微生物燃料电池及介孔磷酸锆阳极材料的电化学研究
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摘要
目前污水处理仍是一种消耗大量电能的处理技术,因此解决污水处理工程中的耗能问题,降低治污成本,对于广大污染严重的发展中国家来说尤为重要。微生物燃料电池能降低污水COD并且能产生电能,因而成为环境与新能源方面研究的热点。但由于产电性能低,电池内阻大以及受结构设计的限制使得微生物燃料电池不能适应大规模的污水处理。
制约微生物燃料电池输出功率的最大因素是发生在阳极上的电子传递过程。在微生物燃料电池最新的研究中,采用对微生物酶分子的蛋白质外壳进行修饰,将电极延伸至酶分子活性中心附近,以缩短电子传递的距离。随着纳米科学和技术的发展,研究者们发现一些纳米材料在微生物或酶的强化稳定和活化方面表现出了很大的潜力。磷酸锆(ZrP)类材料是近年逐步发展起来的一类多功能材料,具有良好的生物相容性,但磷酸锆的导电性能差限制了其作为阳极材料在燃料电池中的应用。
本论文研究的单室空气阴极微生物燃料电池(ACMFC),以石墨毡为阳极,Pt/C(铂/碳纸)为阴极,以空气中的氧为最终电子受体,简化了微生物燃料电池的装置,降低了电池内阻;阳极室采用开放式,不对阳极室通厌氧气体,降低了运行成本;论文研究了装置内流体条件、葡萄糖底物浓度等条件对电池产电性能的影响并评价污水处理效果。测试结果表明最佳水流流速为15.0 mL/min、最适葡萄糖底物的浓度为1.0 g/L,电池的最大功率为90.2 mW/m2。电池运行48 h,对模拟废水的COD去除率可达到81.6 %。
论文第三章分别以表面活性剂及XC-72为模板,磷酸为沉淀剂,通过调节磷酸的量采用水热法合成不同形貌的磷酸锆及ZrP/XC-72复合物。测试结果表明当磷酸的量大于2.4 mol/L时,可以合成厚度为5 nm~10 nm,大小200 nm~300 nm的六方形片状磷酸锆。当磷酸的量为1.2 mol/L时,可以合成具有3 nm介孔结构的无定形磷酸锆。对比片状磷酸锆、介孔磷酸锆及ZrP/XC-72复合物负载葡萄糖氧化酶的电化学性能,测试结果得到电子传递速率分别为1.3 s-1,1.6 s-1,2.0 s-1(扫速为100 mV/s),表明介孔结构比片状结构负载酶的效果好,而ZrP/XC-72复合物负载酶能明显提高电子传递速率。三种材料制备的电极表观负载酶的浓度分别为1.4×10-10 mol/cm2、6.6×10-11 mol/cm2、1.8×10-10 mol/cm2(扫速为100 mV/s),比文献报道的大1~2个数量级。
Currently, sewage treatment technology is a process of exhausting a lot of electrical energy. Solving the energy consumption issue and reducing the anti-pollution cost are especially useful for the developing countries. Microbial fuel cell (MFC) can generate electricity while treating wastewater, so it attracts more attention as a new type of energy recovery technology. The major problems faced by MFC towards commercialization are the high internal resistance and the limitation in the structures designing to harvest more power.
The biggest factor for energy output of battery is electron transfer in anode. In the current study, the modified microbial protein shell can make the electrode extend to the enzyme activity center. The distance of electron transfer is shortened greatly. With the development of nano science and technology, finding some nanomaterials have great potential in strengthening enzymes’stability and activation. Zirconium phosphate is gradually developed in recent years as a kind of multifunctional material. It has good biocompatibility, but the low conductivity limits zirconium phosphate’s application as the anode in fuel cells.
In this paper, we designed an air cathode MFC; Graphite felt and Pt/C were used for anode and cathode, respectively and oxygen in air was the final electron acceptor. Those designs had simplified the MFC devices and reduced internal resistance of battery. An open anode chamber reduced the operation cost. The energy output of MFC at different conditions was compared such as flow rate, concentration of glucose and so on. The results demonstrated that the best flow rate was 15.0 mL/min and optimal concentration of glucose was 1.0 g/L, while the great power output of battery was 90.2 mW/m2. The COD removal rate could reach 81.6 % for working 48 h.
In chapter three of this paper, adjusting the volume of phosphoric acid could prepare the zirconium phosphate with different morphologies in hydrothermal synthesis. In the process, the surfactant was a template and phosphoric acid was the precipitation agent. Carbon was a hard template. Test results showed that when the amount of phosphate was more than 2.4 mol/L, we could make zirconium phosphate to be hexagon nano piece with the size of 200 nm~300 nm and thickness of 5 nm~ 10 nm. When the amount of phosphate was 1.2 mol/L, zirconium phosphate was mesoporous structure materials with bore of 3 nm. Using XC-72 as a template ZrP/XC-72 complex was synthesized. Their abilities of immobilizing GOD were compared. The Ks were 1.3 s-1,1.6 s-1,2.0 s-1 for platelike ZrP, mesoporous ZrP and ZrP/XC-72 respectively. That was the electronic transfer rate of zirconium phosphate with mesoporous structure was faster than platelike zirconium phosphate and ZrP/XC-72 could improve the electronic transfer rate of an electrode. The amount of enzyme loading on the surface of electrode was 1.4×10-10 mol/cm2, 6.6×10-11 mol/cm2 and 1.8×10-10 mol/cm2 respectively. Those were 1~2 orders of magnitude better than that reported in the literature.
制约微生物燃料电池输出功率的最大因素是发生在阳极上的电子传递过程。在微生物燃料电池最新的研究中,采用对微生物酶分子的蛋白质外壳进行修饰,将电极延伸至酶分子活性中心附近,以缩短电子传递的距离。随着纳米科学和技术的发展,研究者们发现一些纳米材料在微生物或酶的强化稳定和活化方面表现出了很大的潜力。磷酸锆(ZrP)类材料是近年逐步发展起来的一类多功能材料,具有良好的生物相容性,但磷酸锆的导电性能差限制了其作为阳极材料在燃料电池中的应用。
本论文研究的单室空气阴极微生物燃料电池(ACMFC),以石墨毡为阳极,Pt/C(铂/碳纸)为阴极,以空气中的氧为最终电子受体,简化了微生物燃料电池的装置,降低了电池内阻;阳极室采用开放式,不对阳极室通厌氧气体,降低了运行成本;论文研究了装置内流体条件、葡萄糖底物浓度等条件对电池产电性能的影响并评价污水处理效果。测试结果表明最佳水流流速为15.0 mL/min、最适葡萄糖底物的浓度为1.0 g/L,电池的最大功率为90.2 mW/m2。电池运行48 h,对模拟废水的COD去除率可达到81.6 %。
论文第三章分别以表面活性剂及XC-72为模板,磷酸为沉淀剂,通过调节磷酸的量采用水热法合成不同形貌的磷酸锆及ZrP/XC-72复合物。测试结果表明当磷酸的量大于2.4 mol/L时,可以合成厚度为5 nm~10 nm,大小200 nm~300 nm的六方形片状磷酸锆。当磷酸的量为1.2 mol/L时,可以合成具有3 nm介孔结构的无定形磷酸锆。对比片状磷酸锆、介孔磷酸锆及ZrP/XC-72复合物负载葡萄糖氧化酶的电化学性能,测试结果得到电子传递速率分别为1.3 s-1,1.6 s-1,2.0 s-1(扫速为100 mV/s),表明介孔结构比片状结构负载酶的效果好,而ZrP/XC-72复合物负载酶能明显提高电子传递速率。三种材料制备的电极表观负载酶的浓度分别为1.4×10-10 mol/cm2、6.6×10-11 mol/cm2、1.8×10-10 mol/cm2(扫速为100 mV/s),比文献报道的大1~2个数量级。
Currently, sewage treatment technology is a process of exhausting a lot of electrical energy. Solving the energy consumption issue and reducing the anti-pollution cost are especially useful for the developing countries. Microbial fuel cell (MFC) can generate electricity while treating wastewater, so it attracts more attention as a new type of energy recovery technology. The major problems faced by MFC towards commercialization are the high internal resistance and the limitation in the structures designing to harvest more power.
The biggest factor for energy output of battery is electron transfer in anode. In the current study, the modified microbial protein shell can make the electrode extend to the enzyme activity center. The distance of electron transfer is shortened greatly. With the development of nano science and technology, finding some nanomaterials have great potential in strengthening enzymes’stability and activation. Zirconium phosphate is gradually developed in recent years as a kind of multifunctional material. It has good biocompatibility, but the low conductivity limits zirconium phosphate’s application as the anode in fuel cells.
In this paper, we designed an air cathode MFC; Graphite felt and Pt/C were used for anode and cathode, respectively and oxygen in air was the final electron acceptor. Those designs had simplified the MFC devices and reduced internal resistance of battery. An open anode chamber reduced the operation cost. The energy output of MFC at different conditions was compared such as flow rate, concentration of glucose and so on. The results demonstrated that the best flow rate was 15.0 mL/min and optimal concentration of glucose was 1.0 g/L, while the great power output of battery was 90.2 mW/m2. The COD removal rate could reach 81.6 % for working 48 h.
In chapter three of this paper, adjusting the volume of phosphoric acid could prepare the zirconium phosphate with different morphologies in hydrothermal synthesis. In the process, the surfactant was a template and phosphoric acid was the precipitation agent. Carbon was a hard template. Test results showed that when the amount of phosphate was more than 2.4 mol/L, we could make zirconium phosphate to be hexagon nano piece with the size of 200 nm~300 nm and thickness of 5 nm~ 10 nm. When the amount of phosphate was 1.2 mol/L, zirconium phosphate was mesoporous structure materials with bore of 3 nm. Using XC-72 as a template ZrP/XC-72 complex was synthesized. Their abilities of immobilizing GOD were compared. The Ks were 1.3 s-1,1.6 s-1,2.0 s-1 for platelike ZrP, mesoporous ZrP and ZrP/XC-72 respectively. That was the electronic transfer rate of zirconium phosphate with mesoporous structure was faster than platelike zirconium phosphate and ZrP/XC-72 could improve the electronic transfer rate of an electrode. The amount of enzyme loading on the surface of electrode was 1.4×10-10 mol/cm2, 6.6×10-11 mol/cm2 and 1.8×10-10 mol/cm2 respectively. Those were 1~2 orders of magnitude better than that reported in the literature.
引文
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