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-TEKPt/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(33μW cm-2,0.18 V)几乎是后者的三倍(11.7μW 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.
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-fl-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-fl-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-fl-CD-Fc/GC electrode as the bioanode) remained 92% of init