基于纳米碳材料的酶生物燃料电池阳极构建与性能研究

发布时间：2018-03-07 15:52

本文选题：酶生物燃料电池　切入点：纳米碳材料　出处：《湖南大学》2015年硕士论文　论文类型：学位论文

【摘要】：酶生物燃料电池(EBFC)是一类以生物酶作为催化剂直接将化学能转化为电能的转换装置,具有清洁、高效、成本低廉、操作简单、燃料可再生等优点,在能源匮乏、环境污染严重的今天备受关注。如今,EBFC的研究主要面临输出功率低下和电池寿命短两大难题,这两大问题制约了EBFC的发展及应用。改善这两大问题可以从酶或中间体的固定材料和固定方法入手。为了提高EBFC的输出功率和使用寿命,选择合适的酶或中间体的固定材料和固定方法是目前EBFC研究的重点。本论文采用不同方法实现葡萄糖氧化酶(GOD)和中间体二茂铁(Fc)的固定,以此构建了几种酶电极,并对酶电极相应的性能进行了研究。具体的研究内容如下:(1)利用芘硼酸的硼酸基团与GOD的糖基之间的反应实现GOD芘基功能化,再利用芘基与CNTs之间强烈的π-π堆积作用实现GOD在CNTs表面的固定,以此修饰GC电极制得GOD-PBA/CNTs/GC酶电极。电化学性能研究表明:与GOD/CNTs/GC电极相比,GOD-PBA/CNTs/GC电极能够负载更多的GOD且稳定性也得到提高。以GOD-PBA/CNTs/GC电极为阳极、E-TEK Pt/C为阴极构建的葡萄糖/氧气EBFC的开路电位(Voc)和短路电流(isc)分别为0.44 V和0.43 m A cm-2,且在0.12 V时最大输出功率密度为28μW cm-2。(2)利用β-环糊精在碱性水热条件下原位还原氧化石墨烯(GO)与HAuCl_4制备金纳米粒子修饰的石墨烯(GNs-Au),利用半胱氨酸的桥‖作用,先将半胱氨酸与二茂铁甲醛通过席夫碱反应共价连接,然后利用半胱氨酸中的巯基与金纳米粒子之间的作用实现中间体在石墨烯表面的固定化,最后用GA将GOD交联到其表面制备生物阳极(GNs-Au-Fc/GOD-GA/GC电极)。与GNs/Fc/GOD-GA/GC电极和GNs-Au/GOD-GA/GC电极相比,GNs-Au-Fc/GOD-GA/GC电极有着明显的优势。该生物阳极与E-ETK Pt/C电极构筑的葡萄糖/氧气EBFC也有着较好的性能。(3)用功能化的CNTs固定二茂铁制得CNTs-Fc纳米材料,然后用CNTs-Fc与IL研磨得到的复合凝胶固定GOD制成GOD@CNTs-Fc/IL复合凝胶,将其涂到电极表面制备了GOD@CNTs-Fc/IL/GC酶电极,并且显示出很好的催化氧化葡萄糖的性能。GOD@CNTs-Fc/IL/GC电极作为生物阳极与E-TEK Pt/C生物阴极构建的EBFC开路电位是0.66 V,最大输出功率60μW cm~(-2)。
[Abstract]:Enzyme biofuel cell (EBFC) is a kind of conversion device which directly converts chemical energy into electric energy with enzyme as catalyst. It has the advantages of cleanness, high efficiency, low cost, simple operation, renewable fuel and so on. Today, serious environmental pollution has attracted much attention. Nowadays, the research of EBFC is faced with two major problems: low output power and short battery life. These two problems restrict the development and application of EBFC. To improve these two problems, we can start with the fixed materials and methods of enzyme or intermediate. In order to increase the output power and service life of EBFC, It is the focus of EBFC research to select suitable immobilization materials and methods of enzyme or intermediate. In this paper, we use different methods to immobilize glucose oxidase and ferrocene ferrocene (Fcc), and construct several enzyme electrodes. The specific research contents are as follows: 1) GOD pyrene functionalization is realized by the reaction between pyrene boric acid borate group and GOD glycosyl group. Using the strong 蟺-蟺 stacking interaction between pyrene group and CNTs, GOD was immobilized on the surface of CNTs. The electrochemical properties of GOD-PBA/CNTs/GC enzyme electrode prepared by modified GC electrode showed that compared with the GOD/CNTs/GC electrode, the GDD PBA / CNTs / GC electrode could support more GOD and the stability was improved. The glucose / TEK Pt/C cathode was constructed by using the GOD-PBA/CNTs/GC electrode as the anode and E-TEK Pt/C as the cathode. The open-circuit potential and short-circuit current of oxygen EBFC were 0.44V and 0.43mAcm-2, respectively, and the maximum output power density was 28 渭 W cm-2.02 at 0.12V) the gold was prepared by in-situ reduction of graphene oxide with 尾 -cyclodextrin under alkaline hydrothermal conditions with HAuCl_4. Nanocrystalline modified graphene GNs-Aun, using cysteine as a bridge, First, cysteine and ferrocene formaldehyde were covalently connected by Schiff base reaction, then the intermediates were immobilized on the surface of graphene by the interaction between thiol in cysteine and gold nanoparticles. Finally, the GNs-Au-Fc / GOD-GA-GC electrode of biological anode was prepared by crosslinking GOD to its surface by GA. Compared with GNs/Fc/GOD-GA/GC electrode and GNs-Au/GOD-GA/GC electrode, the GNs-Au-Fc / GOD-GA-GC electrode has obvious advantages. The glucose / oxygen EBFC constructed by this biological anode and E-ETK Pt/C electrode also has good properties. CNTs-Fc nanomaterials were prepared by immobilization of ferrocene with functionalized CNTs. Then the GOD@CNTs-Fc/IL composite gel was prepared by immobilizing GOD with the composite gel of CNTs-Fc and IL, and the GOD@CNTs-Fc/IL/GC enzyme electrode was prepared by coating it on the surface of the electrode. The EBFC open-circuit potential of CNTs-Fcr / L / GC electrode constructed as a biological anode and E-TEK Pt/C biological cathode is 0.66 V and the maximum output power is 60 渭 W / cm ~ (-2).
【学位授予单位】：湖南大学
【学位级别】：硕士
【学位授予年份】：2015
【分类号】：TM911.4

【参考文献】