一种新型酶生物燃料电池阳极构建及性能研究
收稿日期: 2013-03-15
网络出版日期: 2013-06-13
基金资助
项目受国家自然科学基金(No. 21275041)、湖南省自然科学基金(No. 12JJ2010)、高等学校博士学科点专项科研基金(No. 20110161110009)和长江学者和创新团队发展计划(No. IRT1238)资助.
Construction and Performance of a New Bioanode for Biofuel Cells
Received date: 2013-03-15
Online published: 2013-06-13
Supported by
Project supported by the National Natural Science Foundation of China (No. 21275041), Hunan Provincial Natural Science Foundation of China (No. 12JJ2010), the Specialized Research Fund for the Doctoral Program of Higher Education (No. 20110161110009), and Program for Changjiang Scholars and Innovative Research Team in University (No. IRT1238).
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.
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 . DOI: 10.6023/A13030285
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
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