三维金纳米团簇/多壁碳纳米管-Nafion膜修饰电极的电化学制备及血红蛋白的直接电化学

doi:10.6023/A12110877

化学学报 ›› 2013, Vol. 71 ›› Issue (02): 239-245.DOI: 10.6023/A12110877 上一篇下一篇

研究论文

三维金纳米团簇/多壁碳纳米管-Nafion膜修饰电极的电化学制备及血红蛋白的直接电化学

赵越^a, 洪波^a, 范楼珍^b

a 中国海洋大学环境科学与工程学院青岛 266100;
b 北京师范大学化学学院北京 100875

投稿日期:2012-11-06 发布日期:2013-01-09
通讯作者: 赵越 E-mail:yuezhao@ouc.edu.cn
基金资助:
国家自然基金(No. 41201569/D011102)和中央高校基本科研业务费实验室研究基金项目(No. 201251007).

Electrodeposition of Gold Nanoparticle Clusters on Multi-Wall Carbon Nanotubes and the Direct Electrochemistry of Hemoglobin

Zhao Yue^a, Hong Bo^a, Fan Louzhen^b

a College of Environmental Science and Technology, Ocean University of China, Qingdao 266100;
b College of Chemistry, Beijing Normal University, Beijing 100875

Received:2012-11-06 Published:2013-01-09
Supported by:
Project supported by the National Natural Science Foundation of China (No. 41201569/D011102) and the Fundamental Research Funds for the Central Universities (No. 201251007).

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1. 三维金纳米团簇/多壁碳纳米管-Nafion膜修饰电极的电化学制备及血红蛋白的直接电化学.PDF(181KB)

摘要/Abstract

用改进的全电化学三步法制备三维金纳米团簇/多壁碳纳米管(3D Au/MWCNTs)纳米复合材料, 并用Nafion (Nafion)膜进行涂布固定, 制得3D Au/MWCNTs-Nafion修饰电极. 利用透射电子显微镜(TEM)和能量色散光谱(EDS)对所得纳米复合材料的形貌进行表征. 3D Au/MWCNTs具有金纳米核团簇而成的特殊圆丘状三维结构, 电化学活性表面积(ECSA)比均匀分散的Au/MWCNTs提高了一个数量级, 可有效提高血红蛋白(Hb)在电极表面的负载量. 运用循环伏安法和计时电流法对3D Au/MWCNTs-Nafion修饰电极的生物电催化性质进行研究, 其在Hb溶液中显示了良好的电催化活性和稳定性: 还原氧化峰电流高, 反应可逆性好, 提供了有利于Hb直接电子转移的电化学环境. 固载于Au/MWCNTs-Nafion上的Hb能够保持其生物活性, 对双氧水(H₂O₂)表现出良好的催化性能, 这是3D Au纳米团簇和MWCNTs共同作用的结果. 实验表明, 3D Au/MWCNTs-Nafion修饰电极结构特殊、性能优越, 对Hb的直接电化学研究具有积极的促进作用, 为准确高效的检测Hb及相关生物活性物质提供了新的电极选择.

关键词: 三维结构, 金纳米团簇, 碳纳米管, 血红蛋白, 直接电化学

Three-dimensional structure gold nanoparticle clusters (3D Au) were electrodeposited onto multiwalled carbon nanotubes (MWCNTs) through improved three-step method, which involves: (1) potential cycling (CV, 200 mV·s^-1) from +1.8 to -0.4 V was performed in 0.5 mol/L K₂SO₄ solutions for 10 min in order to produce oxide functional groups (carbonyl, hydroxyl, and carboxyl) at the defect sites located at the ends and/or the sidewalls of MWCNTs, (2) electrochemical oxidation of the Au(III) complex to the Au(V) complex from 2 mol/L K₂PtCl₄+0.1 mol/L K₂SO₄ aqueous solutions by using potential-step method (PS). The potential was jumped from 0.3 V to 1.1 V with different pulse width and this was repeated until a steady pulse current was reached. and (3) electrochemical transformation of the Au(V) complex to Au nanoparticle clusters on the surface of MWCNTs through cycling from +1.0 to -0.26 V in 0.1 mol/L H₂SO₄ solutions to the steady state. For comparison, however, experiments were also carried out with CV in the second step (2 mol/L K₂PtCl₄+0.1 mol/L K₂SO₄ aqueous solution with 190 cycles: these proved to be the optimal conditions). The morphology of 3D Au/MWCNTs electrode was characterized by transmission electron microscopy (TEM) and energy dispersive X-ray spectroscopy (EDS). The voltammetric behavior of hemoglobin (Hb) on 3D Au/MWCNTs-Nafion has been investigated in 10 nmol/L Hb solution (pH=6 PBS) by cyclic voltammetry (CV) and current-time method (CT). Compared with Au+MWCNTs-Nafion (+means mix together), Au/MWCNTs-Nafion (uniform Au nanoparticle dispersion of MWCNTs, which was obtained when the second step adopts cyclic voltammetry instead of potential-step method), 3D Au/MWCNTs-Nafion gave a higher peak current and better reversibility. The higher sensitivity and lower detection limit show that 3D Au/MWCNTs-Nafion can offer a conductive microenvironment for the immobilized Hb to achieve direct electrochemistry. The average coverage (Γ) of Hb immobilized on 3D Au/MWCNTs-Nafion was calculated to be 7.65×10^-9 mol·cm^-2, testifies a high surface-to-volume ratio. Electron transfer rate constant (k_S) was calculated to be 1.8 s^-1, which was proved 3D Au/MWCNTs-Nafion is more conducive to direct electron transfer between Hb and the electrode. Hb/Au/MWCNTs-Nafion potential application towards the electrocatalytic reduction of H₂O₂ was also conducted to show immobilized Hb exhibits excellent biocompatibility and stability. Our work points to a new path for the preparation of 3D Au/MWCNTs nanocomposites, which are promising as electrocatalysts in direct electrochemistry of Hb.

Key words: three dimensional, gold nanoparticle, multi-wall carbon nanotubes, hemoglobin, direct electrochemistry

引用此文

赵越, 洪波, 范楼珍. 三维金纳米团簇/多壁碳纳米管-Nafion膜修饰电极的电化学制备及血红蛋白的直接电化学[J]. 化学学报, 2013, 71(02): 239-245.

Zhao Yue, Hong Bo, Fan Louzhen. Electrodeposition of Gold Nanoparticle Clusters on Multi-Wall Carbon Nanotubes and the Direct Electrochemistry of Hemoglobin[J]. Acta Chimica Sinica, 2013, 71(02): 239-245.

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三维金纳米团簇/多壁碳纳米管-Nafion膜修饰电极的电化学制备及血红蛋白的直接电化学

Electrodeposition of Gold Nanoparticle Clusters on Multi-Wall Carbon Nanotubes and the Direct Electrochemistry of Hemoglobin

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