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  • Exploring substrate/ionomer interaction under oxidizing and reducing environments
    Electrochem. Commun. (IF 4.396) Pub Date : 2018-01-09
    Meron Tesfaye, Andrew MacDonald, Peter J. Dudenas, Ahmet Kusoglu, Adam Z. Weber
    更新日期:2018-01-10
  • Studies of oxide growth location on anodization of Al and Ti provide evidence against the field-assisted dissolution and field-assisted ejection theories
    Electrochem. Commun. (IF 4.396) Pub Date : 2018-01-07
    Mengshi Yu, Ying Chen, Chen Li, Shuo Yan, Huimin Cui, Xufei Zhu, Jianshou Kong

    Electrochemical anodization, a method of obtaining highly-ordered porous oxides of various metal and alloys, has been studied for decades to elucidate the complicated formation mechanism. Both the widely supported field-assisted dissolution theory and the subsequently proposed field-assisted ejection theory suggest that porous oxide forms at the metal/oxide interface and is dissolved at the oxide/electrolyte interface. Here, in order to test this assertion, three-layered oxide films were fabricated on both Al and Ti foils. Both the inner and outer hemispherical bottoms vanish after the second anodization as they are covered by a new growth of oxide. The disappearance of both inner and outer hemispherical bottoms is evidence against the field-assisted dissolution and field-assisted ejection view that oxide grows only at the metal/oxide interface.

    更新日期:2018-01-07
  • 更新日期:2018-01-05
  • All-solid-state lithium batteries – The Mg2FeH6-electrode LiBH4-electrolyte system
    Electrochem. Commun. (IF 4.396) Pub Date : 2018-01-05
    Priscilla Huen, Dorthe B. Ravnsbæk
    更新日期:2018-01-05
  • Liquid-inlet online electrochemical mass spectrometry for the in operando monitoring of direct ethanol fuel cells
    Electrochem. Commun. (IF 4.396) Pub Date : 2018-01-04
    Yu-Hao Hong, Zhi-You Zhou, Mei Zhan, Yu-Cheng Wang, Ying Chen, Shui-Chao Lin, Muhammad Rauf, Shi-Gang Sun
    更新日期:2018-01-04
  • 更新日期:2018-01-03
  • Combining lithography and capillary techniques for local electrochemical property measurements
    Electrochem. Commun. (IF 4.396) Pub Date : 2017-12-28
    Ying Jin, Zhaogui Lai, Peng Bi, Songtao Yan, Lei Wen, Yongchao Wang, Jinshan Pan, Christofer Leygraf

    The relationships between composition, microstructure and electrochemical properties are of fundamental importance in understanding the corrosion of multiphase materials and thus in aiding in the design of new materials. A local electrochemical test system which combines a capillary device with a photolithographic mask has been developed to investigate the local electrochemical properties of a predefined micron-sized area with greater reliability and versatility than existing approaches. Independent electrochemical measurements were conducted on the different phases of a 2205 duplex stainless steel in NaCl solution, demonstrating the feasibility of the developed test system.

    更新日期:2017-12-31
  • In-situ electronic conductivity measurements of LiNi0.45Mn1.485Cr0.05O4 thin films using all-solid-state thin-film batteries
    Electrochem. Commun. (IF 4.396) Pub Date : 2017-12-23
    Morihiro Sato, Takayuki Yamamoto, Munekazu Motoyama, Yasutoshi Iriyama
    更新日期:2017-12-27
  • 更新日期:2017-12-27
  • Photon flux influence on photoelectrochemical water treatment
    Electrochem. Commun. (IF 4.396) Pub Date : 2017-12-23
    Sergi Garcia-Segura, Heather O'Neal Tugaoen, Kiril Hristovski, Paul Westerhoff

    This work quantifies the role of incident light in photoelectrochemical water treatment device efficiency to destroy waterborne pollutants. The conversion of incident photon flux from monochromatic light emitting diodes (285 nm, 300 nm, and 365 nm) into current (i.e., incident photon-to-current efficiency, IPCE) was studied. Identical photocurrent responses were obtained at identical photon flux but using different monochromatic wavelengths. Photocurrent increased with higher incident photon flux from the light emitting diodes (LEDs). However, an exponential decrease in IPCE occurred simultaneously, indicating a lower percentage of those photons converted into electrons. Higher photocurrents indicated more charge carriers photoelectrogenerated greater amount of oxidant species (e.g., radical dot OH) capable of degrading organic pollutants in water. Thus, IPCE aided in optimizing the energy needed to generate radical dot OH and remove pollutants.

    更新日期:2017-12-27
  • Monoethanolamine-enabled electrochemical detection of H2S in a hydroxyl-functionalized ionic liquid
    Electrochem. Commun. (IF 4.396) Pub Date : 2017-12-22
    Qing Huang, Wei Li, Tian Wu, Xiaoling Ma, Kai Jiang, Xianbo Jin

    There is much interest in developing electrochemical sensors for H2S detection using room temperature ionic liquids as electrolytes. To this end, this study compared the electrochemical behavior at a Pt-microdisk electrode of H2S in [Bmim]BF4, [C3OHmim]BF4, and MEA–[C3OHmim]BF4 (1:6.2 M ratio) using cyclic voltammetry. In both [Bmim]BF4 and [C3OHmim]BF4, the electrochemical oxidation/reduction of H2S requires too high/low a potential (about 1.5/− 1.6 V vs. Ag/Ag+), and these ionic liquids are therefore unsuitable for H2S detection. Addition of monoethanolamine (MEA) to [C3OHmim]BF4 significantly increases the H2S absorption capacity through the chemical reaction between MEA and H2S. This chemical absorption enhances the electrochemical response of H2S, in particular generating electroactive HS− ions that lead to an additional and independent anodic peak at around − 0.4 V vs Ag/Ag+ which is suitable for H2S sensing. There is a good linear relationship between the peak current and H2S content in the tested range (60–210 ppm). Moreover, electroactive ambient gases such as CO2 and SO2 show no response at the potentials of HS− oxidation, so do not interfere with H2S detection. Our findings reveal a new kind of ionic liquid electrolyte for the detection of H2S gas with high sensitivity and selectivity.

    更新日期:2017-12-22
  • 更新日期:2017-12-22
  • Self-healing strategy for Si nanoparticles towards practical application as anode materials for Li-ion batteries
    Electrochem. Commun. (IF 4.396) Pub Date : 2017-12-21
    Junfeng Yang, Linchao Zhang, Tao Zhang, Xianping Wang, Yunxia Gao, Qianfeng Fang
    更新日期:2017-12-22
  • Polythiophenes as markers of asphalt and archaeological tar pitch aging. Characterization using solid-state electrochemistry
    Electrochem. Commun. (IF 4.396) Pub Date : 2017-12-20
    Antonio Doménech-Carbó, Géssica Domingos da Silveira, Mª. Ángeles Medina-Alcaide, Adoración Martínez Carmona, David López-Serrano, Trinidad Pasíes-Oviedo, Víctor M. Algarra-Pardo, Leandro Machado de Carvalho, Noemí Montoya
    更新日期:2017-12-20
  • Bridging electrode gaps with conducting polymers around the electrical percolation threshold
    Electrochem. Commun. (IF 4.396) Pub Date : 2017-12-19
    Krishnan Murugappan, Martin R. Castell

    The conducting polymer poly(3,4-ethylenedioxythiophene) (PEDOT) is grown electrochemically using cyclic voltammetry between the gaps of interdigitated Au electrodes with separations of 10, 20, and 50 μm. Three electrical conductivity regimes are identified through resistance measurements and SEM imaging. The first is the insulating region where there are no complete conducting pathways between the electrodes. The second is the percolation region where a few localised conducting polymer bridges have formed. The third is the thin film region where a continuous conducting polymer film connects the electrodes. The demonstration of the ability to reliably generate conducting polymer electrical percolation networks is important for their future use in high sensitivity devices.

    更新日期:2017-12-19
  • Effect of crystal orientation on the corrosion behavior of Mo3Si single crystals in 0.5 M H2SO4
    Electrochem. Commun. (IF 4.396) Pub Date : 2017-12-19
    R. Lopez-Sesenes, I. Rosales, J.G. Gonzalez-Rodriguez

    The corrosion behavior of Mo3Si single crystals with crystallographic orientations 〈100〉, 〈110〉 and 〈111〉 in 0.5 M H2SO4 was analyzed using potentiodynamic polarization curves, electrochemical impedance spectrosopy, and electrochemical noise measurement. The corrosion behavior was different for each crystal orientation. The plane most susceptible to both uniform and localized types of corrosion was the (111) plane; the (110) plane exhibited the lowest susceptibility to uniform corrosion; and the (100) plane was the least susceptible to localized corrosion. These results were explained by differences in surface energy and the number of atoms per unit area.

    更新日期:2017-12-19
  • Electrocatalytic activity of CoFe2O4 thin films prepared by AACVD towards the oxygen evolution reaction in alkaline media
    Electrochem. Commun. (IF 4.396) Pub Date : 2017-12-15
    Jagdeep S. Sagu, Diana Mehta, K.G.U. Wijayantha

    The electrocatalytic behaviour of CoFe2O4 thin films, prepared by aerosol-assisted chemical vapour deposition, towards the oxygen evolution reaction in an alkaline medium is reported. X-ray diffraction and SEM data show that the CoFe2O4 thin films are phase pure and consist of dendrites 0.5–1 μm in diameter rising from the surface with heights ranging from 1 to 3 μm. The CoFe2O4 thin films exhibited an overpotential of 490 mV at a current density of 10 mA cm− 2, and a Tafel slope of 54.2 mV dec− 1. Taking into account the electrochemically active surface area, the intrinsic activity of CoFe2O4 was found to be 1.75 mA cm− 2real at an overpotential of 490 mV. The CoFe2O4 thin films were highly stable and were capable of maintaining catalytic activity for at least 12 h.

    更新日期:2017-12-16
  • Structural effects on the enhancement of ORR activity on Pt single-crystal electrodes modified with alkylamines
    Electrochem. Commun. (IF 4.396) Pub Date : 2017-12-15
    Keiichiro Saikawa, Masashi Nakamura, Nagahiro Hoshi
    更新日期:2017-12-16
  • A new alternative self-assembled-monolayer activation process for electroless deposition of copper interconnects without a conventional barrier
    Electrochem. Commun. (IF 4.396) Pub Date : 2017-12-14
    Giin-Shan Chen, Tzu-Ming Yang, Sung-Te Chen, Yi-Lung Cheng, Jau-Shiung Fang
    更新日期:2017-12-15
  • Lithium dendrite suppression and cycling efficiency of lithium anode
    Electrochem. Commun. (IF 4.396) Pub Date : 2017-12-14
    Peng Zhang, Jiajia Zhu, Miao Wang, Nobuyuki Imanishi, Osamu Yamamoto
    更新日期:2017-12-15
  • Selective detection of morphine in the presence of paracetamol with anodically pretreated dual layer Ti/tetrahedral amorphous carbon electrodes
    Electrochem. Commun. (IF 4.396) Pub Date : 2017-12-13
    Niklas Wester, Jarkko Etula, Tuomas Lilius, Sami Sainio, Tomi Laurila, Jari Koskinen
    更新日期:2017-12-15
  • High energy density in-situ sodium plated battery with current collector foil as anode
    Electrochem. Commun. (IF 4.396) Pub Date : 2017-12-13
    Ashish Rudola, Satyanarayana R. Gajjela, Palani Balaya
    更新日期:2017-12-15
  • Synthesis of Co–B in porous carbon using a metal–organic framework (MOF) precursor: A highly efficient catalyst for the oxygen evolution reaction
    Electrochem. Commun. (IF 4.396) Pub Date : 2017-12-11
    Yanqiang Li, Haibin Xu, Huiyong Huang, Liguo Gao, Yingyuan Zhao, Tingli Ma

    The sluggish anodic oxygen evolution reaction (OER) greatly hinders the working efficiency of electrochemical water splitting to produce hydrogen, and it is therefore important to explore high-performance and cost-effective OER catalysts. In this communication, we report the synthesis of cobalt boride incorporated within porous carbon using a metal–organic framework (MOF) as a precursor. The high catalytic activity of Co–B and the high conductivity of carbon both contribute to the OER catalytic activity of Co–B/C. When used as an OER catalyst, this material shows high catalytic activity, delivering a current density of 10 mA cm− 2 at a low overpotential of 320 mV, as well as outstanding long-term electrochemical durability. This finding is of fundamental and practical importance as it not only extends the application of MOFs, but also introduces a new method for synthesizing highly efficient OER electrocatalysts.

    更新日期:2017-12-11
  • Effect of graphene nanoplatelet edges on the iodide/triiodide redox reaction
    Electrochem. Commun. (IF 4.396) Pub Date : 2017-12-11
    Yuta Ohtani, Hajime Hoshi

    Carbon electrodes have been extensively studied for the development of Pt-free dye-sensitized solar cells. In this study, the influence of graphene nanoplatelet edges on the activity of an electrolyte reaction was investigated. The reaction activities of graphene nanoplatelet aggregates (GNAs) and graphene nanoplatelets (GNs), which have different surface areas, were evaluated by cyclic voltammetry and electrochemical impedance spectroscopy (EIS). The charge transfer resistances (RCT) of the GNAs and GNs were determined from EIS to be 12 Ω and 1.4 × 103 Ω, respectively. The coefficient components (AW) of the diffusion impedance, known as the Warburg impedance, of GNAs and GNs were 63 Ω Hz0.5 and 1.2 × 102 Ω Hz0.5, respectively. From these results, it was found that the edge plane area of the graphene aggregates affects both the reaction resistance and electrolyte diffusion in the carbon film.

    更新日期:2017-12-11
  • Modified Si nanowire/graphite-like carbon nitride core-shell photoanodes for solar water splitting
    Electrochem. Commun. (IF 4.396) Pub Date : 2017-12-11
    Minghui Ning, Zhen Chen, Lin Li, Qingguo Meng, Zhihong Chen, Yongguang Zhang, Mingliang Jin, Zhang Zhang, Mingzhe Yuan, Xin Wang, Guofu Zhou

    Si nanowires (SiNWs) and graphite-like carbon nitride (g-C3N4) are highly promising materials for solar water splitting. In this work, n-type SiNWs (n-SiNWs) are obtained via metal-catalyzed electroless etching. To improve the photoelectrochemical performance of the n-SiNWs, g-C3N4 is deposited on their surface as a coating layer (n-SiNW/g-C3N4). Furthermore, to increase the density of active sites in g-C3N4, barbituric acid (BA) is introduced into precursors before the layer deposition. The n-SiNW/g-C3N4 photoanode shows a negative shift of the onset potential as compared to the bare n-SiNWs. Moreover, a 50% enhancement in the photocurrent density at 1.6 V vs. RHE is achieved on the BA-modified n-SiNW/g-C3N4 as compared to the pristine n-SiNW/g-C3N4.

    更新日期:2017-12-11
  • MnO2-CoP3 nanowires array: An efficient electrocatalyst for alkaline oxygen evolution reaction with enhanced activity
    Electrochem. Commun. (IF 4.396) Pub Date : 2017-12-09
    Xiaoli Xiong, Yuyao Ji, Maowen Xie, Chao You, Lin Yang, Zhiang Liu, Abdullah M. Asiri, Xuping Sun

    It is highly desired to enhance the catalytic activity of MnO2 for the oxygen evolution reaction (OER) in alkaline media. Herein we report the development of MnO2-CoP3 nanowires array on Ti mesh (MnO2-CoP3/Ti) as an efficient 3D OER electrocatalyst with good stability under basic conditions. In 1.0 M KOH, the MnO2-CoP3/Ti requires a current density of 10 mA cm− 2 at overpotential of only 288 mV, which is 120 mV less than that for MnO2/Ti. In addition, such MnO2-CoP3/Ti also exhibits high long-term electrochemical durability.

    更新日期:2017-12-10
  • Fast and complete electrochemical conversion of solutes contained in micro-volume water droplets
    Electrochem. Commun. (IF 4.396) Pub Date : 2017-12-08
    Louis Godeffroy, François Chau, Olivier Buriez, Eric Labbé

    An elegant hanging-droplet or meniscus-based setup is proposed to carry out quantitative electrolyses from either an organic (hydroquinone) or an inorganic (permanganate) substrate. These examples validate the concept of using such easily accessible, fast (1–3 min) and low-cost operating conditions not only for preparative applications (electrosynthesis), but also for pedagogical purposes in minute samples.

    更新日期:2017-12-10
  • Collisions of suspended Prussian Blue nanoparticles with a rotating disc electrode
    Electrochem. Commun. (IF 4.396) Pub Date : 2017-12-07
    Marcin Holdynski, Joanna Dolinska, Marcin Opallo

    The electrochemistry of suspended nanoparticles has attracted some attention as a method of characterizing them. Taking redox-active Prussian Blue nanoparticles as an example, we demonstrate that suspended redox-active inorganic nanoparticles exhibit electrochemical reactivity. When the potential of a rotating disc electrode is sufficiently low or high, a series of injections of a suspension of nanoparticles into an aqueous electrolyte produces sharp current increases resulting from their electroreduction or electrooxidation, respectively. The magnitude of the current steps is linearly dependent on the concentration of the nanoparticles. Much larger current steps are obtained in the presence of H2O2 as a result of catalytic amplification.

    更新日期:2017-12-07
  • Molybdenum dioxide as an alternative catalyst for direct utilization of methane in tubular solid oxide fuel cells
    Electrochem. Commun. (IF 4.396) Pub Date : 2017-12-06
    Xin Yang, Dhruba Panthi, Nader Hedayat, Tianmin He, Fanglin Chen, Wanbing Guan, Yanhai Du

    Direct utilization of methane in conventional tubular solid oxide fuel cells (SOFCs) with a Ni-YSZ anode support was proposed using MoO2 as a partial oxidation catalyst for methane reforming at the cell inlet. A promising stability was achieved for a continuous operation in a mixture of methane and air (1, 1.5) for > 150 h under a load voltage of 0.7 V at 750 °C. The addition of the MoO2 catalyst at the anode inlet made tubular SOFCs with the conventional Ni-YSZ anode an efficient and practically promising candidate for direct hydrocarbon utilization.

    更新日期:2017-12-06
  • Carbon nanotube band electrodes for electrochemical sensors
    Electrochem. Commun. (IF 4.396) Pub Date : 2017-12-06
    Rongzhou Lin, Tuti Mariana Lim, Tuan Tran

    Utilization of carbon nanotubes (CNTs) in fabrication of electrodes for electrochemical detection often faces a conflicting goal: achieving both high response current and high mass transfer coefficient. Typically, electrodes made in a form of CNT ensembles offer high response current as a result of the large number of CNTs. However, these electrodes have substantially low mass transfer coefficients due to overlapping of diffusion fields between neighboring CNTs. To resolve this conflict, we design band electrodes made of vertically-aligned CNT (CNBEs), which are macro-sized in length and submicro-sized in width. We show that the distinct dimensions of the CNBEs allow both high response currents and mass transfer coefficients. We also demonstrate that CNBEs offer excellent detection performances including wide linear range, high sensitivity, and low limit of detection in channel flow voltammetry.

    更新日期:2017-12-06
  • Temperature effect upon the thermoelectrochemical potential generated between lithium metal and lithium ion intercalation electrodes in symmetric and asymmetric battery arrangements
    Electrochem. Commun. (IF 4.396) Pub Date : 2017-12-06
    Jeffrey J. Black, Jason B. Harper, Leigh Aldous

    The evaluation of batteries under thermal gradients is essential for safety and longevity reasons, and to investigate power generation via the thermogalvanic effect. The thermogalvanic Seebeck coefficient of lithium metal (+ 1.0 mV·K− 1) and solid lithium ferri/ferrocyanide intercalation electrodes (− 0.6 mV·K− 1) were determined. The measured Seebeck coefficients of identical asymmetric cells containing both electrodes deviated from the expected values, having Seebeck coefficients which also varied as a function of thermal conditions (+ 0.7 to + 4.3 mV·K− 1). This work demonstrates that the thermal responses of asymmetric battery assemblies are more complex than predicted based upon their individual half-cell performances in symmetric cells.

    更新日期:2017-12-06
  • Facile synthesis of Ni3B/rGO nanocomposite as an efficient electrocatalyst for the oxygen evolution reaction in alkaline media
    Electrochem. Commun. (IF 4.396) Pub Date : 2017-12-05
    Maalavan Arivu, Jahangir Masud, Siddesh Umapathi, Manashi Nath

    Alkaline water electrolysis yielding H2 and O2 is a very promising fuel cell technology for sustainable energy generation. Emphasis has been placed on the development of efficient electrocatalysts based on earth-abundant elements for the kinetically deterred oxygen evolution reaction (OER). Nickel boride nanostructures exhibit enhanced OER catalytic activity, achieving 10 mA cm− 2 at an overpotential of 320 mV. The activity can be greatly improved by incorporating Ni3B in an electrically conducting reduced graphene oxide matrix, which reduces the overpotential further to 290 mV at 10 mA cm− 2, and has a small Tafel slope. The catalytic activity of the Ni3B–rGO nanocomposite shows considerable stability under long-term operating conditions.

    更新日期:2017-12-06
  • Mechanistic aspects of glycerol electrooxidation on Pt(111) electrode in alkaline media
    Electrochem. Commun. (IF 4.396) Pub Date : 2017-12-05
    Regiani M.L.M. Sandrini, Juliane Renata Sempionatto, Enrique Herrero, Juan M. Feliu, Janaina Souza-Garcia, Camilo A. Angelucci

    Glycerol electrooxidation reaction (GEOR) in alkaline media was studied on the Pt(111) electrode with in situ FTIR and electrochemical methods. Cyclic voltammogram profiles display strong electrode deactivation after the first potential scan. Chronoamperometric pulses demonstrate that the deactivation is a result of the reaction intermediates yielded during the faradaic process. In situ FTIR shows evidence that the strongly adsorbed intermediate formed during GEOR is an acyl species which remains present on the surface within the potential window studied.

    更新日期:2017-12-06
  • Engineering of bacterial electrochemical activity with global regulator manipulation
    Electrochem. Commun. (IF 4.396) Pub Date : 2017-12-05
    Yang-Yang Yu, Zhen Fang, Lu Gao, Hao Song, Liang Yang, Baodong Mao, Weidong Shi, Yang-Chun Yong

    The electrochemical activity of electroactive bacteria is unique and essential for bioelectrochemical systems (BES) with promising energy and environment applications. However, the strategies for bacterial electrochemical activity modulation are still limited. Herein, a novel approach for engineering of bacterial electrochemical activity with global regulator (sigma factor RpoS) manipulation was developed. By knockout of rpoS in Pseudomonas aeruginosa PAO1, the biofilm formation on the electrode was enhanced and the bacterial cells were adapted to a new electron shuttle, which promoted the extracellular electron transfer and improved the performance of BES. This work demonstrated that global regulator manipulation could be efficient for electrochemical activity engineering and offered new opportunities for BES applications.

    更新日期:2017-12-06
  • Open circuit potential transients associated with single emulsion droplet collisions at an interface between two immiscible electrolyte solutions
    Electrochem. Commun. (IF 4.396) Pub Date : 2017-12-01
    Antonín Trojánek, Vladimír Mareček, Zdeněk Samec

    Measurements of the open circuit potential (OCP) transients at a sessile aqueous electrolyte drop in contact with a 1,2-dichloroethane (DCE) electrolyte solution were used to detect the collisions of the single DCE-in-water emulsion droplets carrying 0.35 M tetradodecylammonium chloride with the interface between two immiscible electrolyte solutions (ITIES). Analysis of the OCP transients yielded the droplet size distribution, which is comparable with distributions obtained from the current transient measurements at a constant applied potential. These results are supported by the dynamic light scattering measurements and the microscope droplet image processing. Observed potential or current spikes appear to be associated with the single collisions of the emulsion droplets with the ITIES followed by the fast droplet ionic charge injection into the electric double layer at the ITIES possibly involving the transfer of Cl− across the droplet/aqueous phase interface, and by the double layer relaxation.

    更新日期:2017-12-02
  • Terminated nanotubes: Evidence against the dissolution equilibrium theory
    Electrochem. Commun. (IF 4.396) Pub Date : 2017-11-24
    Mengshi Yu, Huimin Cui, Fuping Ai, Longfei Jiang, Jianshou Kong, Xufei Zhu

    Electrochemical anodizations of metals and alloys have attracted increasing attention as a method to fabricate highly ordered porous films. The popular formation mechanism of porous anodic oxides is dissolution equilibrium theory, which indicates that the equilibrium between oxide growth and dissolution via digging manner at the bottom of pores is the major cause of tubular structure. Here, terminated nanotubes with sealed bottoms were discovered while titanium foils were anodized under different conditions. In one terminated nanotube, oxide at the bottom does not grow whereas dissolution from electrolyte still exists. According to the estimated dissolution rate, it only takes approximately 20 s for the bottom of the terminated nanotube to be penetrated absolutely based on dissolution equilibrium theory. Apparently, most anodizations in this work all last for more than 20 s after the appearance of terminated nanotubes. Therefore, the bottom of the terminated nanotube is bound to be penetrated absolutely. Nevertheless, its bottom is sealed completely, namely the experimental results are not consistent with theoretical results based on dissolution equilibrium theory. Hence, terminated nanotubes are evidence against the dissolution equilibrium theory.

    更新日期:2017-11-24
  • A new procedure for the template synthesis of metal nanowires
    Electrochem. Commun. (IF 4.396) Pub Date : 2017-11-23
    J.E. Graves, M.E.A. Bowker, A. Summer, A. Greenwood, C. Ponce de León, F.C. Walsh

    A new procedure for the fabrication of metal nanowires by template-assisted electrodeposition using porous polycarbonate templates is described. A thin sputtered film of silver (≤ 15 nm) was deposited onto one side of the template. The silver seed layer was used to catalyse electroless copper deposition and a copper layer was grown on top (300–500 nm) in less than 10 min. The copper layer served to seal the pores of the template and to form an electrode of high electrical conductivity. The copper layer was easily removed with a chemical etchant to aid the release of the nanowires from the template mask after growth. To demonstrate the process, copper nanowires were prepared by controlled potential deposition and characterised by SEM and TEM. This new procedure has the ability to be applied to the preparation of a wide range of metallic nanostructures over a wide range of scales. It avoids the need for an extended vacuum deposition step and has the advantage of using low-cost metals in a combined short vacuum/wet chemical process so as to form the critical electrode layer for nanowire growth.

    更新日期:2017-11-24
  • Bile acids: Electrochemical oxidation on bare electrodes after acid-induced dehydration
    Electrochem. Commun. (IF 4.396) Pub Date : 2017-11-23
    Jan Klouda, Jiří Barek, Pavel Kočovský, Thomas Herl, Frank-Michael Matysik, Karel Nesměrák, Karolina Schwarzová-Pecková

    Bile acids and sterols in general have long been considered practically inactive for direct redox processes. Herein, a novel way of electrochemical oxidation of primary bile acids is reported, involving an initial acid-induced dehydration step, as confirmed by capillary electrophoresis–mass spectrometry, thereby extending the electrochemical activity of the steroid core. Oxidation potentials were found to be ca + 1.2 V vs. Ag/AgNO3 in acetonitrile on boron doped diamond, glassy carbon, and platinum electrodes in a mixed acetonitrile–aqueous medium employing perchloric acid as a chemical reagent, and as a supporting electrolyte for the voltammetric measurements. The chemical step proved to be effective only for primary bile acids, possessing an axial 7α-hydroxyl group, which is a prerequisite for providing a well-developed voltammetric signal. Preliminary results show that other steroids, e.g., cholesterol, can also be oxidized by employing a similar approach.

    更新日期:2017-11-23
  • Deactivation of the ruthenium excited state by enhanced homogeneous charge transport: Implications for electrochemiluminescent thin film sensors
    Electrochem. Commun. (IF 4.396) Pub Date : 2017-11-23
    Emmet J. O'Reilly, Tia E. Keyes, Robert J. Forster, Lynn Dennany

    The electrochemiluminescent (ECL) performance of three ruthenium-based metallopolymer platforms with different homogeneous charge transfer diffusion coefficients (DCT) is reported. Significantly, simultaneous detection of light and current in tandem with steady-state photoluminescence studies demonstrate that increasing the rate of Ru3 + production via enhanced charge transport results in a decrease in ECL intensity of up to 82% when the concentration of the co-reactant, sodium oxalate, is low, i.e., sub-mM. Spectroelectrochemical studies demonstrate that for maximum sensitivity to be obtained, the electroactive properties of the polymeric support matrix need to be considered in tandem with luminophore, analyte and co-reactant concentrations.

    更新日期:2017-11-23
  • Heavy metal ion detection on a microspot electrode using an optical electrochemical probe
    Electrochem. Commun. (IF 4.396) Pub Date : 2017-11-23
    Santanu Roy, Abhijeet Prasad, Rahul Tevatia, Ravi F. Saraf

    Electrochemical sensors can be used to create portable, attractive, high-sensitivity devices to detect heavy ions in water at a reasonable cost. A novel method of measuring local redox on an electrode using the differential reflectivity measured on an approximately 6 micron diameter spot using a He/Ne laser beam is described. Field focusing and electrode modification enhance the sensitivity, making the method ideal for miniaturization and multiplexing multiple analytes on a monolith electrode. The method is demonstrated by detecting Pb, Hg, and As ions at ppb and ppt levels.

    更新日期:2017-11-23
  • TiP2O7 exhibiting reversible interaction with sodium ions in aqueous electrolytes
    Electrochem. Commun. (IF 4.396) Pub Date : 2017-11-22
    Grace Yee, Sneha Shanbhag, Wei Wu, Kristen Carlisle, Jiang Chang, Jay F. Whitacre

    The reversible electrochemical cycling of sodium ions in several variants of low cost, easy to produce TiP2O7 as the negative electrode material in an aqueous battery is demonstrated for the first time. TiP2O7 is synthesized using a high temperature solid-state route and a low temperature sol gel route. The materials are electrochemically characterized in an aqueous 1 M Na2SO4 electrolyte with a Na0.44MnO2 counter electrode material. While no capacity for sodium ion cycling is reflected in cyclic voltammetry, all observed samples exhibited reversible cycling of sodium ions in galvanostatic cycling with potential limitation. To our knowledge, this is the first report of solid-state synthesized TiP2O7 reversibly cycling sodium ions, and the first report of TiP2O7 reversibly cycling sodium ions in aqueous electrolytes. Discharge specific capacity is found to be positively correlated with crystallite size and low specific currents.

    更新日期:2017-11-23
  • A nanocatalyst network for electrochemical reduction of CO2 over microchanneled solid oxide electrolysis cells
    Electrochem. Commun. (IF 4.396) Pub Date : 2017-11-22
    Libo Yu, Jingjing Wang, Xun Hu, Zhengmao Ye, Craig Buckley, Dehua Dong

    A nanocatalyst network has been successfully prepared over the internal surface of Ni-based cathode support with a microchanneled structure via an impregnation process. Through numerous microchannels within the cathode support, a catalyst precursor solution was effectively delivered to the interface between cathode and electrolyte, resulting in the formation of the nanocatalyst network in the cathode reaction zone and therefore decreased degradation rate during CO2 electrolysis. After four coatings, the robust nanocatalyst network was formed to produce the least degradation, and further catalyst coatings caused concentration polarization.

    更新日期:2017-11-23
  • Epoxy-sealed single Pt nanoelectrodes: Fabrication and electrocatalytic performance for the methanol oxidation reaction
    Electrochem. Commun. (IF 4.396) Pub Date : 2017-11-21
    Hao Wang, Yan Gong, Yongxin Li

    Epoxy-sealed single Pt nanoelectrodes (SPNEs) ranging in size from 3 to 300 nm have been fabricated by a laser-assisted pulling method and characterized by optical microscopy, transmission electron microscopy (TEM) and electrochemical methods. The prepared SPNEs were used to investigate the methanol oxidation reaction (MOR), and the results show that the electrocatalytic activity of the SPNEs towards MOR depends on the radius of the electrode. In the range of electrode radii tested (3 nm–280 nm), the electrocatalytic activity decreases if the radius of the SPNE is either too small or too large, with optimal electrocatalytic efficiency being observed when the radius is about 4.2 nm.

    更新日期:2017-11-21
  • Black phosphorene and PEDOT:PSS-modified electrode for electrochemistry of hemoglobin
    Electrochem. Commun. (IF 4.396) Pub Date : 2017-11-20
    Xiaoyan Li, Xueliang Niu, Wenshu Zhao, Wei Chen, Chunxiao Yin, Yongling Men, Guangjiu Li, Wei Sun

    A black phosphorene (BP) and poly(3,4-ethylenedioxythiophene) -poly(styrenesulfonate) (PEDOT:PSS) composite was prepared with the aim of immobilizing hemoglobin (Hb) directly on the electrode. The incorporation of BP into PEDOT:PSS resulted in a stable film. The Hb immobilized on the electrode exhibited direct electron transfer, showing a pair of well-defined redox peaks, indicating that BP accelerated the direct electrochemistry of Hb. This modified electrode exhibited excellent electrocatalytic performance for the reduction of various substrates and was used for detection in real samples with satisfactory results. This demonstrates the potential applications of BP in electrochemical biosensing.

    更新日期:2017-11-20
  • A novel electrochemical chiral interface based on sandwich-structured molecularly imprinted SiO2/AuNPs/SiO2 for enantioselective recognition of cysteine isomers
    Electrochem. Commun. (IF 4.396) Pub Date : 2017-11-20
    Jie Zhang, Wensheng Tan, Yongxin Tao, Linhong Deng, Yong Qin, Yong Kong

    SiO2 nanospheres were synthesized by the sol–gel method using tetraethoxysilane (TEOS) as the precursor, which was then modified with 3-aminopropyltriethoxysilane (APTES) for the grafting of single bond NH2 to the SiO2 surface. Au nanoparticles (AuNPs) were anchored to the single bond NH2 grafted SiO2, and then l-cysteine (L-Cys) templates were introduced to the SiO2/AuNPs through forming Au single bond S bond. Another layer of SiO2 was then coated on the L-Cys doped SiO2/AuNPs as the coating layer, and then the templates were removed by calcination to form a sandwich-structured molecularly imprinted SiO2/AuNPs/SiO2. Finally, the molecularly imprinted chiral interface was applied for electrochemical enantioselective recognition of Cys isomers, and discernible differences in the current signals could be observed on the differential pulse voltammograms (ID-cys/IL-cys, 2.36).

    更新日期:2017-11-20
  • Effective sulfur-doping in carbon by high-temperature molten salt bath and its electrocatalysis for oxygen reduction reaction
    Electrochem. Commun. (IF 4.396) Pub Date : 2017-11-17
    Li Zhang, Yi Wang, Kai Wan, Jin-hua Piao, Zhen-xing Liang

    A facile high-temperature molten salt bath method was developed to effectively dope sulfur into carbon. Molten potassium sulfide acts as a high-concentration sulfur source and provides an immersion bath, thus favoring sulfur doping. Resultant sulfur-doped carbon shows an exceptionally high sulfur content of 1.50 at.%, manifesting its favorable effect on catalysing the oxygen reduction reaction.

    更新日期:2017-11-20
  • Graphene oxide based photocathode for split photoelectrochemical bioanalysis
    Electrochem. Commun. (IF 4.396) Pub Date : 2017-11-16
    Fang Li, Jun-Xian Shu, Tian-Tian Gu, Xiuming Wu, Yuming Dong, Guang-Li Wang

    In contrast to the many studies employing heavy-metal-containing semiconductors in state-of-the-art photoelectrochemistry, this work presents the first use of graphene oxide (GO) for advanced cathodic PEC analysis. The bioinspired redox reaction between GO and dopamine (DA) led to the formation of reduced GO (RGO) and the simultaneous deposition of the electron acceptor poly(dopamine) on RGO. This greatly stimulated the cathodic photocurrent of the GO-modified indium tin oxide (ITO) (ITO/GO) electrode, making it possible to detect DA rapidly and sensitively through a split photoelectrochemistry strategy (i.e. the reaction between the analyte and the photoelectrode and the recording of the photocurrent signal are conducted in separate devices). This study indicates the great promise of GO by demonstrating an elegant sensing strategy involving an in situ redox reaction followed by PEC analysis. It is hoped that this may open up the exploration of carbon nanomaterials for innovative cathodic photoelectrochemistry in the future.

    更新日期:2017-11-17
  • Manifestation of reactivation of the electrode surface in staircase cyclic voltammetry
    Electrochem. Commun. (IF 4.396) Pub Date : 2017-11-15
    Milivoj Lovrić, Šebojka Komorsky-Lovrić

    An oxidation peak in the cathodic branch of a cyclic voltammogram can be explained by the reversible deactivation and reactivation of the electrode surface. This phenomenon could be caused by the potential-dependent adsorption of the product of an irreversible electrode reaction.

    更新日期:2017-11-16
  • Macroporous platinum electrodes for hydrogen oxidation in ionic liquids
    Electrochem. Commun. (IF 4.396) Pub Date : 2017-11-11
    Ghulam Hussain, M. Veronica Sofianos, Junqiao Lee, Caitlyn Gibson, Craig E. Buckley, Debbie S. Silvester

    Macroporous platinum structures have been prepared by electrodeposition in the interstitial spaces between a 500 nm polystyrene sphere template, onto platinum and glassy carbon electrodes. The structures were analysed with scanning electron microscopy and confocal microscopy. These electrodes are employed for the electrochemical oxidation of hydrogen in the room temperature ionic liquid 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([C2mim][NTf2]). The behaviour on the porous electrodes showed obvious thin-layer characteristics in the cyclic voltammetry, with a strong tendency for hydrogen to accumulate and remain in the pores after being removed from the cell. Plots of peak current vs concentration (10–100% H2) were linear, but currents continued to increase over time. The sensitivities (gradients) of the calibration plots were the highest for the platinum porous structures (compared to the bare, or nanoparticle-modified surfaces). Due to the accumulation of gas, such modified electrodes could be employed as leak-detectors for very low concentrations of hydrogen.

    更新日期:2017-11-11
  • Synthesis of Te-Bi core-shell nanowires by two-step electrodeposition in ionic liquids
    Electrochem. Commun. (IF 4.396) Pub Date : 2017-11-11
    Laura Thiebaud, Sophie Legeai, Jaafar Ghanbaja, Nicolas Stein

    Te-Bi core-shell nanowires were synthesized by electrochemical deposition in ionic liquids without using a template. The nanowires were synthesized in two steps: self-standing single crystal Te nanowires with a diameter of 76.2 ± 28.4 nm and a length of a few microns were electrodeposited first, taking advantage of the templating properties of the mixture of ionic liquids EOPipTFSI:EOPipBr 95:5 mole%. The Bi shell was then deposited on the Te core in EOPipTFSI. The influence of various experimental parameters on Bi shell deposition was studied. Thanks to the higher viscosity of the electrolyte compared to an aqueous medium, a lower growth rate is observed, leading to a thin layer of bismuth. In addition, High Resolution Transmission Electronic Microscopy shows that under optimal conditions the Te nanowires are entirely covered by a homogeneous, compact and polycrystalline Bi shell and that the core/shell interface is smooth.

    更新日期:2017-11-11
  • Sodium sulfonate groups substituted anthraquinone as an organic cathode for potassium batteries
    Electrochem. Commun. (IF 4.396) Pub Date : 2017-11-10
    Jin Zhao, Jixing Yang, Pengfei Sun, Yunhua Xu

    Sodium sulfonate groups substituted anthraquinone was successfully tested as an organic positive electrode material in potassium batteries. As an organic cathode material, enhanced electrochemical performance was demonstrated for anthraquinone-1,5-disulfonic acid sodium salt, notably a good cycling stability and a capacity retention of 78 mAh g− 1 after 100 cycles. The findings offer an effective way to develop high performance organic electrode materials for potassium batteries.

    更新日期:2017-11-11
  • Facile and controllable synthesis at an ionic layer level of high-performance NiFe-based nanofilm electrocatalysts for the oxygen evolution reaction in alkaline electrolyte
    Electrochem. Commun. (IF 4.396) Pub Date : 2017-11-10
    Yansong Zhu, Yueqin Wang, Sanmei Liu, Ruike Guo, Zelin Li

    Controllable loading of NiFe-based semiconductor electrocatalysts is critical for high performance toward the oxygen evolution reaction (OER) because of their low conductivity. In this work, for the first time, Fe(OH)3/NiS composite nanolayers with high-performance for OER are synthesized in a controllable way at an ionic layer level. Specific amounts of NiS and Fe(OH)3 are loaded onto coral-like CuO/Cu microarrays (c-CuO/Cu) in an easily controlled way by successive ionic layer adsorption and reaction (SILAR); the resulting OER activity depends heavily on the number of SILAR cycles. The optimized Fe(OH)3/NiS/c-CuO/Cu electrode exhibits a very low OER overpotential of 257 mV (vs. RHE) at 10 mA/cm2 (with no IR compensation) in 1 M KOH and is stable toward OER for at least 10 h. We also prepared high-performance Fe(OH)3/Ni(OH)2/c-CuO/Cu OER electrocatalysts in a similar way. It is expected that this approach will be used to fabricate further semiconductor electrocatalysts for water splitting.

    更新日期:2017-11-10
  • One-step preparation of microporous Pd@cPIM composite catalyst film for triphasic electrocatalysis
    Electrochem. Commun. (IF 4.396) Pub Date : 2017-11-08
    Shi Xuan Leong, Mariolino Carta, Richard Malpass-Evans, Neil B. McKeown, Elena Madrid, Frank Marken

    Triphasic microporous materials (containing solid, liquid, and gas) are of interest in electrocatalysis. In this exploratory study, a polymer of intrinsic microporosity (PIM-EA-TB) is impregnated with PdCl42 − metal precursor and vacuum‑carbonised to give an electrically conductive microporous heterocarbon with embedded Pd nanoparticles of typically 10–30 nm diameter. This microporous composite catalyst is formed (via spin-coating) as “flakes” of typically 100 nm thickness and 1 to 20 μm diameter that are readily re-deposited onto glassy carbon electrode substrates. Due to the triphasic conditions, Pd@cPIM electrocatalytic reactivity is high but only for gases (H2 oxidation or O2 reduction). This selectivity is observed even in the presence of excess formic acid fuel in the aqueous/liquid phase. The potential for application in membrane-less micro-fuel cells is discussed.

    更新日期:2017-11-10
  • Surprising dependence of the current density of bromate electroreduction on the microelectrode radius as manifestation of the autocatalytic redox-cycle (EC″) reaction mechanism
    Electrochem. Commun. (IF 4.396) Pub Date : 2017-11-07
    Dmitry V. Konev, Anatoly E. Antipov, Mikhail M. Petrov, Maria A. Shamraeva, Mikhail A. Vorotyntsev

    Bromate reduction from strongly acidic solutions under steady-state conditions in the presence of a very small amount of bromine has been studied voltammetrically at disk microelectrodes of various radii. In conformity with theoretical predictions the intensity of the average current density depends on the electrode size in a non-monotonous manner, passing through a maximum for a certain radius. This behavior is a direct consequence of the autocatalytic character of this process where the non-electroactive bromate anion is reduced owing to the catalytic cycle based on the bromine/bromide redox-mediator couple. The experimentally observed dependence of the maximal current density, jmax, on the inverse disc radius, 1/r0, for electrodes of larger sizes approaches a straight line corresponding to the “strong current limit”, which exceeds the diffusion-limited current density for bromate ion.

    更新日期:2017-11-10
  • 更新日期:2017-11-05
  • Reproducible electrochemical analysis of nanostructured Cu2O using a non-aqueous 3-methoxypropionitrile-based electrolyte
    Electrochem. Commun. (IF 4.396) Pub Date : 2017-11-04
    Leyla Shooshtari, Azam Iraji zad, Raheleh Mohammadpour

    Cu2O is an attractive material in terms of semiconducting properties and is considered a leading candidate in all-oxide photovoltaics. Electrochemical analysis of Cu2O, including Mott-Schottky (MS) and impedance spectroscopy (IS), provides a wealth of data on charge carriers, Fermi level and interface properties. MS and IS are usually measured in aqueous solutions. However, Cu2O is easily reduced or oxidized to Cu or CuO in aqueous solutions, the layer peels off after the analysis and there is a small voltage window for the tests. In some cases, an anti-corrosive n-type barrier layer is employed on top of the bare Cu2O electrode to make the measurement possible, which could result in deviation from actual values. Here we introduce a non-aqueous electrolyte based on tetrabutylammonium-tetrafluoroborate in 3-methoxypropionitrile for electrochemical analysis of Cu2O. MS analysis shows reproducible results in terms of dopant density and flat band potential, while the analysis in aqueous (0.5 M Na2SO4) electrolyte shows inconsistent, irreproducible results. In the case of IS, the transport resistivity of the layers was evaluated using the new electrolyte and shows a linear trend with thickness, as expected. The proposed non-aqueous electrolyte can potentially be used for the electrochemical analysis of other sensitive semiconductors.

    更新日期:2017-11-05
  • Effective degradation of carbamazepine using a novel electro-peroxone process involving simultaneous electrochemical generation of ozone and hydrogen peroxide
    Electrochem. Commun. (IF 4.396) Pub Date : 2017-11-03
    Bo Yang, Jianping Deng, Gang Yu, Shubo Deng, Juying Li, Caizhen Zhu, Qiongfang Zhuo, Huabo Duan, Tao Guo
    更新日期:2017-11-05
  • The inhibition of hydrogen peroxide reduction at low potentials on Pt(111): Hydrogen adsorption or interfacial charge?
    Electrochem. Commun. (IF 4.396) Pub Date : 2017-10-31
    Valentín Briega-Martos, Enrique Herrero, Juan M. Feliu

    The hydrogen peroxide reduction reaction (HPRR) on Pt(111) has been studied for the first time in acid to neutral pH values in the absence of anion specific adsorption using the HMRDE configuration. The onset for the reduction is ca. 0.95 V (RHE) for the Pt(111), irrespective of the pH value. At more negative potential values, the reduction is inhibited. It has been found that the diminution of the activity on Pt(111) occurs at the same potential value in the SHE scale for the different pH values. This indicates that this deactivation is not dependent on the hydrogen adsorption process, as has been previously suggested. However, it appears to be related to the interface water reorganization and the potential of zero free charge of the metal surface. In addition, studies in alkaline conditions suggest that the presence of adsorbed OH species promotes the total conversion of hydrogen peroxide to water.

    更新日期:2017-11-01
  • Ni(II)-chelated thio-crown complex as a single redox couple for non-aqueous flow batteries
    Electrochem. Commun. (IF 4.396) Pub Date : 2017-10-27
    Seunghae Hwang, Hyun-seung Kim, Ji Heon Ryu, Seung M. Oh
    更新日期:2017-10-28
  • Electrochemical characterization of natural gold samples using the voltammetry of immobilized particles
    Electrochem. Commun. (IF 4.396) Pub Date : 2017-10-27
    Antonio Doménech-Carbó, Fritz Scholz, Ralf T. Schmitt, Juan Usera, Ana María García Forner, Emilio De la Fuente-Arévalo, Jeyabharathi Chinnaya, Joan Piquero-Cilla, Noemí Montoya
    更新日期:2017-10-27
Some contents have been Reproduced with permission of the American Chemical Society.
Some contents have been Reproduced by permission of The Royal Society of Chemistry.
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