化学学报 ›› 2013, Vol. 71 ›› Issue (12): 1676-1682.DOI: 10.6023/A13050577 上一篇    下一篇

研究论文

高分散镍-硼/纳米多孔铜非晶态合金电极上葡萄糖的电催化氧化

张树金, 郑一雄, 袁林珊, 杨卫华   

  1. 华侨大学材料科学与工程学院 厦门 361021
  • 收稿日期:2013-05-31 出版日期:2013-12-14 发布日期:2013-11-03
  • 通讯作者: 郑一雄 E-mail:yixiongzheng@126.com
  • 基金资助:

    项目受福建省自然科学基金(No. 2010J01292)、福建省纳米材料重点实验室基金(No. NM10-04)、华侨大学高层次人才科研启动基金(No. 08BS205)和国家自然科学基金(No. 21103055)资助.

Electrocatalytic Oxidation of Glucose on Highly Dispersed Ni-B/Nanoporous Cu Amorphous Alloy Electrode

Zhang Shujin, Zheng Yixiong, Yuan Linshan, Yang Weihua   

  1. College of Materials Science and Engineering, Huaqiao University, Xiamen 361021
  • Received:2013-05-31 Online:2013-12-14 Published:2013-11-03
  • Supported by:

    Project supported by the Fujian Provincial Natural Science Foundation (No. 2010J01292), Fund of Fujian Provincial Key Laboratory of Nanomaterials (No. NM10-04), and Program for Excellent Talents in Huaqiao University, China (No. 08BS205), and the National Natural Science Foundation of China (No. 21103055).

通过酸腐蚀去合金法处理热扩散制备的铜基表面铜锌合金得到纳米多孔铜(NPC)材料. 以NPC为载体,采用超声辅助化学镀制备Ni-B/NPC合金电极. X射线衍射(XRD)和扫描电镜(SEM)表明Ni-B/NPC电极呈现由高分散纳米颗粒组成的非晶态结构. 计时电流法(CA)结果表明化学镀5 min制备的Ni-B/NPC电极具有最大的电化学活性表面积(EASA). 循环伏安法(CV)结果表明,与块状镍电极相比,碱性介质中在Ni-B/NPC电极上葡萄糖起始氧化电位负移39 mV,氧化峰电流提高了18.9倍. 采用线性扫描伏安法(LSV)、CA和电化学阻抗谱(EIS)测定Ni-B/NPC电极对葡萄糖电催化氧化的电子转移系数(β)、电催化氧化反应速率常数(k)和葡萄糖的扩散系数(D)等动力学参数. 结果表明高分散Ni-B/NPC非晶态合金电极对碱性介质中葡萄糖的氧化具有较高的电催化活性和稳定性.

关键词: 纳米多孔铜, 超声辅助化学镀, 镍-硼非晶态合金, 葡萄糖, 电催化氧化

As glucose is the richest carbohydrate in nature and has extremely high energy density, direct glucose fuel cell (DGFC) is considered to be a promising power source. Catalyst is the key to the development of DGFC. The expensive noble metal catalysts hinder their commercial applications. Ni is a cheap metal with an excellent catalytic performance. Ni and its compounds using glassy carbon as the carrier have been developed for glucose oxidation, but the smooth surface of glassy carbon could not be conductive to dispersion of nanoparticles. The development of nanoporous materials may overcome the drawback. In this experiment, Cu-based surface Cu-Zn alloy was prepared by thermal diffusion and Nanoporous Copper (NPC) with high surface area was prepared by removing of Zn element from the alloy in 5% H2SO4 solution. NPC supported Nickel-Boron (Ni-B/NPC) alloy electrode was fabricated by ultrasonic-assisted electroless plating. The Ni-B/NPC alloy electrode was characterized by scanning electron microscopy (SEM), X-ray diffraction (XRD) and electrochemical methods. XRD and SEM results showed Ni-B alloy electrode was amorphous structure with high dispersion of Ni-B nanoparticles. Chronoamperometry (CA) result found the prepared Ni-B/NPC amorphous alloy electrode with ultrasonic for 5 min had the highest electrochemical active surface area (EASA) and surface roughness. The CV results of glucose oxidation at the Ni-B/NPC amorphous alloy electrode showed the onset oxidation potential had a negative shift of 39 mV and the oxidation peak current density increased by 18.9 times compared with the bulk Ni electrode in alkaline media. Meanwhile, the kinetic parameters of electrocatalytic oxidation of glucose at the Ni-B/NPC amorphous alloy electrode were determined by linear sweep voltammetry (LSV), CA method and electrochemical impedance spectroscopy (EIS), such as charge transfer coefficient (β), catalytic rate constant (k) and diffusion coefficient (D). The results indicated the good electrocatalytic activity and stability of the highly dispersed Ni-B/NPC amorphous alloy electrode for glucose oxidation in alkaline medium, and the diffusion coefficient of glucose was improved by about two orders of magnitude relative to the reported value at the Ni-Cu/GC electrode. The Ni-B alloy should be a promising anodic catalyst for direct glucose fuel cell.

Key words: nanoporous copper, ultrasonic-assisted electroless, nickel-boron amorphous alloy, glucose, electrocatalytic oxidation