zhou S, et al. B?doped Pd catalyst: Boosting room-temperature hydrogen production from formic acid-formate solutions[J]. Journal of the American Chemical Society, 2014, DOI: 10.1021/ja5008917
[23] Obradovic M D, Gojkovic S L. HCOOH oxidation on thin Pd layers on Au: Self-poisoning by the subsequent reaction of the reaction product[J]. Electrochimica Acta, 2013, 88: 384-389.
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