一种新型酶生物燃料电池阳极构建及性能研究

doi:10.6023/A13030285

摘要/Abstract

通过酸化碳纳米管(CNTs)和β-环糊精(β-CD)之间的范德华力作用, 实现CNTs的β-CD功能化. β-CD具有内腔疏水、外壁亲水的环状结构, 其内腔容易与二茂铁(Fc)形成稳定的主客体包合结构, 实现Fc在碳纳米管上的高效固载; 再将CNTs-β-CD-Fc复合物与葡萄糖氧化酶(GOD)混合, 采用戊二醛实现酶分子间的交联, 形成GOD/CNTs-β-CD-Fc复合物, 然后将其涂覆到玻碳电极(GC)上, 得到一种新型的酶生物燃料电池阳极(GOD/CNTs-β-CD-Fc/GC). 采用同步热分析法、傅里叶变换红外光谱和透射电子显微镜对所制备的CNTs-β-CD-Fc复合物进行了表征, 采用循环伏安法研究了GOD/CNTs-β-CD-Fc/GC电极对葡萄糖氧化的催化性能. 结果表明: 在同等实验条件下, 没有固载Fc的GOD/CNTs- β-CD/GC电极基本无催化电流, 而GOD/CNTs-β-CD-Fc/GC电极表现出比GOD/CNTs-Fc/GC电极更为优越的电催化性能. 进一步以GOD/CNTs-β-CD-Fc/GC电极或GOD/CNTs-Fc/GC电极为酶阳极, 商用催化剂E-TEK Pt/C电极(E-TEK Pt/C/GC)为阴极, 构建葡萄糖/氧气生物燃料电池(EBFC), 结果表明前者的最大功率密度(33 μW·cm^-2, 0.18 V)几乎是后者的三倍(11.7 μW·cm^-2, 0.16 V). 通过记录开路电位随时间的变化研究了EBFC的稳定性, 以GOD/CNTs-β-CD-Fc/GC电极为阳极的EBFC在连续工作9 h后仍保留了92%的开路电位, 表明该电池具有良好的连续工作稳定性. 我们提出的这种新型生物燃料电池阳极的构造方法, 为构建高性能、高稳定性的葡萄糖/氧气EBFC提供了新的思路.

关键词: 碳纳米管, 二茂铁, β-环糊精, 葡萄糖氧化酶, 生物燃料电池

Acid-treated carbon nanotubes (CNTs) were functionalized by β-cyclodextrin (CD) through the van der Waals force between them. It is well-known that CD is toroidal in shape with a hydrophobic inner cavity and a hydrophilic exterior. Based on the recognition of CD to ferrocene (Fc), a water-soluble complex, CNTs-β-CD-Fc, was prepared. Glucose oxidase (GOD) was mixed with CNTs-β-CD-Fc and crosslinked with glutaraldehyde to form enzyme polymer. Then the GOD/CNTs-β-CD-Fc composite was coated on the glassy carbon (GC) electrode and the GOD/CNTs-β-CD-Fc/GC bioanode was obtained. The prepared CNTs-β-CD and CNTs-β-CD-Fc were characterized by thermal gravimeritric analysis, fourier transform infrared spectroscopy and transmission electron microscopy. The electrocatalytic properties of the GOD/CNTs-β-CD-Fc/GC bioanode towards glucose oxidation were investigated by cyclic voltammetry. The results showed that under the same experimental conditions, the GOD/CNTs-β-CD/GC electrode (without Fc) had almost no catalytic currents for glucose oxidation and the GOD/CNTs-β-CD-Fc/GC bioanode had higher electrocatalytic activity towards glucose oxidation than the GOD/CNTs-Fc/GC electrode. The long-term cycle stability of the developed GOD/CNTs-β-CD-Fc/GC bioanode was also evaluated by cyclic voltammetry and the results showed that the GOD/CNTs-β-CD-Fc/GC bioanode had much better stability than the GOD/CNTs-Fc/GC electrode. Taking the commercial E-TEK Pt/C modified GC electrode as the cathode, the maximum power density of the glucose/O₂ biofuel cell (EBFC) based on the GOD/CNTs-β-CD-Fc/GC anode was 33 μW·cm^-2 (at 0.18 V), almost 3 times higher than that of the EBFC based on the GOD/CNTs-Fc/GC anode (11.7 μW·cm^-2 at 0.16 V). The stability of the developed EBFC was also investigated by monitoring the change of the open circuit potential (OCP) of EBFC. After continuous operation for 9 h, the developed EBFC (the GOD/CNTs-β-CD-Fc/GC electrode as the bioanode) remained 92% of initial OCP, suggesting the good operating stability. The proposed strategy for bioanode preparation may provide a new way for the development of glucose/O₂ EBFC with good perfomance and high stability.

Key words: carbon nanotubes, ferrocene, β-cyclodextrin, glucose oxidase, biofuel cells

引用此文

邹琼, 刘娟, 朱刚兵, 张小华, 陈金华. 一种新型酶生物燃料电池阳极构建及性能研究[J]. 化学学报, 2013, 71(08): 1154-1160.

Zou Qiong, Liu Juan, Zhu Gangbing, Zhang Xiaohua, Chen Jinhua. Construction and Performance of a New Bioanode for Biofuel Cells[J]. Acta Chimica Sinica, 2013, 71(08): 1154-1160.

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