废旧金属网阴极微生物电解池产氢性能及阳极微生物群落结构分析

为寻找质优价廉的析氢催化剂,本研究以废旧金属网为单室微生物电解池(MEC)阴极,在不同外加电压下考察其制氢性能. 同时利用16S rDNA扩增测序技术分析原接种污泥、MFC和MEC阳极微生物的菌落特点. 实验结果表明,随着外加电压的增大,MEC产生的最大电流密度和周期运行时间分别呈现增大和缩短的趋势. 外加0.7 V电压时,废旧金属网阴极MEC的氢气产率和电能回收率分别达到0.330±0.012 m³H₂·m^-3·d^-1和177.0±5.6%,远高于0.5 V时的数值,与0.9 V时相差不大. 废旧金属网阴极MEC的产氢能力可以和Pt/C阴极MEC相媲美,且具有良好的运行稳定性. 16S rDNA扩增测序结果显示培养环境对微生物的富集与淘汰有很大影响. 在外加电场环境中MEC阳极的优势菌落地杆菌属(Geobacter)得到很大程度富集,相对丰度高达79.4%以上.     

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.     

TiO_2纳米管双室光电化学池光催化制氢的研究

以阳极氧化法在纯钛表面制备了高度有序的Ti O2纳米管阵列,并通过SEM观察其表面形貌。采用双室光电化学池制氢体系,利用太阳光照Ti O2产生的光电压与双室电解液p H差产生的化学偏压的协同效应,不施加外加电压,可直接在阴极室还原制取氢气。通过在碱性电解液中添加乙二醇为电子给体,将光解水制氢与有机物的降解耦合为一体,提高太阳能的利用率,同时考察了阳极室电解液中添加不同含量乙二醇对Ti O2纳米管光阳级的光电化学性能及产氢量的影响。实验结果表明,乙二醇的添加降低了光生电子-空穴对的复合几率,使Ti O2纳米管的光电流、光电压、产氢量得到显著提高。当添加乙二醇的浓度为10vol%时光电流达到13.7 m A·cm-2,无外加电压条件下,双室光电化学池中的产氢速率最高达到3.8μmol·min-1·cm-2。     

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。     

Co3O4/Ti电催化膜电极制备及其苯甲醇催化氧化性能

本文采用浸渍涂覆法成功制备出多孔Ti负载纳米Co₃O₄电催化膜电极（Co₃O₄/Ti）,以该膜电极为阳极,辅助电极为阴极,构建电催化膜反应器（electrocatalytic membrane reactor,ECMR）用于可控催化氧化苯甲醇制备苯甲醛和苯甲酸,并考察了 Co₃O₄/Ti 膜电极结构、电化学性能以及ECMR不同操作参数对苯甲醇转化率、苯甲醛和苯甲酸选择性的影响. 结果表明,负载Co₃O₄纳米颗粒可以显著提高Ti膜电极的电化学性能和催化活性. 在常温常压下,当反应物苯甲醇浓度为10 mmol·L^-1,pH为7.0,停留时间为5.0 min,电流密度为2.5 mA·cm^-2,苯甲醇的转化率达到49.8%,苯甲醛选择性为51.5%,苯甲酸选择性为23.6%.     

煤基型焦牺牲阳极强化水电解制氢实验研究

传统炭辅助电解水制氢技术将煤、生物质等碳源直接加入阳极室形成浆液,受炭颗粒、氧化基团和电极之间传递影响,反应速率慢,只有在低电流密度下才能实现电解制氢能耗的降低。以煤为碳源、碱活化生物质为黏结剂、石墨为导电颗粒,通过共成型和共热解工艺获得煤基型焦牺牲阳极,并用于炭辅助水电解制氢过程,可在高电流密度下（50 mA/cm²）显著提高炭辅助水电解制氢效率。电化学测试和阳极材料表征表明,煤基型焦牺牲阳极通过自身的牺牲（被氧化）强化阴极反应,进而实现水电解制氢电化学性能的提高。型焦牺牲阳极在1.23 V（vs. RHE）时,制氢电流密度是铂阳极的87倍,Tafel斜率降低了41%。煤基型焦阳极在50 mA/cm²电流密度下阴极产氢速率是铂阳极体系的2.47倍,但电极电位仅为铂阳极的85%。SEM、TGA、BET、FT-IR和XPS结果表明,电解后牺牲阳极自身被氧化,羧基类C=O键被氧化生成CO₂,醚类C–O含量显著增加。研究成果为炭辅助电解水制氢技术提供了全新思路与参考。     

基于阳极甘油氧化电催化的碱/酸混合电解制氢研究（英文）

耦合可再生电能的电解水制氢是一项极具前景的绿氢技术,该技术仍受限于阳极析氧反应(OER)动力学慢、过电位高等问题的限制。在阳极端采用热力学更容易的电氧化反应代替OER,可大幅降低电耗并且在阳极端获得增值产物,是电解制氢的一种新策略。甘油作为生物柴油生产的主要副产品且产能过剩,其电催化氧化(GOR)理论电位比OER低。基于此,本研究工作报道了一种耦合酸性析氢反应(HER)与碱性GOR的混合酸/碱双电解液的制氢电解器,其以泡沫镍(NF)支撑Co₃O₄纳米片(NS)电极(Co₃O₄·NSs/NF)为阳极,商用碳载铂修饰碳布电极为阴极。在阳极端,Co₃O₄·NSs/NF对GOR电催化表现出较低的过电位和转化为甲酸盐的高选择性。在该混合酸/碱双电解液电解槽中,仅仅需要额外施加0.55 V的外加电压,即可达到10 mA·cm^-2的产氢电解电流密度,并可以在阳极将甘油高选择性地转化为甲酸盐,其中产氢的法拉第效率接近100%。本研究工作为电解制氢提供...     

TiO2纳米管双室光电化学池光催化制氢的研究

以阳极氧化法在纯钛表面制备了高度有序的TiO₂纳米管阵列,并通过SEM观察其表面形貌。采用双室光电化学池制氢体系,利用太阳光照TiO₂产生的光电压与双室电解液pH差产生的化学偏压的协同效应,不施加外加电压,可直接在阴极室还原制取氢气。通过在碱性电解液中添加乙二醇为电子给体,将光解水制氢与有机物的降解耦合为一体,提高太阳能的利用率,同时考察了阳极室电解液中添加不同含量乙二醇对TiO₂纳米管光阳级的光电化学性能及产氢量的影响。实验结果表明,乙二醇的添加降低了光生电子-空穴对的复合几率,使TiO₂纳米管的光电流、光电压、产氢量得到显著提高。当添加乙二醇的浓度为10vol%时光电流达到13.7mA·cm^-2,无外加电压条件下,双室光电化学池中的产氢速率最高达到3.8μmol·min^-1·cm^-2。     

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。     

偶氮四唑钾盐的绿色电合成反应耦合WS2纳米片催化电解水制氢

析氧反应(OER)作为动力学缓慢的四电子多步骤反应过程,限制了电催化水分解制氢的反应速率,降低了电催化水分解制氢的整体效率,以热力学更有利的有机含能材料氧化反应替代OER与析氢反应(HER)耦合,在降低槽压制得氢气的同时能得到高附加值的化工产品.本文建立了一种新的耦合体系,在阳极侧制备含能离子盐[偶氮四唑钾盐(K₂AZT)]的同时,阴极侧以碳布负载的二硫化钨纳米片(CC@WS₂ NSs)作为HER催化剂促进H₂的形成.该体系仅需要1.65 V的槽电压即可达到10 m A/cm²的电流密度,相比于CC@WS₂ NSs/CF全解水体系(1.87 V)降低了220 m V.耦合体系在至少15 h内保持平稳运行,表现出优异的稳定性能.通过绿色安全的电化学法制备含能化合物避免了传统有机合成方法高能耗、高风险和高成本等问题,为安全生产含能材料提供了新的合成策略.     

Impact of modified electrodes on boosting power density of microbial fuel cell for effective domestic wastewater treatment:A case study of Tehran

Utilizing microbial fuel cells (MFCs) is a promising technology for energy-efficient domestic wastewater treatment, but it still faces practical barriers such as low power generation. In this study, the LaMnO₃ perovskite-type oxide nanoparticles and nickel oxide/carbon nanotube/polyaniline (NCP) nanocomposite (the cathode and anode catalysts, respectively) have been prepared and used to enhance power density of MFC. The prepared La-based perovskite oxide catalysts were characterized by X-ray diffraction (XRD) and scanning electron microscopies (SEM). The electrocatalytic properties of the prepared catalysts were investigated through cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS) and Tafel plot at ambient temperature. Results show the exchange current densities of LaMnO₃/carbon cloth cathode and NCP nanocomposite/carbon cloth anode were 1.68 and 7 times more compared to carbon cloth cathode, respectively. In comparison to the bare carbon cloth anode, the MFC with the modified electrodes shows 11 times more enhancement in power density output which according to electrochemical results, it can be due to the enhancement of the electron transfer capability. These cathodic and anodic catalysts were examined in batch and semi-continuous modes to provide conditions close to industrial conditions. This study suggests that utilizing these low cost catalysts has promising potential for wastewater treatment in MFC with high power generation and good COD removal efficiency.     

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.     

Nanostructured polyaniline-coated anode for improving microbial fuel cell power output

An approach for improving the power generation of a dual-chamber microbial fuel cell by using a nanostructured polyaniline (PANI)-modified glassy carbon anode was investigated. Modification of the glassy carbon anode was achieved by the electrochemical polymerisation of aniline in 1 M H₂SO₄ solution. The MFC reactor showed power densities of 0.082 mW cm^?2 and 0.031 mW cm^?2 for the nano- and microstructured PANI anode, respectively. The results from electron microscopy scanning confirmed formation of the nanostructured PANI film on the anode surface and the results from electrochemical experiments confirmed that the electrochemical activity of the anode was significantly enhanced after modification by nanostructured PANI. Electrochemical impedance spectroscopic results proved that the charge transfer would be facilitated after anode modification with nanostructured PANI.     

Enhanced power production of microbial fuel cells by reducing the oxygen and nitrogen functional groups of carbon cloth anode

The physicochemical properties of anode material are important for the electron transfer of anode bacteria and electricity generation of microbial fuel cells (MFCs). In this work, carbon cloth anode was pretreated with isopropanol, hydrogen peroxide (H₂O₂) and sodium hypochlorite (NaOCl) in order to reduce the anode functional groups. The influence of functional groups on the electrochemical properties of carbon cloth anode and power generation of MFCs was investigated. The anode pretreatments removed the surface sizing layer of carbon cloth and substantially reduced the contents of C‐O and pyridinic/pyrrolic N groups on the anode. Electrochemical impedance spectroscopy and cyclic voltammetry analyses of the biofilm‐matured anodes revealed an enhanced electrochemical electron transfer property because of the anode pretreatments. As compared with the untreated control (612 ± 6 mW m^?2), the maximum power density of an acetate‐fed single‐chamber MFC was increased by 26% (773 ± 5 mW m^?2) with the isopropanol treated anode. Additional treatment with H₂O₂ and NaOCl further increased the maximum power output to 844 ± 5 mW m^?2 and 831 ± 4 mWm^?2. A nearly inverse liner relationship was observed between the contents of C‐O and pyridinic/pyrrolic N groups on anodes and the anodic exchange current density and the power output of MFCs, indicating an adverse effect of these functional groups on the electricity production of anodes. Results from this study will further our understanding on the microbial interaction with carbon‐based electrodes and provide an important guidance for the modification of anode materials for MFCs in future studies. Copyright © 2016 John Wiley & Sons, Ltd.     

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.     

影响MFC产电能力及污水净化的非生物因素研究

以厌氧污泥接种模拟生活污水, 构建双室无介体型微生物燃料电池(MFC). 以输出功率密度、库仑效率和COD_Cr(化学需氧量)去除率为评价指标, 采用正交设计考察4种非生物因素(即阴、阳极材料、底物和电子受体)对MFC产电及污水净化的影响. 在此基础上进一步探讨阴极离子浓度对电能输出的影响. 结果表明: 对MFC产能及污水净化的影响因素顺序为: 电子受体＞阳极＞阴极＞底物, 最优组合为碳毡-乳酸钠-不锈钢板-铁氰化钾＋溶解氧|向阴极液中投加NaCl可使产电能力显著增强, 最佳投加量为150 mmol•L^－1. 同时, 阴极室定期添加铁氰化钾可维持电流稳定. 试验中, 葡萄糖型、乳酸钠型以及混合型底物模拟污水的COD_Cr均得到有效去除, 平均去除率达85.2%, 显示了研究的MFC具有很强的产电和污水净化能力.     

预嵌锂硬碳和软碳用于锂离子电容器负极的比较研究

锂离子电容器是一种应用前景广阔的电化学储能器件. 目前,活性炭作为锂离子电容器正极被广泛使用. 然而,锂离子电容器负极却有多种不同选择,如硬碳和软碳等碳材料. 本文使用两种具有不同结构和电化学特性的硬碳和软碳材料作为锂离子电容器负极,进行了对比研究. 研究表明,软碳相比于硬碳有更好的电子导电性和更高的可逆容量. 通过在电流范围0.1 ~ 12 A·g^-1下进行充放电测试,分别研究了两种碳基电极在不同涂覆厚度下的倍率性能. 结果显示,硬碳电极在大电流下有更好的倍率特性. 然后,以活性炭为正极,预嵌锂的硬碳和软碳为负极,锂片为锂源和参比电极,分别组装了三电极软包锂离子电容器. 根据三电极充放电测试,分别研究了不同预嵌锂量的硬碳和软碳所组装的锂离子电容器的电化学性能. 结果表明,合适的负极预嵌锂容量可以提升锂电容的能量密度、功率密度和循环稳定性. 最后,大容量硬碳和软碳基软包锂离子电容器被分别组装,软碳基锂电容实现了最高的能量密度21.2 Wh·kg^-1（基于整个器件质量）,硬碳基锂电容实现最高的功率密度5.1 kW·kg^-1.     

A membrane electrode assembly for the electrochemical synthesis of hydrocarbons from CO2(g) and H2O(g)

We report the electrochemical reduction of CO₂ into hydrocarbons using a new electrochemical membrane reactor holding a yet unreported membrane electrode assembly comprising a copper mesh cathode and a Ti felt coated with mixed metal oxide (MMO) catalyst anode separated by a proton conductive membrane. CO_2(g) was supplied to the cathodic reduction compartment, whilst humidified N₂ was supplied to the anodic oxidation compartment. The MMO anode produces protons transported across the proton exchange membrane and electrons transported via the external circuit to the copper cathode to reduce CO_2(g). Production rates of methane, propane, propene, iso-butane and n-butane were determined as a function of cell potential at temperatures between 30 and 70 °C and relative humidity between ca. 25% and 75%. Maximum methane concentration and the current efficiency for production of hydrocarbons were 3.29 ppm and 0.12%, respectively. Whilst the observed product spectrum is desirable, such low current efficiencies require systematic optimization of the catalytic membrane system, in particular an improved cathode with an optimum contact between proton conducting membrane, electrode and catalyst is desired.     

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.     

活性炭纤维电极生成羟基自由基降解酸性红B

分别采用具有吸附催化性能的活性炭纤维(ACF)作为阳极和阴极对水中偶氮染料酸性红B (ARB)的电化学降解情况进行了系统研究. 研究表明两种体系均可较好降解ARB, 可达到色度完全去除, 但ACF作为阴极电芬顿对有机物的矿化程度远远高于以ACF作为阳极时的矿化程度, 其TOC去除率达到70%, 高于阳极体系的30% TOC去除率. 通过电子自旋捕集技术(ESR)检测两种反应体系中产生的活性中间体, 发现在两种体系中均有高活性的羟基自由基生成, ACF阴极体系中产生的羟基自由基的量远远高于阳极体系产生量, 这是阴极体系有机物矿化效果较好的根本原因. 还对电流强度和初始pH的影响进行了研究, 并对两个体系反应机理进行了讨论.