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Table of Content

    28 February 2017, Volume 23 Issue 1
    Table of Contents
    Cover and Table of Contents for VOL.23 No.1
    2017, 23(1):  0. 
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    Articles
    Application of Composite Ionic Liquid in Electro-oxidation Activation of a C-H Bond
    CHEN Zi-ying, WU Qian-qian, ZHANG Jian-qing, ZHU Ying-hong, MA Chun-an
    2017, 23(1):  1-6.  doi:10.13208/j.electrochem.160315
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    In this paper, the ionic liquid/carbon nanotube composite material was prepared through modifying the ionic liquid 1-ethyl-3-methylimidazolium acetate to multi-walled carbon nanotubes. The electro-oxidation properties of p-methoxy toluene (p-MT) were studied using the composite as an electrolyte. The effects of scanning speed, temperature and substrate concentration were studied by cyclic voltammetry and chronoamperometry. The electrochemical kinetics of p-MT in this system was also studied. The results showed that the electrochemical oxidation of p-MT in the composite electrolyte solution was irreversible. The process was mainly controlled by diffusion, and the diffusion coefficient (D) was 7.69×10-10 cm2.s-1. Increasing the reaction temperature and the concentration of substrate could promote the electro-oxidation of the C-H bond to the corresponding aldehyde, and the selectivity of p-methoxybenzaldehyde (p-MBA) could improve to 95%. The electrolysis in one-pot was more efficiency and achieved better selectivity than that in the H-type.

    Electrochemical Nucleation of Invar Alloy on Glassy Carbon Electrode
    HUANG Xian-jie, YAN Hui, HUANG Shuai-shuai, YANG Fang-zu*, TIAN Zhong-qun, ZHOU Shao-min
    2017, 23(1):  7-12.  doi:10.13208/j.electrochem.160318
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    Abstract: The linear sweep voltammetry, cyclic voltammetry and potential step methods were used to study the electrodeposition mechanism of Invar nickel-iron alloy (the mass fraction of nickel was 32~36%) on glassy carbon electrode surface in the weak acidic bath. The results demonstrate that the electrodeposition is was a diffusion controlled irreversible electrode process in this system. The Scharifker-Hill (SH) theory theoritic model (SH) were was used employed to fitting the experimental data and the result shows that the codeposition of Invar alloy on glassy carbon electrode surface conformed to the diffusion controlled three-dimensional instantaneous nucleation mechanism. The kinetic parameters were obtained by the Heerman-Tarallo (HT) theory theoretic model (HT). When the step potential shifted from -1.11 V to -1.17 V, the active nucleation sites density (N0) increased from 0.72×105 cm-2 to 1.91 ×105 cm-2. The nucleation rate constant (A) raised from 40.35 s-1 to 194.38 s-1 and the diffusion coefficient (D) was(7.67±0.15)×10-5 cm2•s-1, remaining basically constant.

    Electrochemical Synthesis of Porous Polyaniline Electrodes Using HKUST-1 as a Template and their Electrochemical Supercapacitor Property
    LUAN Qiong, XUE Chun-feng, ZHU Hong-ye, YANG Fu-juan, MA Xu-li,HAO Xiao-gang
    2017, 23(1):  13-20.  doi:10.13208/j.electrochem.160201
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    Excellent electrode plays vital important role in the performance of supercapacitors. Polyaniline (PANI) with good conductivity is often used to prepare electrode. However, its available surface is limited and results in a poor supercapacitance in many cases. It is desirable to fabricate an electrode containing electroactive PANI with high surface area deriving from its porous structure. Here, the metal-organic framework (MOF) material with high surface area was selected as a hard template for synthesizing porous PANI. Microporous PANI composite electrodes (Micro-PANI/CC) were fabricated by depositing aniline on to carbon cloth (CC) pre-coated with MOF material of HKUST-1 using a unipolar pulse electro-polymerization method. At the same time, the PANI electrodes (PANI/CC) were also synthesized on blank carbon cloth for further comparatively studying their supercapacitor performances. Their microstructure and morphology were characterized by using XRD and SEM. Results indicate that the micro-PANI/CC electrode was composed of aggregated nanosized PANI spheres with pore structure. The cyclic voltammetry, constant current charge and discharge, impedance and stability tests were performed to evaluate the supercapacitor properties in 0.5 mol·L-1 sulfuric acid electrolyte. Specific capacitances of micro-PANI/CC and PANI/CC electrodes were 895.6 F·g-1 and 547.6 F·g-1  at scan rate of 2 mV·s-1 , respectively. At the same given conditions, the specific capacitance of micro-PANI/CC electrode was always 1.64 times higher than that of PANI/CC electrode. Meanwhile, the micro-PANI/CC electrode exhibited better rate capability, lower resistance and better stability of charge and discharge than PANI/CC. all the results imply that the microporous PANI templated from HKUST-1 could be a good candidate for the electrode of supercapacitors.

    Sn-Doped α-Fe2O3 Photocatalyst containing Oxygen Vacancy for Water-splitting
    Wang Zu-hua, Niu Dong-fang, Li Hui-cheng, Du Rong-bin, XU Heng, Zhang Xin-sheng
    2017, 23(1):  21-27.  doi:10.13208/j.electrochem.160412
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    The α-Fe2O3 nanoparticles containing oxygen vacancies were synthesized in atmospheric N2 by dip-dropping method without a high vacuum employed before annealing. The influences of annealing atmosphere and Sn-doping on the photocatalytic performance of α-Fe2O3 nanoparticles were studied by annealing the photocatalyst in N2 or air and adding SnCl4 to the precursor directly. The results showed that the current density of Sn-doping α-Fe2O3 annealed in N2 at 550 °C and 1.23 V (vs. RHE) was 35 times greater than that of pristine α-Fe2O3 annealed in N2 at 550 °C and 15 times greater than that of Sn-doping α-Fe2O3 annealed in air at 550 °C, which indicated that both Sn-doping and annealing in N2 were indispensible to obtain a good performance for α-Fe2O3 nanoparticles. Mott-Schottky curves and electrochemical impedance spectroscopic data proved that both Sn-doping and oxygen vacancy could lead to the increase of the donors concentration and conductivity, which resulted in the enhanced performance of α-Fe2O3 nanoparticles. The photocatalytic performance tested in the electrolyte containing sacrifice solvent confirmed that the Sn-doping could facilitate the surface reaction, which was another key factor contributed to the enhanced performance of α-Fe2O3 nanoparticles.

    Preparation and Electrochemical Properties of Attapulgite-Supported Nitrogen-Doped Carbon@NiCo2O4Composites for Supercapacitors
    WAN Hui, YING Zong-rong, LIU Xin-dong, LU Jian-jian, ZHANG Wen-wen
    2017, 23(1):  28-35.  doi:10.13208/j.electrochem.160523
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    In this work, the attapulgite-supported nitrogen-doped carbon (ANC) was prepared by in-situ chemically polymerizing polyaniline coating upon attapulgite, followed by high temperature heat treatment, and then NiCo2O4was reacted onto the surface of ANC by a combination of hydrothermal reaction and calcination to synthesize ANC@NiCo2O4 composites. The chemical composition and morphology of the samples were characterized by Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM) and N2 adsorption/desorption. The electrochemical properties were evaluated by means of constant current charge discharge (GCD) and cyclic voltammetry (CV). The results showed that due to the high specific surface area and porous structure of ANC, the NiCo2O4 particles were uniformly located on the surface, resulting in large contact reaction areas with the electrolyte and improved electrochemical performance. At a current density of 1 A·g-1, the specific capacitance was up to 945.5 F·g-1, while at a current density of 16 A·g-1, it was 587.6 F·g-1, i.e., the capacitance retention was 62.1%, revealing a better rate performance. After 2000 cycles of charge-discharge process at a high current of 12 A·g-1, the capacitance retention was 74.1%, higher than 48.7% of pure NiCo2O4, which indicated that the as-prepared composite electrode materials had excellent electrochemical durability.

    Preparations of MnO2 Reference Electrodes for Corrosion Monitoring of Reinforced Concrete
    YANG Li, XU Bing, WANG Hai,DONG Ze-hua
    2017, 23(1):  36-44.  doi:10.13208/j.electrochem.160328
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    In this work, the solid reference electrode was assemblied by using the electrochemically synthesized manganese dioxide (MnO2) (EMD) powder, gel electrolyte and thin mortar layer for the durability evaluation of concrete. The EMD reference electrode exhibited higher potential stability (< 10 mV drift) than the chemically synthesied MnO2 (CMD) based on half year potential tests in the saturated Ca(OH)2 solution and hardened mortar. In addition, the EMD electrode was almost insensitive to the presences of chloride ion and corrosion inhibitor. Electrochemical impedance and polarization curves indicate that the EMD electrode had lower charge transfer resistance,higher exchange current density and lower temperature coefficient than the CMD electrode. The EMD electrode could be a potential candidate as the long-term reference electrode for the durability management of concrete infrastructure.

    Aligning Electronic Energy Levels on the Anatase TiO2(101) Surface
    ZHAO Jun-jie, CHENG Jun
    2017, 23(1):  45-52.  doi:10.13208/j.electrochem.160418
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    As one of the most commonly-used materials for photocatalysis and solar energy conversion, titanium dioxide (TiO2) has been extensively studied for more than 40 years. Its photoelectrochemical activity crucially depends on the band positions at the interface. In this work, the valence band maximum (VBM) and conduction band minimum (CBM) of a model TiO2 surface are computed using the standard work function method at the level of Perdew-Burke-Ernzerhof (PBE) density functional, which are then converted to the scale of the standard hydrogen electrode (SHE) by subtracting the absolute SHE potential. Comparing with the rutile TiO2(110) surface, we find a similar upshift in the VBM and CBM upon the adsorption of water molecules on the anatase TiO2(101) surface, and the band gap error intrinsic to the PBE functional can be mainly attributable to mis-positioning of the VBM. In addition, in contrast to the finding on the rutile TiO2(110) surface that the adsorption of 1 monolayer water largely recovers the band alignment of the aqueous interface, our preliminary calculations indicate that on the anatase TiO2(101) surface there is a considerable difference between the simplified model with the adsorption of 1 monolayer water and the fully solvated interface, suggesting the necessity to include the water molecules beyond the first adsorption layer in order to realistically represent the anatase TiO2 water interface.

    Direct Electrochemistry of Glucose Oxidase Based on WS2 Quantum Dots and its Biosensing Application
    LI Chen-lu, PENG Hua-ping, HUANG Zhong-nan, SHENG Yi-lun, WU Pei-wen, LIN Xin-hua
    2017, 23(1):  53-58.  doi:10.13208/j.electrochem.160829
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    In this study, a novel electrochemical glucose biosensor has been developed by immobilizing glucose oxidase (GOx) on tungsten disulfide quantum dots (WS2 QDs) on the surface of glassy carbon electrode (GCE). Transmission electron microscopy, UV-vis spectroscopy and cyclic voltammetry were employed to characterize the morphology, structure, and electrochemical behaviors of the as-prepared WS2 QDs and the biofilm modified electrode. The results suggested that the WS2 QDs could accelerate the electron transfer between the electrode and the immobilized enzyme, which enabled the direct electrochemistry of GOx without any electron mediator. Besides, the immobilized GOx in WS2 QDsfilm exhibited excellent electrocatalytic activity toward oxidation of glucose due to the excellent biocompatibility of the WS2 QDs. The proposed GOx/WS2 QDs biofilm electrode exhibited a linear response to glucose concentration in the ranges of 25 ~ 100 μmol·L-1 and 100 ~ 600 μmol·L-1, and the detection limit of the biosensor was as low as 5.0 μmol·L-1. The biosensor also exhibited good selectivity, reproducibility and long-term stability, which might be potenially used for the detection of the real samples.

    Performance of Piperidine Ionic Liquid Based Mixed Electrolyte in Li/LiCoO2 Cell
    Cheng Hu,Nie Xiao-yan, Shen Ye-dan,
    2017, 23(1):  59-63.  doi:10.13208/j.electrochem.160218
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    The N-methyl-N-ethyl (propyl, butyl) piperidinium bis (trifluo romethanesulfonyl) imide (PP12(3,4)TFSI) ionic liquids were prepared, and their influences on the performances of Li/LiCoO2 cells were investigated. The electrochemical performance and thermostability of ionic liquids based mixed electrolytes were characterized by electrochemical methods and thermogravimetric analysis. The results showed that the piperidine ionic liquids could improve the thermostability of organic electrolyte, and the size of their side chain had played an important role on the electrochemical performance of Li/LiCoO2 cell. The Li/LiCoO2 cell used the electrolyte mixed with PP13TFSI exhibited the best electrochemical performance among the three ionic liquids. The initial discharge capacity reached 156.9 mAh·g-1 at the rate of 150 mA·g-1 and 3.0 ~ 4.35 V. The discharge capacity upon 200 cycles was 133.9 mAh·g-1, and the capacity retention was 85.5%. The cycle performance was much better than that in conventional organic electrolytes.

    Effect of Pressure on Ion Selectivity in Biomimetic Nanopores with pH-Tunable Polyelectrolyte Brushes
    SHAN Hui-xia, ZENG Zhen-ping, YE Li-xian, SHU Feng
    2017, 23(1):  64-71.  doi:10.13208/j.electrochem.160104
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    Biomimetic ionic channels of synthetic nanopores functionalized with pH-tunable polyelectrolyte (PE) brushes have significant application potentials for active transport control of ions, fluids, and bioparticles on the nanoscale. Ion selectivity is an important phenomenon of ion transport in nanofluidic devices, which has great theoretical significance and practical values. We propose a pressure control scheme to control the ion selectivity in biomimetic nano-systems with pH-tunable PE brushes. Effects of the solution properties (i.e., pH and background salt concentration), the applied voltage and pressure on ion selectivity are comprehensively investigated. The results show that ion selectivity is sensitive to pressure. Unlike the influence of voltage on ion selectivity which is subject to pH and background salt concentration with uncertain directions and uncontrollable speeds, the influence of pressure on ion selectivity is not restricted by the properties of the solution, and has fixed directions and flexible and controllable speeds. The obtained result is a good inspiration for the design of synthetic nanopores functionalized with pH-tunable PE brushes.

    The Problem of the Anode Electrolyte in H-Type Electrolytic Cell for Electrochemical Reduction of Carbon Dioxide
    ZHANG Rui, LV Wei-xin, LEI Li-xu
    2017, 23(1):  72-79.  doi:10.13208/j.electrochem.160121
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    Electrochemical reduction of carbon dioxide (CO2) was studied in the H-type electrolytic cell. It was found that the voltage between the cathode and the anode would increase during the long time electrolysis process, for this reason the electrolytic process would be unsustainable. After the experimental investigations carried out by constant potential electrolysis, constant current electrolysis, pH test and KHCO3 concentration analysis of anode electrolyte before and after the electrolysis, the increase in cell voltage might be caused by the following process: H+, that was generated from the anodic oxygen evolution reaction, reacted with HCO3- to form water and CO2, and the HCO3-in the anode chamber was consumed; then K+ in the anode chamber was forced to spread into the cathode chamber which led to the decrease of the electrolyte concentration in the anode chamber. Therefore, the conductivity of the electrolyte solution in the anode chamber decreased, resulting in the rise of the anode potential. This phenomenon may happen in the alkaline electrolyte in an anode cell, therefore, in order to ensure the electrolysis process sustainable and keep high energy conversion efficiency, the anode electrolyte cannot be any alkaline substance.

    Effects of Flame Retardant on the Rate Capability and Safety Performances of the Soft-Package 5Ah Lithium Ion Battery
    LV Yan-zhuo, WANG Xiao-he, QIN Yi-ming, WANG Zhen-bo, KE Ke
    2017, 23(1):  80-85.  doi:10.13208/j.electrochem.160119
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    The 5 Ah soft packed lithium ion batteries with LiNi 0.4Co0.2Mn0.4 O2 as the positive electrode material and the organic electrolytes with different amounts of fire retardants as the electrolyte solution were prepared. The effects of the fire retardant amount (5 %,10 %,20 %) of the fire retardants on the rate performances, short-circuit characteristics and overcharged behaviors of the 5 Ah soft packed lithium ion battery were investigated by electrochemical methods. The results indicated that the best rate performances were obtained by adding 5 vol.% of the fire retardants in the electrolyte solution when the battery was discharged at 1C and 2C. The battery had the lowest surface temperature with 20 vol.% of fire retardant in the electrolyte solution when it was over-charged. The batteries could not catch fire and explode when the battery were short-circuited.

    An Investigation in the Performance of Lithium Sulfur Battery with a TiC Coated Separator
    FANG Jian-hua, CAO Yong, YANG Mao-ping, ZHENG Ming-sen, DONG Quan-feng
    2017, 23(1):  86-90.  doi:10.13208/j.electrochem.160606
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    To improve the specific capacity and cycle stability of lithium-sulfur (Li-S) battery, a TiC/Celgard coating separator was developed and its performance in Li-S battery was investigated. The electrochemical test results confirmed that the TiC coating layer could significantly increase the capacity and cycle stability. At a high rate of 2C, it still delivered the capacity of 650 mAh?g-1. At 0.5C, the specific capacity was maintained at 841.3 mAh?g-1 after 100 cycles.
    Application of Adamantane Schiff Base Nickel Complexes/Graphene Oxide/Glassy Carbon Modified Electrode in Detection of Carmine
    GUO Peng, LIU Zheng, LI Hai-ying, Ma Li-ming
    2017, 23(1):  91-98.  doi:10.13208/j.electrochem.160210
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    The Schiff base nickel complexes/graphene oxide/glassy carbon electrodes were prepared by embedded method and electrodeposition on which were used to quantitatively detect the contents of carmine. Cyclic voltammetry, chronoamperometry, scanning electron microscopy (SEM) and other methods were employed to characterize properties and morphologies of the modified electrodes. The results show that the adamantane double Schiff base nickel complexes/graphene oxide/glassy carbon electrode had high electric catalytic activity toward carmine oxidation reaction, and might provide an easy and quick way to detect carmine content with good reproducibility.

    Latest and Hot Papers
    Latest and Hot Papers
    ZHUANG Lin
    2017, 23(1):  99-100.  doi:10.13208/j.electrochem.160573
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    Nanostructured Material-Based Biofuel Cells: Recent Advances and Future Prospects C. Zhao, P. Gai, R. Song, Y. Chen, J. Zhang, J.-J. Zhu Chem. Soc. Rev. DOI: 10.1039/C6CS00044D 关于生物燃料电池纳米结构电极材料的综述,引用了265篇参考文献.