不锈钢网阴极微生物燃料电池的产电性能研究

构建了一个以曝气池污泥为阳极接种微生物、碳毡为阳极、无任何修饰的不锈钢网为阴极的双室微生物燃料电池. 通过输出电压、功率密度以及电化学阻抗等考察了阴极面积对电池产电性能的影响,并对电池的长期运行稳定性进行评价. 研究结果表明,不锈钢网作为微生物燃料电池的阴极性能稳定. 当不锈钢网面积为2 × 2 cm²时,最大输出电压达到0.411 V,功率密度为0.303 W•m^-2,内阻841 Ω,极化内阻80 Ω. 增大阴极面积至2 × 4 cm²,最大输出电压能达到0.499 V,内阻减小至793 Ω. 不锈钢网价格便宜,具有长期运行稳定性,适宜做MFCs的阴极.     

无膜生物电化学制氢反应器的产气特性

研究了无膜生物电化学制氢反应器的设计及产气特性。设计和组装的电化学制氢反应器为无膜电化学制氢反应器。它是以碳毡作为阳极,以负载一定量Ni-Al-Sn（Ni-50%、Al-45%、Sn-5%）合金粉催化剂的石墨板作为阴极,乙酸钠作为电解质。其工作原理是在两极间外加一定电压,阳极区的微生物降解有机物产生电子到达阴极,质子在阴极得到电子生成氢气。主要考察了阳极碳毡数量、环境温度、外加电压等因素对产气速率和氢气选择性的影响。结果表明,当阳极面积为900cm²、环境温度为30℃、外加电压为0.9V时,反应器产气速率最高可达4.21m³/(d·m³),氢气选择性最高为70.4%。     

温度对形成MEC阳极膜的影响

为探究温度对MEC(Microbial electrolytic cell)阳极膜形成的影响,本实验采用单池MEC产氢装置,在外加电解电压1. 0V,p H=7的厌氧环境下,利用厌氧活性污泥为接种物,以乙酸钠为底物,分别在温度为15℃,25℃,35℃,45℃,55℃的条件下进行MEC阳极膜的培养及阳极膜的产氢能力验证实验。培养过程中,通过测定电解电流,p H值,氢气含量,电化学活性、膜生物量等指标的变化,以分析温度对MEC阳极膜形成的影响;验证实验中则通过测定氢气含量说明各温度条件下培养的膜的产氢能力。实验结果表明,在温度从15℃逐渐升至55℃的过程中,各实验组产生的最大电流先逐渐增大,而后又逐渐减小,最大电流分别为13. 5mA、17. 9mA、22. 5mA、1. 1mA、0. 5mA,相比之下,高温较低温更不利于电活性微生物的生长富集,而中温(25～35℃)最利于其生长繁殖。其中,在35℃时呈现出较大的电流值,最大电流值为22. 5mA,在35℃时氢气含量也最高,高达24. 49%,所以35℃是MEC阳极膜形成的最佳温度。     

MoS2/GQDs催化剂的制备及微生物电解池的产氢性能研究

通过水热法合成了一系列MoS₂/GQDs复合材料,并制成碳基复合电极。利用电化学测试手段挑选出最佳电极后用于微生物电解池（MEC）阴极的产氢性能研究。实验结果显示： Na₂MoO₄、半胱氨酸和GQDs的最佳原料配比为375:600:1,制备出的MoS₂/GQDs呈现明显的爆米花样纳米片结构,片层厚度在10 nm左右,当碳纸负载量为1.5 mg·cm^-2时,MoS₂/GQDs碳纸电极的析氢催化能力最佳。在MEC产氢实验中,MoS₂/GQDs阴极MEC的产气量、氢气产率、库仑效率、整体氢气回收率、阴极氢气回收率、电能回收率和整体能量回收率分别为51.15±3.15 mL·cycle^-1、0.401±0.032 m³H₂·m³d^-1、91.16±0.054%、66.64±5.39%、72.44±2.60%、217.26±7.42%和77.37±1.50%,均略高于Pt/C阴极MEC或与之媲美。另外,MoS₂/GQDs具有良好的长期稳定性,且价格便宜,有利于实际应用。     

MoS_2/石墨烯复合阴极材料的制备及微生物电解池催化产氢性能

采用水热法合成了一系列MoS_2/石墨烯(Gr)复合物,并制成碳基复合电极.利用扫描电子显微镜、透射电子显微镜、线性扫描伏安法等手段对材料进行表征,研究了MoS_2/Gr电极作为微生物电解池(MEC)阴极的产氢性能.结果表明,MoS_2/Gr复合材料呈现三维层状结构,且负载在石墨烯上的MoS_2为无定形MoS_2.(NH_4)_2MoS_4和氧化石墨烯的最佳原料配比为1∶1,当滴涂量为1.5mg/cm~2时,电极的析氢催化能力最强.在MEC产氢实验中,MoS_2/Gr阴极MEC的平均产氢电流密度、产氢率、库仑效率、氢气回收率和阴极氢气回收率分别为(9.96±0.65)A/m~2,(0.424±0.041)m~3H_2/(m~3·d),(89.11±5.87)%,(70.47±6.78)%和(78.86±2.49)%,均高于Pt/C阴极MEC;其能量回收率也与后者相媲美.另外,MoS_2/Gr具有良好的长期稳定性,且价格便宜,适于实际应用.     

生物电化学系统降解多环芳烃萘及微生物群落研究

采用单室空气阴极微生物燃料电池(MFC)反应器构型, 以不同浓度萘为基底物质, 考察MFC的产电性能、 萘降解率、 化学需氧量(COD)和总有机碳含量(TOC)降解率及MFC阴阳极微生物活性和多样性. 结果表明, 循环伏安曲线受不同浓度萘的影响变化较为明显, 随着萘浓度的增大, 最大功率密度呈下降趋势, 且萘对MFC的阴极电极电势影响较大; 当萘的浓度为15 mg/L时, MFC最大功率密度可达(645.841±28.08) mW/m ²; 对萘的降解率高达100%, 且MFC对COD和TOC的降解率随着萘浓度的提高而增大, 但是增大的速率逐渐减小. 对MFC阳极微生物膜进行高通量测序发现, Geobacter是优势菌属, 相对丰度达81%, 阴极主要以Aquamicrobium为主.     

双极室联合处理啤酒废水的微生物燃料电池

构建了双极室连续流联合处理废水的微生物燃料电池(MFC), 该MFC阳极室的出水直接用于阴极室的进水, 利用阴极室的好氧微生物进一步降解有机物. 以啤酒废水作底物, 研究了该MFC的产电性能和废水处理效果. 结果表明, 采用双极室连续流MFC可以大大提高废水的处理效果, 对啤酒废水化学需氧量(COD)的总去除率可达92.2%~95.1%, 其中阳极室中COD去除率为47.6%~56.5%. MFC的开路电压为0.451 V, 最大输出功率为2.89 W/m³. 实验中抑制MFC性能的主要因素是阴极的极化损失, 通过降低进入阴极室溶液的COD浓度、采用优质的阴极材料和加大阴极室内的曝气量等方法进一步优化电池的性能.     

生物阴极微生物燃料电池不同阴极材料产电特性

以葡萄糖(COD初始浓度为2000 mg/L, COD为化学需氧量)为阳极燃料底物, 考察了碳纤维刷和柱状活性碳颗粒作为生物阴极微生物燃料电池(MFC)阴极材料的产电性能. 研究结果表明, 碳纤维刷MFC的启动时间比碳颗粒MFC的长, 达到稳定状态后的恒负载(300 Ω)电压(0.324 V)比碳颗粒阴极MFC的(0.581 V)低. 极化分析结果表明, 碳纤维刷MFC和碳颗粒MFC的最大功率密度分别为24.7 W/m3(117.2 A/m3)和50.3 W/m3(167.2 A/m3). 电化学交流阻抗谱(EIS)测定结果表明, 由于电极材料对微生物生长和分布状态存在不同的影响, 使得碳纤维刷阴极MFC的极化内阻大于碳颗粒阴极MFC的极化内阻.     

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。     

电极面积对老龄垃圾渗滤液为底物的微生物燃料电池性能影响

构建生物阴极型双室微生物燃料电池,处理老龄垃圾渗滤液。研究了阳极与阴极面积比值对微生物燃料电池产电能力和对老龄垃圾渗滤液处理效果的影响。结果表明,阳极与阴极面积比为1:2、2:2、2:1的3组生物阴极型微生物燃料电池输出电压分别为408、452、396mV,最大电功率密度分别为145.73、237.65、136.50mW/m³,内阻分别为350、200、400Ω,COD的去除率分别为21.18%、20.20%、22.31%。3组微生物燃料电池运行30d后,垃圾渗滤液中氨氮、硝酸盐氮、亚硝酸盐氮浓度均下降,其中,氨氮去除率分别为80.88%、73.61%和66.17%,其去除效果与产电性能相关。     

Combining phosphate species and stainless steel cathode to enhance hydrogen evolution in microbial electrolysis cell (MEC)

Microbial electrolysis cells (MEC) must work around neutral pH because of microbial catalysis at the anode. To develop a hydrogen evolution cathode that can work at neutral pH remains a major challenge in MEC technology. Voltammetry performed at pH 8.0 on rotating disk electrodes showed that the presence of phosphate species straightforwardly multiplied the current density of hydrogen evolution, through the so-called cathodic deprotonation reaction. The mechanism was stable on stainless steel cathodes whereas it rapidly vanished on platinum. The phosphate/stainless steel system implemented in a 25 L MEC with a marine microbial anode led to hydrogen evolution rates of up to 4.9 L/h/m² under 0.8 V voltage, which were of the same order than the best performance values reported so far.     

复合材料NiOx-ZSM-5的制备及微生物电解池催化析氢性能

在Na₂O-TPABr-Al₂O₃-SiO₂-H₂O溶胶体系中加入碳球, 采用水热晶化法合成ZSM-5分子筛载体, 负载镍盐制备复合材料NiO_x-ZSM-5. 利用X射线衍射(XRD)、 扫描电子显微镜(SEM)、 透射电子显微镜(TEM)、 X射线光电子能谱(XPS)、 氮气吸附-脱附和电化学测试等手段对样品进行表征, 利用微生物电解池(MEC)评价其催化析氢性能. 结果表明, 在碳球作用下ZSM-5分子筛为纳米粒子聚集的椭球形貌, 介孔比表面积和介孔孔容明显增加. 浸渍焙烧后的黑色斑点NiO_x覆盖在晶隙形成的介孔表面和分子筛的表面. 相比于纯NiO, 镍盐浸渍量为40%的复合材料中多价态镍氧的吸收峰向高结合能方向移动, 多价态镍、 铝原子和氧空位活性位数量明显 增多, 显著提高了复合材料的电催化活性, 使其具有较高电流密度(8.45 mA/cm²)和较低起始析氢过电位 (151 mV), 优于NiO电极. 在MEC运行周期内, 复合材料的平均析氢电流密度为(28.64±7.4) A/m², 总产气量为(52.67±1.64) mL, H₂纯度为(89.07±0.06)%, 略高于商用Pt/C电极[(89.05±0.05)%], 产氢效率(0.571 m³?m^-3?d^-1)和库仑效率[(76.7±5.4)%]与Pt/C阴极相近, 表明复合材料是一种低成本和高效率的析氢材料.     

空气阴极生物燃料电池电化学性能

为提高生物燃料电池(MFC)的输出功率, 降低内阻和有机物处理成本, 实验以空气电极为阴极, 泡沫镍(铁)为阳极,葡萄糖模拟废水为基质构建了直接空气阴极单室生物燃料电池, 考察了电池的电化学性能. 结果表明, MFC的开路电压为0.62 V, 内阻为33.8 Ω, 最大输出功率为700 mW·m-2 (4146 mW·m-3污水), 电子回收率20%. 放电曲线、循环伏安测试表明, MFC首次放电比容量和比能量分别为263 mAh·g-1 COD(化学需氧量)和77.3 mWh·g-1 COD, MFC充放电性能及稳定性均较好. 电化学交流阻抗谱(EIS)分析表明, 随放电时间的延长, 电池阻抗增大, 这是导致电池输出电压逐渐降低的原因之一. MFC运行8 h, COD的去除率为56.5%, 且COD的降解符合表观一级反应动力学.     

Nanopolyaniline Coupled with an Anticorrosive Graphene as a 3D Film Electrocatalyst for Efficient Oxidation of Toluene Methyl C−H Bonds and Hydrogen Production at Low Voltage

A graphene-wrapped polyaniline nanoparticles film embedded in carbon cloth (CC/PANI/G) was fabricated and used as a 3D anodic electrocatalyst for oxidation of toluene methyl C−H groups. The methyl C−H bonds can be oxidized effectively at the CC/PANI/G anode with 99.9 % toluene conversion at a low applied voltage of only 1.0 V, which implies low energy input. Importantly, 86.6 % of toluene methyl C−H groups were converted to benzoyl groups (C=O), and hydrogen was produced efficiently at the cathode. The electrocatalytic efficiency at the CC/PANI/G anode was higher at lower voltage (1.0 V) than at higher voltage (1.5 V), and more hydrogen was produced at the corresponding cathode. The synergistic effect between the dynamic redox chemistry of nanoPANI and the excellent conductivity and anticorrosive action of graphene determined the high electrocatalytic efficiency of the oxidation of toluene methyl C−H groups at the CC/PANI/G anode. Owing to the chemical bonding between graphene and PANI, the anticorrosive CC/PANI/G anodic electrocatalyst was durable and effective for oxidation of toluene methyl C−H groups in acidic environment. This approach provides advanced electrode materials for transforming stable chemical bonds (C−H) into useful functional groups (C=O), which will be beneficial for the synthesis of organic intermediates with coupled hydrogen production.     

纳米NiO-Y复合阴极材料的制备及微生物电解池催化产氢性能

在Y分子筛的溶胶反应体系中加入碳球,经老化、水热晶化反应得到纳米Y分子筛,通过等体积浸渍（incipient-wetness impregnation,IWI）方式负载镍盐前驱体,经焙烧制备纳米NiO-Y复合材料,采用XRD、SEM、TEM、XPS、TG-DTG和N₂吸附-脱附等手段对其物理化学性质进行表征。结果表明,合成的NiO-Y复合材料样品的晶粒粒径为500 nm,具有微-介孔多级孔道结构。总比表面积达到774.3 m²/g,孔容为0.495 cm³/g,有利于暴露更多的活性位。通过线性扫描和塔菲尔曲线电化学测试评价发现,当镍盐负载量为30%（质量分数）时,纳米NiO-Y复合材料作为微生物电解池阴极具有较高的电催化活性。在运行周期内,样品的最大析氢电流密度达到22.87 A/m²,产气总量中H₂含量占73.71%,产氢效率为0.393 m³/（m³·d）,与Pt/C阴极产氢效率相近。     

Electrodialysis for clean-up of strongly alkaline samples in ion chromatography

An electrodialysis method is described for the off-line neutralization of strongly alkaline samples containing trace levels of common inorganic anions. This method uses an electrodialysis cell comprising three compartments separated from each other by cation-exchange membranes. These compartments comprise an anode compartment housing, a platinum wire anode and 10 ml of a suitable hydrogen ion donating medium, a sample compartment which contains 1 ml of the alkaline sample, and a cathode compartment housing a platinum wire cathode and a dilute solution of sodium hydroxide. During electrodialysis at either constant applied current or constant applied power, hydrogen ions from the anode compartment displace sodium ions from the sample, thereby effecting neutralization.

Experimental parameters, such as the magnitude of the applied current or power, the type of cation-exchange membrane used and the design of the cell have been studied and optimum results were obtained using a Neosepta CM-2 membrane, of area 616 mm² supported between two perspex discs, with an applied current of 150 mA or applied power of 3 W. Under these conditions, a 1 ml sample of 1 M sodium hydroxide could be neutralized in 11 min. The most effective hydrogen ion donating medium consisted of a 2:1 (w/v) slurry of BioRad AG 50W-X8 (200–400 mesh, H⁺ form) cation-exchange resin in 1 mM octanesulfonic acid. Recoveries of solute anions (3–10 μg/ml) from the dialysed solution were close to quantitative, except for fluoride and nitrite, which gave recoveries of less than 60%. It is suggested that low recoveries for these ions are due to formation of neutral, protonated species within the membrane with subsequent loss by diffusion.     

Application of an electrochemical membrane reactor to the thermochemical water splitting IS process for hydrogen production

The Bunsen reaction (SO₂ + I₂ + 2H₂O = H₂SO₄ + 2HI) in the thermochemical IS process to produce hydrogen was successfully employed using an electrochemical membrane reactor. H₂SO₄ and HI were concentrated in the anode side and the cathode side of the reactor, respectively. I₂ is the dominant bulk of the recycling chemicals in this process, and I₂ concentration at the outlet of the reactor was reduced ca. 93% by using this technique. The electric energy consumption for the reaction was about 50% smaller by reducing the concentration of I₂ indicating that the IS process can be operate efficiently at low I₂ concentration. The reaction was carried out for 4 h, and the HI concentration was increased by 26%. This amount was the same within 10% as the values calculated from the total loaded electricity. In order to decrease the overpotential at the anode side, small amount of HI was added to the anode side solution. The total voltage was reduced by 0.03 V by the addition of HI.     

污泥水解液基质微生物燃料电池的研究

研究不同污泥热水解时间下水解液特性及其对微生物燃料电池（MFC）产电的影响.水解时间由2 h增至96 h,水解液pH基本稳定于7.4 ~ 8.0;水解时间增加,其电导率逐渐提高至2.53 mS·cm^-1,COD浓度和碱度也不断增加,水解液的缓冲能力不断得到提高.MFC最大功率密度达到25 W·m^-3,COD去除率呈现先增后降,水解6 h时达到最大（47%）;库仑效率在预水解4 h时达到最高（71%）.阳极室pH下降可归因于NH⁴⁺、Na⁺、Ca²⁺、Mg²⁺等阳离子迁移,其中NH⁴⁺的迁移量最大.