不同碳源催化化学气相沉积制备自支撑C/Ni-Fiber复合电极材料的电容脱盐性能

以甲烷、乙烯、乙醇和正丁醇为碳源,通过催化化学气相沉积在具有三维开放网络结构的烧结8μm-Ni金属纤维上沉积碳的方法,制备了以金属Ni纤维网络为集流极、沉积碳为离子存储库的薄层大面积自支撑C/Ni-fiber复合电极材料.用扫描电子显微镜（SEM）、透射电子显微镜（TEM）、热重分析（TGA）、X射线衍射（XRD）、N₂-吸脱附等温线和循环伏安与电化学阻抗谱对电极材料进行了表征,并考察了其作为电极的电容脱盐性能.乙烯、甲烷、正丁醇和乙醇为碳源的沉积碳形态分别为鱼骨状碳纳米管（CNTs）、石墨烯面取向与轴平行的CNTs、棒状和蠕虫状碳纳米纤维（CNFs）.C/Ni-fiber复合电极材料对NaCl的电吸附容量顺序为:乙烯>正丁醇>甲烷>乙醇,这与复合电极的电化学特性、孔结构和碳的纳米结构相关.在1.2 V的工作电压下,以乙烯为碳源制备的C/Ni-fiber复合电极材料对水溶液中NaCl(100 mg·L^-1)的电吸附容量达159μmol·g^-1.     

自支撑CNTs/SMF-Ni电极上电催化氧气氧化茴香醚合成茴香醛

以具有三维开放网络结构的薄层大面积烧结8 μm金属纤维(SMF-Ni, SMF-SS(316L不锈钢))为基底, 通过乙烯催化化学气相沉积在金属纤维表面生长碳纳米管(CNTs)的方法, 制备了整体式CNTs/SMF-Ni (CNTs: 50% (w))和CNTs/SMF-SS (CNTs: 40% (w))复合材料. 研究表明, 以CNTs/SMF-Ni 为阴极材料、SMF-SS为阳极材料, 具有很高的直接电催化氧气氧化对甲氧基甲苯(茴香醚)合成对甲氧基苯甲醛(茴香醛) 的活性, 反应物转化率和产物选择性分别达95.4%和96.5%, 电流效率可超过80%.     

磺化石墨烯/活性炭复合电极的制备及其不对称电容器脱盐

在还原剂NaBH₄存在下, 采用对氨基苯磺酸重氮盐与氧化石墨(GO)表面共价键合制备磺化石墨烯(GP-SO₃H). 傅里叶变换红外光谱(FTIR)证明磺酸基团在石墨烯表面接枝. 采用扫描电子显微镜(SEM)研究了磺化石墨烯的表面形貌. 以磺化石墨烯为添加剂, 制备了磺化石墨烯/活性炭(GP-SO₃H/AC)复合电极. 循环伏安及阻抗分析结果表明, 该复合电极的电容特性及导电性有明显改善. 以活性炭电极为对电极组装了不对称电容器(GP-SO₃H/AC|AC), 研究了该不对称电容器的电化学脱盐性能. 与对称电容器(AC|AC)相比, 不对称电容器中由于电极内磺酸基团对反离子的屏蔽作用, 电容器的电流效率达到89.4%以上, 脱盐量提高2.4倍, 单个循环脱盐量达到10.87 mg/g.     

NiO/CNTs的制备及其电化学电容行为研究

用改良的沉淀法在酸化处理过的碳纳米管(CNTs)上沉积氢氧化镍, 经300 ℃热分解得到NiO/CNTs复合电极材料. 采用X射线衍射(XRD)、热重分析(TGA)、扫描电镜(SEM)和Brunauer-Emmett-Teller (BET)比表面积分析等方法对合成的材料进行了物理表征|用循环伏安法和充放电测试对其电化学性能进行了研究. 结果表明, CNTs的引入在一定程度上提高了NiO的分散性, 从而大大增加了复合电极材料的比电容和倍率容量. 掺入20% CNTs后复合电极的比电容达到最高值(309 F•g^－1)|掺入40% CNTs的复合电极材料扣除CNTs对容量的贡献后(本实验测试CNTs的比容量为35 F•g^－1), NiO的放电容量可达420 F•g^－1, 明显高于纯相NiO的容量(175 F•g^－1), 并且材料的倍率容量也显著提高.     

柔性复合织物电极Graphene/Cotton和MnO2/Graphene/Cotton的合成及在电化学电容器中的应用

通过热还原法成功地制备出了柔性复合织物电极石墨烯/棉布(graphene/cotton)。热还原条件对电极的导电性能具有较大的影响。导电柔性织物电极graphene/cotton特有的多级结构使其既有利于进一步负载膺电容材料,又有利于电子和电解质离子的传输与扩散。通过电化学沉积方法,利用导电柔性织物电极graphene/cotton进一步制备出了电极MnO₂/graphene/cotton。利用扫描电子显微镜(SEM),傅里叶变换红外(FTIR)光谱,四探针测试法等表征技术对电极的结构进行了较为详细的表征。结果表明电极MnO₂/graphene/cotton的比电容可以达到536 F·g^-1。良好的电化学性能和柔性使得此类电极在柔性储能材料应用中具有极大的应用前景。     

活性炭电极的改性及对Co2+,Mn2+和Ni2+的电吸附性能

以商用活性炭(AC)为原料,分别采用磷酸和氢氧化钠改性的方法制备了两种不同的改性活性炭电极材料.采用扫描电子显微镜(SEM)、透射电子显微镜(TEM)、 Brunauer-Emmett-Teller(BET)测试、傅里叶变换红外光谱(FTIR)和X射线光电子能谱(XPS)等手段以及电化学分析方法,对改性前后活性炭材料的表面性质和电化学性能进行了探究.结果表明, H3PO4改性使活性炭的孔隙分布更加密集, NaOH改性使活性炭表面的孔隙结构更加清晰均匀; H₃PO₄和NaOH改性均使活性炭的比表面积增加.循环伏安测试结果表明,改性前后活性炭电极在低扫描速率下均具备良好的双电层特性,并且两种改性处理均能提高活性炭电极的比电容;当扫描速率为5 mV/s时,未改性、 H₃PO₄以及NaOH改性活性炭电极的比电容分别为36.51, 77.25和85.19 F/g.电吸附实验结果证明,两种改性活性炭电极对Co²⁺, Mn²⁺和Ni²⁺均有较好的去...     

金复合介孔SBA-15吸附血红蛋白在H2O2电催化反应中的应用

以P123嵌段共聚物表面活性剂为模板剂制备介孔氧化硅SBA-15,并用沉积-沉淀(DP)法在SBA-15介孔表面负载纳米Au颗粒制备得到金复合介孔SBA-15材料(Au-SBA-15).再以Au-SBA-15材料制备玻碳修饰电极,将血红蛋白固定于修饰电极上用循环伏安法考察其对不同浓度H₂O₂溶液的电催化反应.在固定了血红蛋白的Hb/Au-SBA-15/GC修饰电极上,H₂O₂在+0.95 V处出现了氧化峰,且随着H₂O₂浓度的增大峰电流不断增加,说明金复合介孔氧化硅材料具有良好的生物兼容性,有利于血红蛋白的固定,其修饰电极对H₂O₂溶液具有一定的电催化作用.     

二氧化锰/石墨烯纸电极的制备及其电化学性能

通过电化学法使溶液中的Mn²⁺电解氧化为MnO₂,沉积复合在石墨烯片膜上,形成由MnO₂/石墨烯复合材料构成的纸电极。 采用X射线衍射(XRD)、扫描电子显微镜(SEM)和透射电子显微镜(TEM)、循环伏安(CV)和恒流放电等技术手段对纸电极材料的结构、形貌以及电化学性能进行了研究。 结果表明,MnO₂球形颗粒均匀地沉积在石墨烯片膜上,形成了厚度45 μm的纸电极,经过380 ℃煅烧后,纸电极中的MnO₂晶型由γ-MnO₂转化为β/γ-MnO₂混合晶型,是良好的柔性Li/MnO₂电池的电极材料。 MnO₂/石墨烯纸电极在室温下0.1C放电容量达269 mA·h/g,而且电化学阻抗低、柔韧性好。     

皱褶表面介孔镍钴硫化物微球的制备及其超电性能

通过一步水热法分别合成了α-NiS、Co₃S₄和CoNi₂S₄纳米介孔电极材料,并研究了其电化学性能。 X射线衍射(XRD)、扫描电子显微镜(SEM)和透射电子显微镜(TEM)研究表明,介孔硫化物是由单相纳米颗粒堆叠组装而成,其中二元系的CoNi₂S₄由纳米片自组装形成了具有皱褶表面的微球形貌。 电化学性能研究表明,二元系的CoNi₂S₄比α-NiS、Co₃S₄具有更高的比电容、更佳的倍率特性和优异的循环稳定性。 在扫描速率为5 mV/s时,CoNi₂S₄材料在6 mol/L KOH电解液中比电容高达1678.3 F/g,优于α-NiS (787.4 F/g)和Co₃S₄(1532.7 F/g),在扫描速率从5 mV/s增加到100 mV/s时,其电容保持率为45.8%,比α-NiS(30.2%)和Co₃S₄(29.3%)高出约15%。 在15A/g的电流密度下,经过900次循环充-放电后,二元系的CoNi₂S₄的电容仍保持在96.3%,库伦效率保持在94.3%左右,说明镍钴双金属硫化物具有优异的循环稳定性能和充放电可逆性。     

碳包覆碳酸钴锂离子电池负极材料的制备及电化学性能

以葡萄糖作为碳源,通过简单的水热反应获得菱形碳包覆碳酸钴(CoCO₃/C)复合材料,并研究了其作为锂离子电池负极材料的电化学性能.晶型和表面形貌通过X射线衍射(XRD)、扫描电子显微镜(SEM)和透射电子显微镜(TEM)进行表征,用热重-差热分析法(TG-DTA)来测试CoCO₃/C材料中碳的含量,用拉曼光谱分析无定型碳的存在. Barrett-Joyner-Halenda (BJH)则用来分析材料的孔径分布情况.实验表明,碳包覆不仅在CoCO₃颗粒表面包覆了一层无定性碳,使得CoCO₃材料在充放电过程中保持结构的稳定性,也形成了一些大约30 nm左右的介孔,这种孔的存在有助于电解液中离子的传输,从而提高材料的电化学性能.电极材料在0.90C(1.00C = 450 mAh•g^-1)倍率下进行循环测试, 500次后的容量仍保持在539 mAh•g^-1,显示出了较好的循环性能.当增加到3.00C倍率时CoCO₃/C容量为130 mAh•g^-1,再恢复到0.15C倍率时容量依然能够达到770 mAh•g^-1,表现出了CoCO₃/C具有良好的稳定性.     

低热固相法制备纳米MnO2/CNT超电容复合电极的循环稳定性

为了改善纳米MnO2超级电容器电极的充放电循环稳定性,以Mn(OAc)2·4H2O、NH4HCO3和碳纳米管(CNT)为原料,采用低热固相反应得到前驱体,再经焙烧和酸处理,制备了一系列CNT含量不同的纳米MnO2/CNT复合电极材料,并用X射线衍射(XRD)、透射电镜(TEM)和Brunauer-Emmett-Teller(BET)比表面积测定方法对其进行了表征.XRD分析结果表明,复合材料中的MnO2为纳米γ-MnO2.研究了复合电极在1 mol·L-1 LiOH电解质中的电化学性能,并与不含CNT的纯纳米MnO2电极进行了比较.结果表明,含CNTs为10%(w,质最分数,下同)和20%的MnO2/CNT复合电极的循环稳定性远优于纯纳米MnO2电极的循环稳定性,其中含10%CNTs的MnO2/CNT复合电极不仪具有良好的循环稳定性,而且在1000 mA·g-1高倍率充放电条件下仍具有200 F·g-1的高比电容.     

Amperometric and voltammetric detection of hydrazine using glassy carbon electrodes modified with carbon nanotubes and catechol derivatives

A simple procedure was developed to prepare a glassy carbon (GC) electrode modified with carbon nanotubes (CNTs) and catechol compounds. First, 25 microL of DMSO-CNTs solutions (0.4 mg/mL) was cast on the surface of GC electrode and dried in air to form a CNTs film. Then the GC/CNTs modified electrode immersed into a chlorogenic acid, catechine hydrate and caffeic acid solution (electroless deposition) for a short period of time (2-80s). The cyclic voltammogram of the modified electrode in aqueous solution shows a pair of well-defined, stable and nearly reversible redox couple (quinone/hydroquinone) with surface confined characteristics. The combination of unique electronic and electrocatalytic properties of CNTs and catechol compounds results in a remarkable synergistic augmentation on the response. The electrochemical reversibility and stability of modified electrode prepared with incorporation of catechol compound into CNTs film was evaluated and compared with usual methods for attachment of catechols to electrode surfaces. The transfer coefficient (alpha), heterogeneous electron transfer rate constants (k(s)) and surface concentrations (Gamma) for GC/CNTs/catechol compound modified electrodes were calculated through the cyclic voltammetry technique. The modified electrodes showed excellent catalytic activity, fast response time and high sensitivity toward oxidation of hydrazine in phosphate buffer solutions at pH range 4-8. The modified electrode retains its initial response for at least 2 months if stored in dry ambient condition. The properties of modified electrodes as an amperometric sensor for micromolar or lower concentration detection of hydrazine have been characterized.     

Amperometric glucose biosensor based on electrodeposition of platinum nanoparticles onto covalently immobilized carbon nanotube electrode

A new amperometric biosensor for glucose was developed based on adsorption of glucose oxidase (GOx) at the gold and platinum nanoparticles-modified carbon nanotube (CNT) electrode. CNTs were covalently immobilized on gold electrode via carbodiimide chemistry by forming amide linkages between carboxylic acid groups on the CNTs and amine residues of cysteamine self-assembled monolayer (SAM). The fabricated GOx/Au_nano/Pt_nano/CNT electrode was covered with a thin layer of Nafion to avoid the loss of GOx in determination and to improve the anti-interferent ability. The immobilization of CNTs on the gold electrode was characterized by quartz crystal microbalance technique. The morphologies of the CNT/gold and Pt_nano/CNT/gold electrodes have been investigated by scanning electron microscopy (SEM), and the electrochemical performance of the gold, CNT/gold, Pt_nano/gold and Pt_nano/CNT/gold electrodes has also been studied by amperometric method. In addition, effects of electrodeposition time of Pt nanoparticles, pH value, applied potential and electroactive interferents on the amperometric response of the sensor were discussed.

The enzyme electrode exhibited excellent electrocatalytic activity and rapid response for glucose in the absence of a mediator. The linear range was from 0.5 to 17.5 mM with correction coefficient of 0.996. The biosensor had good reproducibility and stability for the determination of glucose.     

Synthesis and Electrochemical Investigation of Tetra Amino Cobalt (II) Phthalocyanine Functionalized Polyaniline Nanofiber for the Selective Detection of Dopamine

A new electrochemical sensing platform based on tetra‐amino cobalt (II) phthalocyanine (TACoPc) ingrained polyaniline (PANI) nanofiber composite (TACoPc/PANI hybrid) has been developed for the selective detection of dopamine. The uniform fibrous network of PANI/TACoPc hybrid was synthesized by a one‐step oxidative polymerization at room temperature. The synthesized nanocomposite was characterized using field emission scanning electron microscopy (FESEM), energy dispersive X‐ray (EDX), fourier transmission infrared spectroscopy (FTIR), raman spectroscopy, X‐ray diffraction (XRD) and UV‐Visible spectroscopy. The electrochemical behavior of the TACoPc/PANI hybrid material was studied by using different electrochemical techniques, including cyclic voltammetry (CV) and chronoamperometry in 0.1 M phosphate buffer solution (PBS) of pH 7 by modifying the glassy carbon electrode (GCE). Due to the synergistic impact of PANI and TACoPc, the suggested altered electrode provided superior catalytic performance for dopamine even in the presence of ascorbic acid. It exhibited a linear reaction with a high sensitivity of 1.212 μA/μM cm^?2 and a low detection limit of 0.064 μM over the 20–200 μM concentration range in 0.1 M PBS. One of the commonly faced problems of interference of ascorbic acid and uric acid in the electrochemical detection of dopamine was completely excluded from this modified electrode which led to an increase in the catalytic activity of the material for the detection of dopamine in the presence of ascorbic acid.     

Characterization of nanoporous gold electrodes for bioelectrochemical applications

The high surface areas of nanostructured electrodes can provide for significantly enhanced surface loadings of electroactive materials. The fabrication and characterization of nanoporous gold (np-Au) substrates as electrodes for bioelectrochemical applications is described. Robust np-Au electrodes were prepared by sputtering a gold-silver alloy onto a glass support and subsequent dealloying of the silver component. Alloy layers were prepared with either a uniform or nonuniform distribution of silver and, post dealloying, showed clear differences in morphology on characterization with scanning electron microscopy. Redox reactions under kinetic control, in particular measurement of the charge required to strip a gold oxide layer, provided the most accurate measurements of the total electrochemically addressable electrode surface area, A(real). Values of A(real) up to 28 times that of the geometric electrode surface area, A(geo), were obtained. For diffusion-controlled reactions, overlapping diffusion zones between adjacent nanopores established limiting semi-infinite linear diffusion fields where the maximum current density was dependent on A(geo). The importance of measuring the surface area available for the immobilization was determined using the redox protein, cyt c. The area accessible to modification by a biological macromolecule, A(macro), such as cyt c was reduced by up to 40% compared to A(real), demonstrating that the confines of some nanopores were inaccessible to large macromolecules due to steric hindrances. Preliminary studies on the preparation of np-Au electrodes modified with osmium redox polymer hydrogels and Myrothecium verrucaria bilirubin oxidase (MvBOD) as a biocathode were performed; current densities of 500 μA cm(-2) were obtained in unstirred solutions.     

A Microwave Synthesis of Mesoporous NiCo2O4 Nanosheets as Electrode Materials for Lithium‐Ion Batteries and Supercapacitors

A facile microwave method was employed to synthesize NiCo₂O₄ nanosheets as electrode materials for lithium‐ion batteries and supercapacitors. The structure and morphology of the materials were characterized by X‐ray diffraction, field‐emission scanning electron microscopy, transmission electron microscopy and Brunauer–Emmett–Teller methods. Owing to the porous nanosheet structure, the NiCo₂O₄ electrodes exhibited a high reversible capacity of 891 mA h g^?1 at a current density of 100 mA g^?1, good rate capability and stable cycling performance. When used as electrode materials for supercapacitors, NiCo₂O₄ nanosheets demonstrated a specific capacitance of 400 F g^?1 at a current density of 20 A g^?1 and superior cycling stability over 5000 cycles. The excellent electrochemical performance could be ascribed to the thin porous structure of the nanosheets, which provides a high specific surface area to increase the electrode–electrolyte contact area and facilitate rapid ion transport.     

NiCo_2O_4 decorated PANI–CNTs composites as supercapacitive electrode materials

Hierarchical Ni Co_2O_4/PANI/CNTs hybrid composites were designed and fabricated having a layer of Ni Co_2O_4 on the surface of PANI encapsulated CNTs with different morphologies. Physicochemical attributes of the synthesized composites were examined by FTIR, UV–visible and X-ray diffraction(XRD)techniques. Morphological aspects were evaluated by field-emission scanning microscopy(FESEM),electron diffraction spectroscopy(EDS), high resolution transmission electron microscopy(HRTEM) and selected area electron diffraction(SAED) studies. Electrochemical measurements revealed an improved specific capacitance of 2250 F/g at a scan rate of 5 m V/s and 2000 F/g at a current density of 1 A/g with good rate capability using a three-electrode system. These enhanced features are achieved from the well designed nanostructure and the synergistic contributions of individual components in the electrode material.     

Electrocatalysis and Amperometric Detection of the Reduced Form of Nicotinamide Adenine Dinucleotide at Toluidine Blue/Zinc Oxide Coated Electrodes

Thin toluidine blue (TBO) and zinc oxide (ZnO) hybrid films have been grown on glassy carbon electrode (GCE) and indium tin oxide coated (SnO₂) glass electrodes by using cyclic voltammetry (CV). Scanning electron microscopy (SEM) images revealed spherical and beads‐like shape of highly oriented TBO/ZnO hybrid films. Energy dispersive spectrometry (EDS) results declared that the films composed mainly of Zn and O. Moreover, TBO/ZnO hybrid films modified electrode is electrochemically active, dye molecules were not easily leached out from the ZnO matrix and the hybrid films can be considered for potential applications as sensor for amperometric determination of reduced nicotinamide adenine dinucleotide (NADH) at 0.0 V. A linear correlation between electrocatalytic current and NADH concentration was found to be in the range between 25 μM and 100 μM in phosphate buffer. In addition, we observed that dopamine, ascorbic acid and uric acid are not interference in amperometric detection of NADH in this proposed method. In addition, TBO/ZnO hybrid film modified electrode was highly stable and its response to the NADH also remained relentless.