钛片热氧化法制备光敏电极的研究

本文研究了以钛片为基底的TiO₂多晶薄膜电极的制备条件。发现在钛片热氧化和TiO₂膜的还原时,在气流中添加少量的水蒸气可解决TiO₂膜与基底结合不良的问题。制备了不同膜厚的光敏电极,研究了膜厚和光电流的关系。用热导法观察了氢气气氛下还原TiO₂的现象,研究了半导体化温度对光电流的影响。用制得的电极在日光下分解水制氢,能量转换效率为1.2%。     

质子交换膜燃料电池Pt/C阴极氧还原动力学模拟

质子交换膜燃料电池的商业化应用迫切要求降低其Pt载量. 本文通过Pt/C氧还原电极的动力学模型计算,研究了Pt/C电极中的氧分布、生成电流以及满足实际应用的最小Pt载量. 结果表明：燃料电池Pt/C电极,阴极产生严重浓差极化的催化层厚度为40mm;功率密度达到1.4 W•cm^-2（2.1 A•cm^-2@0.67 V）的电池性能需要3mm左右的Pt/C阴极催化层,阴极Pt载量为0.122 mg•cm^-2,即可使膜电极的阴极铂用量低于0.087 g•kW^-1.     

纳米氧化锰负载钛基电催化膜制备及处理含酚废水性能研究

以多孔钛膜为基膜,醋酸锰为锰源,采用溶胶凝胶法制备出负载纳米氧化锰的钛基电催化膜（nano-MnO_x/Ti膜）. 运用X射线衍射(XRD)、 X射线光电子能谱(XPS)、场发射扫描电子显微镜(FESEM)、循环伏安法(CV)、交流阻抗法（EIS）和计时电流法(CA)等测试手段,对MnO_x/Ti膜电极的微观形貌、晶型、电化学性能等进行表征. 结果表明：所得催化剂是由直径为50 nm的γ-MnO₂和Mn₂O₃纳米棒所组成,且均匀分布于Ti膜上,负载催化剂后钛膜电极电化学性能和催化性能明显提高,催化剂与基体之间键合的形成提高其稳定性. 以棒状nano-MnO_x/Ti膜电极为阳极构建电催化膜反应器(ECMR)处理含酚废水,当苯酚溶液浓度为10mmol·L^-1,电流密度为0.25mA·cm^-2、停留时间为15 min时,COD去除率可达95.1%.     

共基质改善MFC处理链霉素废水及产电性能的研究

以K_3[Fe(CN)_6]和NaCl混合溶液为阴极液,以驯化的人工湖泊底泥为微生物菌种,以链霉素废水为阳极液,构建微生物燃料电池实验系统,研究添加共基质前后微生物燃料电池的废水处理效果与同步发电性能。结果表明,以链霉素废水为阳极液的微生物燃料电池的产电能力及废水处理效果均较差,并且随着链霉素浓度的增大而进一步恶化;但将葡萄糖作为共基质添加至阳极链霉素废水后,微生物燃料电池的产电能力和废水处理效果均显著提高。链霉素浓度为50 mg/L时,未添加共基质的微生物燃料电池处理链霉素废水的COD去除率为52%,产电电流密度为25 m A/m~2,输出电压为4.72 m V;添加共基质后,COD去除率为92%,稳态产电电流密度为300 m A/m~2,稳态输出电压为54 m V。     

复合菌体及单一菌体催化的微生物燃料电池产电机理初步研究

利用淡水沉积物作为接种源构建了微生物燃料电池,考察苯酚对该微生物燃料电池性能的影响.结果表明,在淡水沉积物接种的微生物燃料电池中,电流的产生是由富集在电极表面的细菌引起的.苯酚降低了细菌消耗葡萄糖的速率,并在加入相同量葡萄糖的情况下,延长了产电时间.另一方面,实验还研究了一株从沉积物微生物燃料电池中分离出的单菌株的产电情况.该菌株在微生物燃料电池中需要借助自身代谢产生有电极反应活性的中间产物才能产电.GC-MS分析表明,中间产物中有吩嗪类物质,该类物质可在该细菌细胞与石墨电极之间充当电子传递介体,实现电子从细胞向电极的传递.     

Na2Ti3O7纳米片原位制备与钠离子电池负极材料应用

报道了Na₂Ti₃O₇纳米片的原位生长和钠离子电池负极材料的应用。通过简单的腐蚀市售的钛片制备出相互连接的微纳结构的Na₂Ti₃O₇纳米片。此外,腐蚀后的钛片在不用添加导电剂或粘结剂的情况下,可以直接作为电极材料使用。这种电极材料表现出优越的电化学性能,在50 mA·g^–1的电流密度下具有175 mAh·g^–1的可逆容量,在2000 mA·g^–1的电流密度下循环3000周后,其容量仍保持120 mAh·g^–1,容量保持率为96.5%。Na₂Ti₃O₇纳米片电极的优越电化学性能归因于二维结构具有较短的离子/电子扩散路径以及无粘结剂结构能有效的增加电极的电子传导能力。结果表明,这种微纳结构能够有效地克服Na₂Ti₃O₇作为电极材料离子/电子导电性差的缺点。因此,这种无粘结剂结构的Na₂Ti₃O₇纳米片负极材料是一种很有潜力的钠离子负极材料。     

化学修饰炭黑在微生物燃料电池中的生物产电行为

研究发现微生物燃料电池从启动到稳定运行的过程中往往存在一种现象,就是在高电流密度下,微生物燃料电池的输出电压会出现逆转,从而限制了微生物燃料电池的规模化应用,以及它在污废水处理、脱盐等方面的功能.
　　前期研究发现,微生物燃料电池的性能逆转现象与阳极材料的电容性能有关.电极材料的电容越大,越有利于微生物燃料电池的产电性能稳定,换言之,阳极材料电容不足导致产电性能逆转.但是超级电容活性炭的制作工艺繁琐,成本高,且导电性弱,不能满足微生物燃料电池的应用需求.炭黑的导电能力强、化学稳定性高、成本低,但作为微生物燃料电池的阳极则产生产电性能逆转现象.
　　化学修饰(如酸、碱活化或者添加具有赝电容性质的金属氧化物等)可以提高材料的电容性能.低温条件(80 oC)下,对低电容材料—炭黑进行HNO3和KOH的化学活化处理,并在此基础上,进一步用5%Fe3O4修饰,采用辊压工艺,以质量分数为60%的聚四氟乙烯乳液为粘结剂,制作微生物燃料电池的阳极,与空气阴极构建单室微生物燃料电池系统.采用傅里叶变换红外光谱(FTIR)、比表面积测试、材料表面pH和X射线能量分析光谱(EDX)等手段表征炭黑活化前后的物理、化学性质;接触角润湿性测试表征活化前后电极表面的亲疏水性.电化学循环伏安法测试活化前后,电极的电子存储能力.
　　与蒸馏水的pH相比较,材料表面pH分析表明炭黑材料经化学活化处理后,其表面pH无明显变化; FTIR和EDX测试表明化学活化处理使得炭黑表面引入含O(N)官能团;吸附-脱附曲线分析表明化学活化后,炭黑的比表面积减小,微孔与介孔的体积比增加;接触角测试表明炭黑阳极活化处理后,电极表面亲水性增加;循环伏安测试证实,化学活化后的炭黑阳极电容得到0.1–0.8 F/cm2的增长.结合燃料电池的产电性能测试,发现只有当炭黑阳极电容不小于1.1 F/cm2时,微生物燃料电池的产电逆转现象才会消失.炭黑阳极的化学活化方法为微生物燃料电池的性能稳定提供了一种简便、低成本的方法.     

聚苯胺/膨胀石墨电极的制备及其用于聚合物半电池的研究

以膨胀石墨作为基底电极, 采用恒电位法合成了聚苯胺(PAn), 并探讨了在膨胀石墨基底电极上电聚合生成PAn的电化学条件. 结果表明: 聚合电位为0.8 V, 苯胺和硫酸的浓度分别为0.2和0.3 mol/L的条件下电聚合得到的PAn具有最佳的电化学活性. 分别以PAn/膨胀石墨和金属Mg为工作电极, 铂片为辅助电极, 饱和甘汞电极为参比电极组成三电极体系, 测定PAn/膨胀石墨和Mg在0.1 mol/L的NaNO₂, MgCl₂, Mg(NO₃)₂及磷酸盐缓冲液(PBS)等不同电解质溶液中的极化曲线, 实验结果表明电解液的种类对PAn的稳定性影响不大, 而Mg在0.1 mol/L NaNO₂溶液中的稳定性最高. 以PAn/膨胀石墨作为阴极, 金属Mg为阳极, 0.1 mol/L NaNO₂为电解液组装成Mg│NaNO₂│PAn电池, 并考察了基于该聚合物电极的电池在电流密度为30 mA•g^－1时的恒电流放电行为. 相比于其它电解液, 该电池在0.1 mol/L NaNO₂电解液中具有较高的开路电位(1.84 V)和放电比容量(0.19 Ah•g^－1).     

化学修饰炭黑在微生物燃料电池中的生物产电行为（英文）

研究发现微生物燃料电池从启动到稳定运行的过程中往往存在一种现象,就是在高电流密度下,微生物燃料电池的输出电压会出现逆转,从而限制了微生物燃料电池的规模化应用,以及它在污废水处理、脱盐等方面的功能.前期研究发现,微生物燃料电池的性能逆转现象与阳极材料的电容性能有关.电极材料的电容越大,越有利于微生物燃料电池的产电性能稳定,换言之,阳极材料电容不足导致产电性能逆转.但是超级电容活性炭的制作工艺繁琐,成本高,且导电性弱,不能满足微生物燃料电池的应用需求.炭黑的导电能力强、化学稳定性高、成本低,但作为微生物燃料电池的阳极则产生产电性能逆转现象.化学修饰(如酸、碱活化或者添加具有赝电容性质的金属氧化物等)可以提高材料的电容性能.低温条件(80℃)下,对低电容材料—炭黑进行HNO3和KOH的化学活化处理,并在此基础上,进一步用5%Fe3O4修饰,采用辊压工艺,以质量分数为60%的聚四氟乙烯乳液为粘结剂,制作微生物燃料电池的阳极,与空气阴极构建单室微生物燃料电池系统.采用傅里叶变换红外光谱(FTIR)、比表面积测试、材料表面pH和X射线能量分析光谱(EDX)等手段表征炭黑活化前后的物理、化学性质;接触角润湿性测试表征活化前后电极表面的亲疏水性.电化学循环伏安法测试活化前后,电极的电子存储能力.与蒸馏水的p H相比较,材料表面pH分析表明炭黑材料经化学活化处理后,其表面pH无明显变化;FTIR和EDX测试表明化学活化处理使得炭黑表面引入含O(N)官能团;吸附-脱附曲线分析表明化学活化后,炭黑的比表面积减小,微孔与介孔的体积比增加;接触角测试表明炭黑阳极活化处理后,电极表面亲水性增加;循环伏安测试证实,化学活化后的炭黑阳极电容得到0.1–0.8F/cm2的增长.结合燃料电池的产电性能测试,发现只有当炭黑阳极电容不小于1.1 F/cm2时,微生物燃料电池的产电逆转现象才会消失.炭黑阳极的化学活化方法为微生物燃料电池的性能稳定提供了一种简便、低成本的方法.     

Fe2O3/rGO纳米复合物的制备及其储锂和储钠性能

金属氧化物可通过电化学转换反应与锂离子及钠离子发生多电子可逆结构转换,是一类极具应用前景的高容量锂离子和钠离子电池负极材料。实验以氧化石墨烯和铁盐为前驱体,采用简单的溶剂法,成功将Fe₂O₃纳米单晶粒子均匀负载于石墨烯的导电片层上,获得Fe₂O₃/rGO(还原氧化石墨烯)纳米复合材料。复合电极在锂离子和钠离子电池中都表现出优异的充放电性能和循环稳定性。实验结果表明石墨烯的包覆不仅能降低Fe₂O₃发生转换反应的电荷传递阻抗,而且能够稳定电极在循环过程中带来的结构转变,极大改善电极大电流充放能力和循环稳定性。本研究为发展高容量的锂离子和钠离子电池负极材料提供了可行的途径。     

Optimization of Bioelectricity Generation in Fed-Batch Microbial Fuel Cell: Effect of Electrode Material,Initial Substrate Concentration,and Cycle Time

Effective wastewater treatment and electricity generation using dual-chamber microbial fuel cell (MFC) will require a better understanding of how operational parameters affect system performance. Therefore, the main aim of this study is to investigate the bioelectricity production in a dual-chambered MFC-operated batch mode under different operational conditions. Initially, platinum (Pt) and mixed metal oxide titanium (Ti-TiO₂) electrodes were used to investigate the influence of the electrode materials on the power generation at initial dissolved organic carbon (DOC) concentration of 400 mg/L and cycle time of 15 days. MFC equipped with Ti-TiO₂ electrode performed better and was used to examine the effect of influent DOC concentration and cycle time on MFC performance. Increasing influent DOC concentration resulted in improving electricity generation, corresponding to a 1.65-fold increase in power density. However, decrease in cycle time from 15 to 5 days adversely affected reactor performance. Maximum DOC removal was 90?±?3 %, which was produced at 15-day cycle time with an initial DOC of 3,600 mg/L, corresponding to maximum power generation of about 7,205 mW/m².     

石墨烯基杂化材料在微生物燃料电池电极中的应用

微生物燃料电池（MFC）是利用生物催化剂将污水有机物中的化学能直接转化为电能的技术,因其功率密度和能量转化效率低,电极制作成本高,限制了其大规模实际应用。因此如何提高电极的催化性能并降低电极制作成本成为MFC的研究重点方向。由于石墨烯基杂化材料具有良好的导电性和催化特性,因此石墨烯基杂化材料成为在MFC电极应用中的热点之一。本文综述了近年来MFC石墨烯基杂化电极材料的最新研究进展,重点讨论了改性石墨烯电极、金属及非金属/石墨烯杂化电极、金属氧化物/石墨烯杂化电极、聚合物/石墨烯杂化电极和石墨烯凝胶电极的设计思路和制备方法及其催化性能,着重分析了石墨烯基阳极和阴极杂化材料对MFC产电性能的影响。最后对石墨烯基杂化材料在MFC应用中存在的问题及研究前景进行了总结和展望。     

微生物燃料电池生物阴极

微生物燃料电池(microbial fuel cells, MFCs)利用微生物处理废水的同时产电,是一种清洁可再生能源技术。近年来新兴起的生物阴极是指阴极室中的功能微生物附着在电极表面形成生物膜,电子由电极传递给微生物并发生相应的生物电化学反应;是微生物燃料电池研究的一个重要方向。本文根据厌氧、好氧操作体系的不同将生物阴极进行分类;归纳总结了微生物组成、电极和分隔材料的研究进展,探讨了生物阴极在去除污染物和生成高附加值产品中的实际应用,并提出了其将来发展的可能方向。     

Microbial Fuel Cells: The Effects of Configurations,Electrolyte Solutions,and Electrode Materials on Power Generation

This objective of this study is to conduct a systematic investigation of the effects of configurations, electrolyte solutions, and electrode materials on the performance of microbial fuel cells (MFC). A comparison of voltage generation, power density, and acclimation period of electrogenic bacteria was performed for a variety of MFCs. In terms of MFC configuration, membrane-less two-chamber MFCs (ML-2CMFC) had lower internal resistance, shorter acclimation period, and higher voltage generation than the conventional two-chamber MFCs (2CMFC). In terms of anode solutions (as electron donors), the two-chamber MFCs fed with anaerobic treated wastewater (AF-2CMFCs) had the power density 19 times as the two-chamber MFCs fed with acetate (NO₃ ⁻2CMFCs). In terms of cathode solutions (as electron acceptors), AF-2CMFCs with ferricyanide had higher voltage generation than that of ML-2CMFCs with nitrate (NO₃ ⁻ML-2CMFCs). In terms of electrode materials, ML-2CMFCs with granular-activated carbon as the electrode (GAC-ML-2CMFCs) had a power density 2.5 times as ML-2CMFCs with carbon cloth as the electrode. GAC-ML-2CMFCs had the highest columbic efficiency and power output among all the MFCs tested, indicating that the high surface area of GAC facilitate the biofilm formation, accelerate the degradation of organic substrates, and improve power generation.     

Microbial fuel cell based on Klebsiella pneumoniae biofilm

In this paper we reported a novel microbial fuel cell (MFC) based on Klebsiella pneumoniae (K. pneumoniae) strain L17 biofilm, which can utilize directly starch and glucose to generate electricity. The electrochemical activity of K. pneumoniae and the performance of the MFC were evaluated by cyclic voltammetry, scanning electron microscope (SEM) and polarization curve measurement. The results indicated that an established K. pneumoniae biofilm cells were responsible for the direct electron transfer from fuels to electrode during electricity production. The SEM observation proved the ability of K. pneumoniae to colonize on the electrode surface. This MFC generated power from the direct electrocatalysis by the K. pneumoniae strain L17 biofilm.     

Nanoporous gold electrode prepared from gold compact disk as the anode for the microbial fuel cell

The electrodes (anode and cathode) have an important role in the efficiency of a microbial fuel cell (MFC), as they can determine the rate of charge transfer in an electrochemical process. In this study, nanoporous gold electrode, prepared from commercially available gold-made compact disk, is utilized as the anode in a two-chamber MFC. The performance of nanoporous gold electrode in the MFC is compared with that of gold film, carbon felt and acid-heat-treated carbon felt electrodes which are usually employed as the anode in the MFCs. Electrochemical surface area of nanoporous gold electrode exhibits a 7.96-fold increase rather than gold film electrode. Scanning electron microscopy analysis also indicates the homogeneous biofilm is formed on the surface of nanoporous gold electrode, while the biofilm formed at the surface of acid-heat-treated carbon felt electrode shows rough structure. Electrochemical studies show although modifications applied on carbon felt electrodes improve its performance, nanoporous gold electrode, due to its structure and better electrochemical properties, acts more efficiently as the MFC’s anode. The maximum power density produced by nanoporous gold anode is 4.71 mW m^?2 at current density of 16.00 mA m^?2, while this value for acid-heat-treated carbon felt anode is 3.551 mW m^?2 at current density of 9.58 mA m^?2.     

Using 3D Composite Electrode Materials for Electricity Generation from Swine Wastewater in a Dual‐Chamber Microbial Fuel Cells

Swine wastewater has a high concentration of organic matter, suspended solids, and higher ammonia nitrogen, odor, complex polluting ingredients, and large emissions. A two‐chambered cubic microbial fuel cell (MFC) was used to evaluate the effect of a novel three‐dimensional (3D ) electrode made of 3D iron composites and 3D stainless composites on the electricity generation. Swine wastewater with a total chemical oxygen demand (TCOD ) of 3688 ± 300 mg/L was used as the feedstock in the anode chamber. The MFC reactor was incubated with an initial pH of 7.0 in an air shaker with a temperature of ~35°C and 100 rpm in the fed‐batch mode. A fixed external resistance (R ) of 100 Ω was connected between the electrodes, and the closed‐circuit potentials of the MFCs were recorded every 5 min. The results showed that using an iron–carbon fiber composite 3D electrode resulted in a peak electricity generation of 321 mV on the first 2 days and maintained a stable voltage of 163 mV during the second to sixth days. The COD removal efficiency could reach 75%. Using a stainless–carbon fiber 3D electrode could generate a peak voltage of only 29.5 mV and a stable voltage of 15.2 mV with a COD removal efficiency of 54%.     

Photoelectrochemical oxidation behavior of methanol on highly ordered TiO2 nanotube array electrodes

The highly ordered titanium dioxide nanotube array (HOTDNA) electrodes were prepared in hydrofluoric acid solution by electrochemical anodic oxidation technique on a pure titanium sheet. The HOTDNA electrodes were characterized by X-ray diffraction, SEM microscopy, and UV–vis spectra. It has shown high density, well ordered and uniform titanium dioxide nanotube array film covered on these electrodes and the TiO₂ structure depending on the heating condition, the anatase phase of TiO₂ appeared when heating to 500 °C. The photoelectrochemical characteristics of methanol in 0.5 M Na₂SO₄ on the HOTDNA electrodes were investigated. The cyclic voltammetry, photocurrent-time and open-circuit photopotential response of methanol on the HOTDNA electrode were represented and significant photogenerated current was observed upon illumination in the UV regions with the light of 253.7 nm central wavelength. The effect of variables such as light intensity, applied potential, and methanol concentration on the photoelectrochemical response was investigated. It was found that the photocurrent was greatly influenced by these factors.     

Effect of Temperature on the Catalytic Ability of Electrochemically Active Biofilm as Anode Catalyst in Microbial Fuel Cells

In this study we report the effect of temperature on the catalytic ability of an electrochemically active biofilm based on mixed‐culture to oxidize acetate and found the optimum temperature showing maximal catalytic activity and power output. Electrochemical characterization of biofilm and power output and internal resistance of microbial fuel cell (MFC) have been investigated at different temperatures. When temperature increased from 30 to 45 °C the catalytic ability of biofilms to oxidize acetate increased following the Arrhenius law with apparent activation energy of 44.85 kJ/mol. At temperatures higher than 48 °C, however, the bioelectrocatalytic current decreased. At 53 °C the bacterial metabolism was in inactivation. The optimum working temperature of the biofilm was 45 °C, producing current of 1339 µA cm^?2. This current was almost three times higher than 527 µA cm^?2 at 30 °C. The MFC performance at different temperatures showed consistent temperature dependence to that of a semi‐batch cell, which implies that anode catalytic ability in MFC is the main limit factor for increasing power output. A maximum power output of 1065 mW m^?2 was also observed at 45 °C and it was 1.5 times higher than 764 mW m^?2 at 30 °C. The increased MFC performance from 30 °C to 45 °C is lower in comparison with about three times higher increase in semi‐batch cells. This could be due to other factors such as proton migration rate in membrane of MFC, which can be seen from that the internal resistance value of 121.5 Ω in the MFC at 45 °C was only slightly lower than 177.6 Ω at 30 °C. Also, some other factors such as cell configuration which would limit the power output and can be further optimized. This work contributes to the study of influence from temperature on anodic electrochemically active biofilm activity and their subsequent influence on MFC performance and reports the optimal temperature for biofilm activity based on mixed‐culture.     

葡萄糖在Ti/NanoTiO2-ZrO2修饰电极上电催化氧化

在无水乙醇和乙酰丙酮混合溶液中,电解Ti金属制得前驱体Ti(OCH2CH3)4-y(acac)y,再加入ZrCl4,将上述溶液直接水解、干燥后,在450℃煅烧2 h,粉体通过X射线衍射(XRD)分析表明:纳米TiO2-ZrO2粉体呈单分散结构。扫描电子显微镜(SEM)测试表明,颗粒平均尺寸为30~40 nm。通过溶胶-凝胶法制得高活性的Ti/NanoTiO2-ZrO2修饰电极,采用循环伏安研究发现,Ti/NanoTiO2-ZrO2电极对葡萄糖氧化具有高催化活性。在NaBr电解液中,Br-在Ti/NanoTiO2-ZrO2电极表面氧化为Br2,Br2间接电氧化葡萄糖。