酶生物燃料电池的制备及其性能研究
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摘要
酶生物燃料电池利用生物催化剂酶直接把化学能转化为电能,是一种清洁、高效、安静运行的电化学发动机,具有燃料来源广泛、反应条件温和、生物相容性好等优点,是一种可再生的绿色能源。酶生物燃料电池的研究主要集中在寻找固定酶的新方法上及对电池放电性能的测试上。本文详述了酶电极的制备方法,研究了单极室和“三合一”酶生物燃料电池的制备及其性能测试方面的内容。
聚合物修饰电极由于具有三维空间结构,薄膜内有大量的电活性中心,十分有利于电催化。同时制备方法简单,电极使用寿命长,从而得以广泛使用。本文制备聚合物膜修饰电极,将此化学修饰电极应用于酶生物燃料电池中的阳极,充当固定化酶电极的电子介体作用。
本文主要研究工作如下:
1.用循环伏安法制备了聚亚甲基绿修饰电极(PMG/CME),探讨了该修饰电极的电化学聚合过程、表征、循环伏安性质及修饰电极对NADH的电催化特作用,实验发现PMG/CME对NADH有明显的电催化作用,结果满意。
2.制备了单极室酶生物燃料电池。阳极采用电化学沉积法固定化ADH-NAD~+,阴极仍采用传统方法,Pt/C催化剂的碳纸,阴极和质子交换膜热压在一起,组装单极室酶生物燃料电池。利用乙醇和纯氧分别作为阳极和阴极的燃料,ADH-NAD~+酶作为催化剂,用于催化燃料乙醇的氧化脱氢。实验结果表明,该电化学沉积法单极室酶燃料电池的开路最高电压达到735mV。在外阻负载为3kΩ时,电池的稳定输出电压为395 mV,电池的稳定输出功率密度达到62.4μW/cm~2。酶在间歇使用过程中的工作寿命为两个月之多。
3.新设计了一个具有三层结构的酶电极:第一层为聚亚甲基绿(PMG)膜和NAD~+的混合溶液;第二层为PMG膜;第三层是含有离子吸附型的固定化酶(固定化ADH),它们一起组装成“三合一”膜电极。用乙醇和氧气分别做为阳极和阴极的燃料,对“三合一”酶生物燃料电池一系列电化学性能进行检测,在外加负载为300Ω,电池的最大电流密度为170±4.3μA/cm~2,稳定输出电压为425 mV左右,电池的稳定输出功率密度达到72.3μW/cm~2,开路电压最大可达到630 mV。结果表明这种固定化酶的方法有利于酶生物燃料电池的电子传递。
Enzymatic biofuel cell is a device converting chemical energy directly with the biocatalysts, which has the advantage of abundant fuel resource, mild reaction condition and good biology consistency. In enzymatic biofuel cell aspect, more attention is concentrated on new method to immobilized enzyme. The details of preparation methods of enzymatic electrodes are especially described. This paper researched into the preparation and performance of single-compartmentalized and membrane electrode assembly enzymatic biofuel cells.
The polymer films have three dimension configurations, which supply much available energy field. There are a lot of active groups in the polymer films. The polymer films have electrochemical catalyze characteristics. Because of its easy preparation and strong attachment to the electrode surface, the polymer modified electrode has distinguished itself as one of the most widely used chemically modified electrodes. This work prepared polymer chemically modified electrode, which acted as electron medium of immobilized enzyme electrode.
The main research work is as follows:
1. First of all, we prepared poly-(methylene green) chemically modified electrode by cyclic voltammetric method. We studied the PMG/CME of electropolymerization process, characterization, electrochemical behavior and electrocatalyzing NADH. The experiment result is PMG/CME has obvious electrocatalysis to NADH.
2. We report the assembly of single-compartmentalized enzymatic biofuel cell. The alcohol dehydrogenase (ADH) and NAD~+ was immobilized in the PMG/CME by co-electrodepositing method as bioanode for the oxidation of alcohol. We used tradition method Pt/C catalyzer as cathode, oxygeon as cathodic fuel. Experiment indicated that the maximum open circuit voltage could reach 735 mV. The maximum output power density was 62.4μW/cm~2, output potential was about 395 mV at an external optimal load of 3 kΩand enzyme lifetime was two months.
3. We designed a three-layer structural enzymatic electrode. The first layer is PMG and NAD~+, the second layer is PMG, the third layer is ion adsorption ADH. Then we fabricated membrane electrode assembly enzymatic biofuel cell. We also used tradition method Pt/C catalyzer as cathode, oxygeon as cathodic fuel. Also we measured the performance of membrane electrode assembly enzymatic biofuel cell. Experiment indicated that the maximum current density was 170±4.3μA/cm~2 and the maximum output power density was 72.3μW/cm~2 and the output potential was about 425 mV at an external optimal load of 300Ω. The maximum open circuit voltage could reach 630 mV. Dehydrogenase enzymes immobilized in the poly-methylene green membrane have shown high catalytic activity and can promote the direct bioelectrocatalysis for alcohol's oxidation.
聚合物修饰电极由于具有三维空间结构,薄膜内有大量的电活性中心,十分有利于电催化。同时制备方法简单,电极使用寿命长,从而得以广泛使用。本文制备聚合物膜修饰电极,将此化学修饰电极应用于酶生物燃料电池中的阳极,充当固定化酶电极的电子介体作用。
本文主要研究工作如下:
1.用循环伏安法制备了聚亚甲基绿修饰电极(PMG/CME),探讨了该修饰电极的电化学聚合过程、表征、循环伏安性质及修饰电极对NADH的电催化特作用,实验发现PMG/CME对NADH有明显的电催化作用,结果满意。
2.制备了单极室酶生物燃料电池。阳极采用电化学沉积法固定化ADH-NAD~+,阴极仍采用传统方法,Pt/C催化剂的碳纸,阴极和质子交换膜热压在一起,组装单极室酶生物燃料电池。利用乙醇和纯氧分别作为阳极和阴极的燃料,ADH-NAD~+酶作为催化剂,用于催化燃料乙醇的氧化脱氢。实验结果表明,该电化学沉积法单极室酶燃料电池的开路最高电压达到735mV。在外阻负载为3kΩ时,电池的稳定输出电压为395 mV,电池的稳定输出功率密度达到62.4μW/cm~2。酶在间歇使用过程中的工作寿命为两个月之多。
3.新设计了一个具有三层结构的酶电极:第一层为聚亚甲基绿(PMG)膜和NAD~+的混合溶液;第二层为PMG膜;第三层是含有离子吸附型的固定化酶(固定化ADH),它们一起组装成“三合一”膜电极。用乙醇和氧气分别做为阳极和阴极的燃料,对“三合一”酶生物燃料电池一系列电化学性能进行检测,在外加负载为300Ω,电池的最大电流密度为170±4.3μA/cm~2,稳定输出电压为425 mV左右,电池的稳定输出功率密度达到72.3μW/cm~2,开路电压最大可达到630 mV。结果表明这种固定化酶的方法有利于酶生物燃料电池的电子传递。
Enzymatic biofuel cell is a device converting chemical energy directly with the biocatalysts, which has the advantage of abundant fuel resource, mild reaction condition and good biology consistency. In enzymatic biofuel cell aspect, more attention is concentrated on new method to immobilized enzyme. The details of preparation methods of enzymatic electrodes are especially described. This paper researched into the preparation and performance of single-compartmentalized and membrane electrode assembly enzymatic biofuel cells.
The polymer films have three dimension configurations, which supply much available energy field. There are a lot of active groups in the polymer films. The polymer films have electrochemical catalyze characteristics. Because of its easy preparation and strong attachment to the electrode surface, the polymer modified electrode has distinguished itself as one of the most widely used chemically modified electrodes. This work prepared polymer chemically modified electrode, which acted as electron medium of immobilized enzyme electrode.
The main research work is as follows:
1. First of all, we prepared poly-(methylene green) chemically modified electrode by cyclic voltammetric method. We studied the PMG/CME of electropolymerization process, characterization, electrochemical behavior and electrocatalyzing NADH. The experiment result is PMG/CME has obvious electrocatalysis to NADH.
2. We report the assembly of single-compartmentalized enzymatic biofuel cell. The alcohol dehydrogenase (ADH) and NAD~+ was immobilized in the PMG/CME by co-electrodepositing method as bioanode for the oxidation of alcohol. We used tradition method Pt/C catalyzer as cathode, oxygeon as cathodic fuel. Experiment indicated that the maximum open circuit voltage could reach 735 mV. The maximum output power density was 62.4μW/cm~2, output potential was about 395 mV at an external optimal load of 3 kΩand enzyme lifetime was two months.
3. We designed a three-layer structural enzymatic electrode. The first layer is PMG and NAD~+, the second layer is PMG, the third layer is ion adsorption ADH. Then we fabricated membrane electrode assembly enzymatic biofuel cell. We also used tradition method Pt/C catalyzer as cathode, oxygeon as cathodic fuel. Also we measured the performance of membrane electrode assembly enzymatic biofuel cell. Experiment indicated that the maximum current density was 170±4.3μA/cm~2 and the maximum output power density was 72.3μW/cm~2 and the output potential was about 425 mV at an external optimal load of 300Ω. The maximum open circuit voltage could reach 630 mV. Dehydrogenase enzymes immobilized in the poly-methylene green membrane have shown high catalytic activity and can promote the direct bioelectrocatalysis for alcohol's oxidation.
引文
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