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  • Fabrication of highly effective self-humidifying membrane electrode assembly for proton exchange membrane fuel cells via electrostatic spray deposition
    Electrochem. Commun. (IF 4.396) Pub Date : 2018-06-15
    Beom-Soo Koh, Jung-Hun Yoo, Eun-Kwang Jang, Vasanth Rajendiran Jothi, Chi-Young Jung, Sung Chul Yi
    更新日期:2018-06-15
  • Closed bipolar electrode system for a liquid-junction-free reference electrode integrated in an amperometric probe sensor
    Electrochem. Commun. (IF 4.396) Pub Date : 2018-06-15
    Siti Masturah binti Fakhruddin, Kumi Y. Inoue, Ryoto Tsuga, Tomokazu Matsue
    更新日期:2018-06-15
  • 更新日期:2018-06-13
  • Electrodeposition of rhenium with suppressed hydrogen evolution from water-in-salt electrolyte
    Electrochem. Commun. (IF 4.396) Pub Date : 2018-06-12
    Q. Huang, T.W. Lyons

    The electrodeposition of rhenium was studied using a “water-in-salt” type of electrolyte with a superhigh concentration of lithium chloride supporting salt to suppress the proton activity. Cyclic voltammetry and DC plating were carried out on rotating disc electrodes to characterize the electrolyte and to prepare thin films. Electrolytes without metal cations were also studied, where the cathodic reduction of proton was significantly suppressed when the concentration of supporting salt approached the solubility limit. Film cracks were eliminated for rhenium films deposited from this superhigh ionic strength electrolyte.

    更新日期:2018-06-12
  • Nitrogen-doped carbon-based electrocatalysts synthesised by ball-milling
    Electrochem. Commun. (IF 4.396) Pub Date : 2018-05-31
    Roberta Sibul, Elo Kibena-Põldsepp, Sander Ratso, Mati Kook, Maike Käärik, Maido Merisalu, Päärn Paiste, Jaan Leis, Väino Sammelselg, Kaido Tammeveski
    更新日期:2018-06-01
  • Electrochemical analysis of ascorbic acid and uric acid on defect-engineered carbon nanotube networks with increased exposure of graphitic edge planes
    Electrochem. Commun. (IF 4.396) Pub Date : 2018-05-31
    Rui Lei, Hongwei Ni, Rongsheng Chen, Huazhi Gu, Bowei Zhang

    In this work, defect-engineered carbon nanotube networks are grown in situ on a 316L stainless steel substrate using chemical vapor deposition and an annealing treatment. The defective carbon nanotube networks can be applied directly as electrodes for the simultaneous determination of ascorbic acid and uric acid using cyclic voltammetry and differential pulse voltammetry. Carbon nanotube networks annealed at 500 °C enable simultaneous determination of ascorbic acid and uric acid with linear responses from 100 to 3000 μM and from 10 to 150 μM, respectively. The excellent electrocatalytic activity of the defective carbon nanotube networks is attributed to the engineered defects and the large number of exposed edge planes.

    更新日期:2018-06-01
  • Chemical reactivity of Ga-based liquid metals with redox active species and its influence on electrochemical processes
    Electrochem. Commun. (IF 4.396) Pub Date : 2018-05-30
    Benchaporn Lertanantawong, Panjaphong Lertsathitphong, Anthony P. O'Mullane
    更新日期:2018-05-31
  • Modification of glassy carbon with polypyrrole through an aminophenyl linker to create supercapacitive materials using bipolar electrochemistry
    Electrochem. Commun. (IF 4.396) Pub Date : 2018-05-29
    Nigel Patterson, Anna Ignaszak

    Bipolar electrochemistry was applied to create new supercapacitive composite materials. A glassy carbon substrate was functionalized with polypyrrole through aminophenyl bridges. The composites were studied by XPS and SEM to characterize their structure. The electrical properties of the material was also tested. The specific capacitance of the material was found to be 11 mF/cm2, and the degradation potential over pure polypyrrole was improved (up to 0.70 V). Other electrochemical tests performed were short term charge-discharge and coulometry to obtain the diffusion coefficient.

    更新日期:2018-05-29
  • 更新日期:2018-05-24
  • 更新日期:2018-05-24
  • 更新日期:2018-05-24
  • A FeP powder electrocatalyst for the hydrogen evolution reaction
    Electrochem. Commun. (IF 4.396) Pub Date : 2018-05-19
    Fulong Wang, Xudong Yang, Baoxia Dong, Xu Yu, Huaiguo Xue, Ligang Feng
    更新日期:2018-05-19
  • In situ observation of Cu electrodeposition and dissolution on Au(100) by high-speed atomic force microscopy
    Electrochem. Commun. (IF 4.396) Pub Date : 2018-05-17
    Taiki Yoshioka, Hisayoshi Matsushima, Mikito Ueda

    The initial stages of Cu electrodeposition and dissolution on an Au(100) electrode in sulfuric acid solution were studied by high-speed atomic force microscopy. Dynamic observations revealed that Cu islands formed on the Au terraces within a few seconds. The islands grew to approximately 100 nm as two thick layers overlapped. The AFM height profile results indicated that each layer consisted of 3–8 atomic layers. Dissolution occurred when an anodic potential was applied, with the bottom layer dissolved preferentially. Correlation of these observations with electrochemical data from cyclic voltammetry indicated differences in the rates of deposition and dissolution.

    更新日期:2018-05-18
  • Experimental study on the diffusion of hydrogen along individual grain boundaries in nickel
    Electrochem. Commun. (IF 4.396) Pub Date : 2018-05-16
    Z.X. Ma, X.L. Xiong, L.N. Zhang, H. Zhang, Y. Yan, Y.J. Su

    Whether hydrogen diffusion can be accelerated by grain boundaries (GBs) still remains controversial. In this study, the impact of different types of GBs within the directionally solidified polycrystalline nickel specimens on hydrogen diffusion was directly observed at room temperature by combining Electron Back Scattered Diffraction (EBSD) and scanning Kelvin probe force microscopy (SKPFM). The results suggest that the coherent Σ3 twin GB provides a fast path for hydrogen diffusion, while the random GB cannot significantly accelerate the transport of hydrogen atoms. In addition, this study confirms that SKPFM is a reliable technique to allow the detection of the local diffusion and distribution of hydrogen in metals with high lateral resolution down to the GBs.

    更新日期:2018-05-17
  • Embedding leaf tissue in graphene ink to improve signals in electrochemistry-based chemotaxonomy
    Electrochem. Commun. (IF 4.396) Pub Date : 2018-05-17
    Li Fu, Yuhong Zheng, Pengchong Zhang, Jiangwei Zhu, Haoyang Zhang, Luxi Zhang, Weitao Su
    更新日期:2018-05-17
  • Preparation of defective ZnFe2O4/graphene composites and their charge storage properties
    Electrochem. Commun. (IF 4.396) Pub Date : 2018-05-17
    Shuhua Yang, Zhenzhen Han, Jing Sun, Xiaopeng Yang, Cuncheng Li, Rutao Wang, Bingqiang Cao
    更新日期:2018-05-17
  • Formation of a thin-layer of nickel hydroxide on nickel phosphide nanopillars for hydrogen evolution
    Electrochem. Commun. (IF 4.396) Pub Date : 2018-05-12
    Kun Xiong, Liping Huang, Yuan Gao, Haidong Zhang, Yue Zhuo, Huizhen Shen, Yao Wang, Lishan Peng, Zidong Wei
    更新日期:2018-05-12
  • Electrochemical desulfurization of solid copper sulfides in strongly alkaline solutions
    Electrochem. Commun. (IF 4.396) Pub Date : 2018-05-11
    Jiakang Qu, Hongwei Xie, Qiushi Song, Zhiqiang Ning, Haijia Zhao, Huayi Yin
    更新日期:2018-05-11
  • Continuous capacitive deionization with regenerative rotating film electrodes
    Electrochem. Commun. (IF 4.396) Pub Date : 2018-05-11
    Konstantinos Dermentzis, Wolfgang Wessner
    更新日期:2018-05-11
  • Effect of an Fe(II)-modified trivalent chromium conversion process on Cr(VI) formation during coating of AA 2024 alloy
    Electrochem. Commun. (IF 4.396) Pub Date : 2018-05-11
    J. Qi, B. Zhang, Z. Wang, Y. Li, P. Skeldon, G.E. Thompson

    A trivalent chromium conversion coating formed in an Fe(II)-containing solution on AA2024 alloy has been investigated by high resolution analytical electron microscopy, ion beam analysis, Raman spectroscopy and electrochemical tests. It is shown that preferential oxidation of Fe(II) species by H2O2 at cathodic sites on the alloy surface suppresses the oxidation of Cr(III) species, hence reducing the Cr(VI) content of the coating. The addition of Fe(II) species has only minor influences on the general composition of the coating, the kinetics of coating growth and the corrosion protection of the alloy.

    更新日期:2018-05-11
  • Flame-like Ni(OH)2 strongly promotes the dissociation of water and can be used to produce an excellent hybrid electrocatalyst for the hydrogen evolution reaction in alkaline media
    Electrochem. Commun. (IF 4.396) Pub Date : 2018-05-08
    Yun Zhou, Chongfeng Sun, Xigang Yang, Gang Zou, Hongjing Wu, Shengqi Xi

    In this communication, Ni(OH)2 with a flame-like morphology was successfully electrodeposited on nickel foam (NF) using a ZnO buffer layer. The flame-like Ni(OH)2/NF exhibited efficient activity for the hydrogen evolution reaction (HER) in alkaline media, requiring overpotentials of only 56.4 and 115.8 mV to reach current densities of 10 and 100 mA·cm−2, respectively, with a low Tafel slope of 52.8 mV dec−1. These results are nearly comparable to those of commercial Pt/C. The significant improvement in HER activity could be attributed to the flame-like morphology of Ni(OH)2, which may strongly promote the dissociation of water and accelerate the formation of Had. This work also provides a new approach to designing efficient hybrid catalysts for the hydrogen evolution in alkaline media.

    更新日期:2018-05-09
  • Hybrid rinse solvent processing highly flat perovskite films on planar substrate
    Electrochem. Commun. (IF 4.396) Pub Date : 2018-05-07
    Fanli Meng, Xinding Lv, Jiaojiao Wu, Yan-Zhen Zheng, Guozhong Cao, Xia Tao
    更新日期:2018-05-08
  • Electroless atomic layer deposition of copper
    Electrochem. Commun. (IF 4.396) Pub Date : 2018-05-05
    Kailash Venkatraman, Aniruddha Joi, Yezdi Dordi, Rohan Akolkar

    Electrochemical ALD enables the atomically-precise deposition of Cu films; however, in the traditional embodiment of electrochemical ALD, the underpotential deposition (UPD) step necessitates external electrode potential manipulation. This renders the process unsuitable for uniform deposition onto highly-resistive or electrically-isolated micro-patterned surfaces. To address this deficiency, we report herein the feasibility of electroless Cu ALD process consisting of: (i) Electroless UPD of a sacrificial Zn adlayer mediated by an organic reductant, followed by (ii) Spontaneous surface-limited redox replacement of the Zn adlayer by a Cu monolayer. These steps when repeated sequentially enable multilayered Cu films with minimal roughness.

    更新日期:2018-05-05
  • The missing piece of the puzzle regarding the relation between the degree of superhydrophobicity and the corrosion resistance of superhydrophobic coatings
    Electrochem. Commun. (IF 4.396) Pub Date : 2018-05-05
    A. Bahgat Radwan, Aboubakr M. Abdullah, Mohammad K. Hassan

    This work supplies the missing piece of the puzzle regarding the unclear relation between the water contact angle (WCA) of a superhydrophobic coating (SHC) and its corrosion protection performance. Generally, an increase in the WCA of a coating increases its corrosion protection behavior. However, in some cases it has been reported that an increase in the WCA, inexplicably, reduces its corrosion protection efficiency. This work uses measurements of the dielectric properties of a SHC to reveal the main reason behind a significant increase in the corrosion protection efficiency of a SHC when there are minor or no changes in the values of the measured WCA.

    更新日期:2018-05-05
  • Reconsider the depolarization behavior of copper electrodeposition in the presence of 3-mercapto-1-propanesulfonate
    Electrochem. Commun. (IF 4.396) Pub Date : 2018-05-04
    Chun-Cheng Lin, Chi-Chang Hu

    3-mercapto-1-propanesulfonate (MPS) accelerates the copper deposition rate through making the reduction of cupric ions into cuprous ions be kinetically favorable in the two-step, single-electron-transfer route. The depolarization ability of MPS shows a strong dependence on current density and its accelerating characteristic declines with the current density. The fading depolarization phenomenon is a critical reason for the void formation under the high current density plating condition although employing higher current densities to shorten the plating time for copper damascene process is the objective to push forward. Consequently, the polarizing species suppressing the deposition rate at the corner and sidewall of the vias should be strong enough to prevent copper from growing too fast, and the concentration of depolarizing additives may also need to increase to promote the growth rate at the bottom. Careful reconsideration of additives should be done to achieve the void-free filling at high current density electrodeposition.

    更新日期:2018-05-04
  • A mathematical model for initiation and growth of anodic titania nanotube embryos under compact oxide layer
    Electrochem. Commun. (IF 4.396) Pub Date : 2018-05-04
    Siwei Zhao, Chen Li, Tianfang Wei, Chengyuan Li, Mengshi Yu, Huimin Cui, Xufei Zhu

    The kinetics for initiation and growth of anodic titania nanotubes is not clear yet, because nanotubes are usually formed rapidly and initiation of nanotube embryos cannot be observed. By decoupling oxide growth and dissolution, nanotube embryos are fabricated beneath a pre-formed compact layer. Based on theories of ionic and electronic current, as well as the oxygen bubble mould effect, a mathematical model is developed for embryo initiation. The model exhibits high fidelity to measured current-time transients. Based on this model, the mechanism of nanotube embryo growth under different thickness of pre-formed layers is quantitatively explained. The embryos initiate without exposure to electrolyte, which is evidence against the traditional field-assisted dissolution theory.

    更新日期:2018-05-04
  • Highly activated screen-printed carbon electrodes by electrochemical treatment with hydrogen peroxide
    Electrochem. Commun. (IF 4.396) Pub Date : 2018-05-04
    M.I. González-Sánchez, B. Gómez-Monedero, J. Agrisuelas, J. Iniesta, E. Valero

    An easy effective method for the activation of commercial screen-printed carbon electrodes (SPCEs) using H2O2 is presented to enhance sensing performances of carbon ink. Electrochemical activation consists of 25 repetitive voltammetric cycles at 10 mV s−1 using 10 mM H2O2 in phosphate buffer (pH 7). This treatment allowed us to reach a sensitivity of 0.24 ± 0.01 μA μM−1 cm−2 for the electroanalysis of H2O2, which is 140-fold higher than that of untreated SPCEs and 6-fold more than screen-printed platinum electrodes (SPPtEs). Electrode surface properties were characterized by SEM, EIS and XPS. The results revealed atomic level changes at the electrode surface, with the introduction of new carbon‑oxygen groups being responsible for improved electro-transfer properties and sensitivity. Our method was compared with other previously described ones. The methodology is promising for the activation of commercial carbon inks-based electrodes for sensor applications.

    更新日期:2018-05-04
  • Impurity-induced discharges in plasma electrolysis
    Electrochem. Commun. (IF 4.396) Pub Date : 2018-05-04
    M.P. Kamil, H.W. Yang, Y.G. Ko

    The mechanism of impurity-induced discharges in plasma electrolysis (PE) was elucidated on the basis of a novel microstructural interpretation. We identified the presence of impurity compounds decorating the rim of the micro-pores, which were ‘fingerprint’ of plasma discharge activities. The formation mechanism of inorganic layer by PE was suggested based on the distribution of impurities and a transient diffusion pattern accompanying plasma discharges.

    更新日期:2018-05-04
  • Dihemic c4-type cytochrome acting as a surrogate electron conduit: Artificially interconnecting a photosystem I supercomplex with electrodes
    Electrochem. Commun. (IF 4.396) Pub Date : 2018-05-04
    Sven C. Feifel, Kai R. Stieger, Mahdi Hejazi, Xie Wang, Marianne Ilbert, Athina Zouni, Elisabeth Lojou, Fred Lisdat

    Connection of photosystem I (PSI) with electrodes has been shown to create artificial photosynthetic systems that hold promise for the synthesis of solar fuels. The high quantum yields of PSI require efficient electron transfer from the electrode to the reaction center of PSI in order to restock the light-induced holes, a task which in nature is performed by small redox proteins. Here, we have investigated the potential “wiring” properties of a dihemic c-type cytochrome (cyt c4), in order to efficiently connect PSI with electrodes. Cyt c4 has shown direct electron transfer (DET) with both hemes in electrical communication with two different electrode materials (ITO and Au) and on the basis of cyt c4-multilayer electrodes “self-exchange” properties can also be deduced. Investigation of cyt c4 in combination with PSI within an inverse opal ITO electrode has shown the dihemic protein to be a valuable molecular electron conduit, able to interconnect the photoenzymatic reaction with the 3D electrode. The properties have been compared with those of electrodes based on monohemic cyt c derived from horse heart.

    更新日期:2018-05-04
  • Porous and three dimensional titanium nitride supported platinum as an electrocatalyst for oxygen reduction reaction
    Electrochem. Commun. (IF 4.396) Pub Date : 2018-05-03
    Yuying Zheng, Jian Zhang, Hengtong Zhan, Dalei Sun, Dai Dang, Xin Long Tian

    The development of a catalyst that is both effective and robust is desirable, but remains a challenge for those aiming to commercialize polymer electrolyte membrane fuel cells. Thus, a facile method is proposed to develop hierarchical and three-dimensional titanium nitride (TiN) architectures, with the robust non‑carbon material being implemented as the Pt support. The resulting catalyst (Pt/TiN) demonstrates high activity and stability, and the experimental data confirm the critical significance of the novel TiN support.

    更新日期:2018-05-03
  • Understanding the redox reactions of adjacent carboxyl groups and anhydride groups following citric acid treatment of defect-containing multiwalled carbon nanotubes
    Electrochem. Commun. (IF 4.396) Pub Date : 2018-05-03
    Jiuting Chen, Fumitaka Kobayashi, Kouya Eguchi, Keiko Waki

    Although carbon materials have been widely used in battery applications, the origin of the redox reaction appearing in the important potential region is not well understood. Moreover, typical functionalization treatments that use diluted strong acids are limited by strong oxidation and the properties of water-based solutions. Thus, most treatments cannot precisely control the nature of functional groups. The present work investigates a citric acid treatment that selectively fixes carboxyl and anhydride groups onto multiwalled carbon nanotubes at low temperatures. The results show that the edges of the defect structures of multiwalled carbon nanotubes provide suitable positions at which redox-active adjacent carboxyl groups and anhydride groups can form during citric acid treatment.

    更新日期:2018-05-03
  • Irradiation-induced point defects enhance the electrochemical activity of 3C-SiC: An origin of SiC corrosion
    Electrochem. Commun. (IF 4.396) Pub Date : 2018-04-27
    Yuki Maeda, Kazuhiro Fukami, Sosuke Kondo, Atsushi Kitada, Kuniaki Murase, Tatsuya Hinoki

    As silicon carbide (SiC) is an inert material, it has attracted attention as an alternative material for the core components of nuclear fuel cladding. However, the corrosion of SiC under neutron irradiation has been reported, and this has been a bottleneck issue. Here, we semi-quantitatively introduced point defects into single crystal 3C-SiC layers by ion irradiation, and investigated their corrosion behavior in terms of the electrochemical activity associated with the point defects. The results showed a shift in corrosion potential and an increase in the corrosion current due to the introduction of defects. However, in the case of aluminum (Al)-doped SiC, these changes were more moderate than in the cases of the nitrogen (N)- or boron (B)-doped material, implying that Al-doped SiC has a better tolerance against corrosion.

    更新日期:2018-04-27
  • Anodic titanium oxide photonic crystals prepared by novel cyclic anodizing with voltage versus charge modulation
    Electrochem. Commun. (IF 4.396) Pub Date : 2018-04-24
    N.A. Sapoletova, S.E. Kushnir, K.S. Napolskii

    Photonic crystals based on titania are of great practical importance in modern photonics owing to a variety of possibilities for their applications in optoelectronics, sensorics, and solar photovoltaics. However, the reproducible, scalable, and low-cost method of the preparation of titania photonic crystals with desired optical characteristics is still absent. Here the novel anodizing regime with voltage versus electric charge modulation, U(Q), is suggested for the precise morphology control of anodic porous films of valve metals oxides. The potential of the suggested approach is demonstrated on the preparation of high-quality one-dimensional titania photonic crystals. A new type of anodic titania nanotubes possessing periodic change of inner diameter and constant outer diameter is prepared using sine-wave modulation of applied voltage with electric charge. The possibility to tune the position of photonic band gap within the whole visible spectrum is shown.

    更新日期:2018-04-25
  • Stability of molecular radicals in organic non-aqueous redox flow batteries: A mini review
    Electrochem. Commun. (IF 4.396) Pub Date : 2018-04-22
    Craig G. Armstrong, Kathryn E. Toghill

    The application of novel organic redox materials is a plausible pathway towards techno-economic energy storage targets due to their low cost and sustainable design. Their operation in non-aqueous redox flow batteries affords researchers the opportunity to innovate, design and optimise these new chemistries towards practical energy densities. Despite this, the identification of high capacity organics which also display long-term stability is inherently challenging due to the high reactivity of molecular radicals.

    更新日期:2018-04-25
  • Seriatim ECSTM-ECPMIRS of the adsorption of carbon monoxide on Cu(100) in alkaline solution at CO2-reduction potentials
    Electrochem. Commun. (IF 4.396) Pub Date : 2018-04-22
    Jack H. Baricuatro, Youn-Geun Kim, Carol L. Korzeniewski, Manuel P. Soriaga

    It was recently demonstrated that the sequential or seriatim application of electrochemical scanning-tunneling microscopy (ECSTM) and differential electrochemical mass spectrometry (DEMS) enables the correlation, under actual reaction conditions, of a specific structure on a Cu electrode surface with the generation of a particular CO-reduction product. As an extension of the operando hyphenated-technique approach, we paired ECSTM with electrochemical polarization-modulation IR reflection-absorption spectroscopy (ECPMIRS) to identify a delineating potential that affected the coverage, the molecular orientation, and the adlattice structure of CO adsorbed on Cu(100) in 0.1 M KOH under CO2-reduction conditions. The results may have significant ramifications on the theory-based reaction mechanism for the formation of C2 compounds, as well as insights into the mode of coordination between CO and zerovalent Cu.

    更新日期:2018-04-25
  • Corrosion of metal electrodes in deep eutectic solvents
    Electrochem. Commun. (IF 4.396) Pub Date : 2018-04-12
    Davide Di Marino, Marwan Shalaby, Stefanie Kriescher, Matthias Wessling

    Deep eutectic solvents (DESs) represent a green and non-expensive substitute for ionic liquids as non-aqueous electrolytes (NAEs). Electrochemical applications in NAEs benefit from the extended potential windows, due to the absence or minimization of water. However, interactions between electrode and electrolyte, as well as their degradation, embody a relevant but unexplored territory for the implementation in electrochemical systems. Electrochemical characterization of six electrode–electrolyte couples (three electrodes in two different DESs) were conducted by means of cyclic voltammetry and chronoamperometry. Besides conventional electrochemical characterization, ICP-OES, TOC, SEM and EDX measurements were used to track the transformations in the system. This work represents a first attempt to develop a methodology for the characterization of electrode corrosion in DESs.

    更新日期:2018-04-17
  • An ultra-high vacuum electrochemical/mass spectrometry study of anodic decomposition of a protic ionic liquid
    Electrochem. Commun. (IF 4.396) Pub Date : 2018-04-12
    Sean E. Goodwin, Joshua S. Gibson, Robert G. Jones, Darren A. Walsh

    Protic ionic liquids (PILs) are ionic liquids that are formed by proton transfer from Brønsted acids to Brønsted bases, and which are being proposed for use in a wide range of electrochemical devices. In this contribution, we describe electrolysis of the PIL diethylmethylammonium trifluoromethanesulfonate at Pd, Pt, and Au electrodes in an ultra-high vacuum chamber connected to a mass spectrometer. At potentials negative of about −0.8 V vs. Pd/H, reduction of the PIL cations occurs, liberating H2. Positive of about 2.2 V vs. Pd/H, electrooxidation of the PIL anions occurs, resulting in the detection of a number of fragments of the trifluoromethanesulfonate ions using the mass spectrometer. Notably, electrooxidation of the PIL anions occurs at the same potential, regardless of whether Pt, Au, or Pd is used as the electrode. In contrast, electrooxidation of water in the PIL occurs at different potentials in the PIL as the electrode composition changes. These results show that the electrochemical window of the PIL is independent of the electrode composition, but if water is present in the liquid, this independence is masked by the electrolysis of water.

    更新日期:2018-04-17
  • Electrochemical synthesis of ammonia using ruthenium–platinum alloy at ambient pressure and low temperature
    Electrochem. Commun. (IF 4.396) Pub Date : 2018-04-12
    Revanasiddappa Manjunatha, Alex Schechter

    Ammonia was electrochemically produced from nitrogen and water using a ruthenium–platinum (RuPt) alloy catalyst cathode and a nickel anode at ambient pressure and room temperature. The rate of ammonia formation was 5.1 × 10−9 gNH3 s−1 cm−2 with a 13.2% faradaic efficiency at an applied potential of 0.123 V vs. RHE; it reached 1.08 × 10−8 gNH3 s−1 cm−2 at 0.023 V. Ammonia production was investigated under selected potentials and temperatures. Real-time direct electrochemical mass spectrometric (DEMS) analysis of the evolved gases was performed at various applied potentials. In general, the mass-to-charge ratio signals of hydrogen and ammonia were detected, and their intensities increased with increasing potentials; however, there was no trace of a hydrazine signal. Compared to metallic ruthenium and platinum catalysts, RuPt showed a synergistic effect toward electrochemical formation of ammonia due to co-catalysis.

    更新日期:2018-04-17
  • Electrochemical behavior of ferritin at the polarized water|1,2-dichloroethane interface
    Electrochem. Commun. (IF 4.396) Pub Date : 2018-04-12
    Hiroki Sakae, Yusuke Toda, Takashi Yokoyama

    The electrochemical behavior of ferritin at the polarized water|1,2-dichloroethane (DCE) interface was studied, mainly under acidic conditions. No obvious voltammetric responses were observed under neutral and alkaline conditions where ferritin formed an uncharged nanocage structure. On the other hand, large electrochemical responses were obtained in the positive potential region under acidic conditions where ferritin was disassembled into positively charged subunits. These responses varied slightly with the concentration of the supporting electrolyte in the organic phase and changed drastically with the concentration of ferritin and under repetitive sweeps. In addition, depending on the applied potential and the concentration of ferritin, a white film was formed at the interface. This electrochemical behavior could be attributed to ion transfer and the adsorption/desorption of positively charged ferritin subunits with the interfacial activity accompanied by the facilitated ion transfer of the organic supporting electrolyte anion.

    更新日期:2018-04-12
  • Electrochemical characterization of bed electrodes using voltammetry of single granules
    Electrochem. Commun. (IF 4.396) Pub Date : 2018-04-11
    Jose Rodrigo Quejigo, Luis F.M. Rosa, Falk Harnisch

    In the search for high surface area electrodes and higher volumetric performances for bioelectrochemical systems, the use of bed electrodes has become a vital field of research. In bed electrodes, conductive particles, i.e. granules, are used as bulk material and are polarized for biofilm growth. One intrinsic constraint of bed electrodes is that these cannot be analyzed by dynamic electrochemical techniques like cyclic voltammetry (CV) due to their high internal resistance and poor polarization behavior. Therefore, solutions to elucidate the extracellular electron transfer (EET) fundamentals in bed electrodes are needed. In this study we show, using the example of a Geobacter-based bed electrode, that the thermodynamics of the EET of single granules can be revealed. This is achieved by cyclic voltammetry of single granules. A novel 3D-printed clamp working electrode is presented which can be exploited further for electrochemical analysis of biotic and abiotic electrode particles.

    更新日期:2018-04-12
  • Impact of the metal electrode size in half-cells studies: Example of graphite/Li coin cells
    Electrochem. Commun. (IF 4.396) Pub Date : 2018-04-10
    Lénaïc Madec, Hervé Martinez

    When half-cells are used to evaluate and understand electrochemical performance and interface properties of a given electrode, the metal electrode size is rarely mentioned. To evaluate such impact on the electrochemical performance and interphase formation, graphite/Li coin cells were used. Undersizing the Li metal electrode led to significantly lower charge/discharge capacities even at C/20 rate due to incomplete lithiation/delithiation processes of the graphite electrode edge. It also led to the formation of non-uniform Li metal deposits as well as to a graphite SEI film with a thickness and composition gradient across the electrode. Oversized Li led, however to homogeneous graphite SEI film. Overall, these results highlight the critical role of the metal electrode size in half-cells and should apply to all half-cells studies using other metal electrodes such as Na, K, Mg.

    更新日期:2018-04-10
  • Simultaneous study of different regions of an electrode surface with a novel spectroelectrochemistry platform
    Electrochem. Commun. (IF 4.396) Pub Date : 2018-04-07
    Jesus Garoz-Ruiz, Aranzazu Heras, Alvaro Colina

    A spectroelectrochemistry device capable of studying different regions of an electrode surface simultaneously is presented in this work. It is based on two reflection probes placed in a near-normal arrangement with respect to an electrode surface, part of which has been deliberately modified. As expected, the electrochemical signal contains information related to the whole system, it being impossible to distinguish which behaviour corresponds to the unmodified and which to the modified part of the electrode. Spectroelectrochemistry provides an excellent solution because the reflection probes fully explain the electrochemical response, allowing deconvolution of the electrochemical behaviour from an optical point of view under exactly the same experimental conditions. To demonstrate the usefulness of this platform, a highly oriented pyrolytic graphite electrode is partially modified with commercially available carbon nanotubes or graphene, and the oxidation of dopamine at different parts of the electrode is studied simultaneously. A remarkable decrease in the onset oxidation potential is observed at the modified surfaces compared to the bare electrode. This work highlights the advantages of spectroelectrochemistry for the characterization of materials and the comparison of electrode surfaces, laying the groundwork for novel experiments in which simultaneous measurement is a key factor.

    更新日期:2018-04-08
  • Analysis of quasi-reversible cyclic voltammograms: Transformation to scan-rate independent form
    Electrochem. Commun. (IF 4.396) Pub Date : 2018-04-06
    Tamás Pajkossy

    A simple procedure is suggested by which cyclic voltammograms, CVs, pertaining to partially diffusion controlled charge transfer reactions can be analyzed. Using this procedure, from a set of CVs taken at varied scan rates, two scan-rate independent, hysteresis-free functions can be calculated. One of them is the diffusion-free polarization curve, the other is the semi-integrated form of the reversible CV.

    更新日期:2018-04-07
  • Detection of abasic DNA by means of impedance spectroscopy
    Electrochem. Commun. (IF 4.396) Pub Date : 2018-04-06
    F. Heinrich, M. Riedel, F. Lisdat

    Abasic sites can occur in DNA for different reasons, and thus the detection of this special molecular structure has turned into the focus of research. Here we have investigated the hybridization of abasic ssDNA to immobilized ssDNA probes by impedance spectroscopy. For this purpose three different abasic 25mer ssDNA (abasic site near the electrode; in the middle and near the solution) are studied in comparison to fully complementary 25mer ssDNA. For all abasic strands the surface binding can be followed concentration dependent via impedance spectroscopy; however, the concentration range and the maximum impedance change are found to be different compared to fullmatch ssDNA. Here, the position of the abasic site within the DNA strand significantly determines the signal behavior, and thus even allows a partial discrimination between the different abasic DNA strands. By investigating the binding in parallel by SPR, only slightly smaller surface concentrations are detected for the abasic strands in comparison to the fullmatch strand. This points to the formation of different DNA structures when abasic sites are contained.

    更新日期:2018-04-07
  • A new strategy for the electrolytic removal of organics based on adsorption onto granular activated carbon
    Electrochem. Commun. (IF 4.396) Pub Date : 2018-04-06
    M. Muñoz-Morales, C. Sáez, P. Cañizares, M.A. Rodrigo

    In this paper, a new strategy for the electrochemical treatment of organic pollutants is introduced. This is based on the concentration of organics by adsorption onto granular active carbon (GAC) with the consequent production of a more highly concentrated solution of organics in methanol, which is then electrolyzed. Electrolysis in methanol supporting media allows the complete removal of the pollutant and reaction intermediates. Suitable conductivity of the electrolyte was obtained simply by adding sodium hydroxide. Results obtained in the tests carried out in this work show a great improvement in the efficiency of the removal of clopyralid when using this technology, which could lead to very important energy savings. This experiment opens the possibility of using electrochemical technology more efficiently for the degradation of diluted wastes, which is currently a very inefficient process.

    更新日期:2018-04-06
  • Voltammetric behaviour of Cu alloys toward hydrogen peroxide and organic species
    Electrochem. Commun. (IF 4.396) Pub Date : 2018-04-06
    Stefano Ruggeri, Emily Miles, Fabrizio Poletti, Laura Pigani, Chiara Zanardi, Barbara Zanfrognini, Elia Corsi, Nicolò Dossi, Renato Seeber, Fabio Terzi

    The communication reports on the electrocatalytic properties exhibited by five Cu alloys (Cu-Zn, Cu-Sn, Cu-Ni, Cu-Zn-Ni, Cu-Al) and of pure Cu, Ni and Al in the reduction or oxidation of a number of representative species. A prototypical strong oxidising agent, namely hydrogen peroxide, and some of the most important oxidisable species, namely methanol, ethanol, and formaldehyde, are tested. Both cathodic and anodic processes are facilitated by using specific alloys in the case of strong oxidants and different organic molecules, respectively.

    更新日期:2018-04-06
  • Electrochemical behavior of self-assembled DNA–gold nanoparticle lattice films
    Electrochem. Commun. (IF 4.396) Pub Date : 2018-04-05
    Sergio Kogikoski Jr, Lauro T. Kubota
    更新日期:2018-04-06
  • Unified theoretical treatment of the Eirrev, CE, EC and CEC mechanisms under voltammetric conditions
    Electrochem. Commun. (IF 4.396) Pub Date : 2018-04-03
    A. Molina, M. López-Tenés, E. Laborda

    Via a thoughtful analysis it is demonstrated that the mathematical problem of the voltammetry of a simple charge transfer process of any reversibility degree at a macrointerface is totally equivalent to those of the CE, EC and CEC mechanisms such that they all can be reduced to a formally identical one-variable problem. The simplicity and generality of the resulting boundary value problem makes it very easy and rapid the study of the response in any voltammetric technique by analytical or numerical methods.

    更新日期:2018-04-03
  • Sunlight induced photoelectrochemical anticorrosion effect of corrosion product layers on electrogalvanized steel in simulated seawater
    Electrochem. Commun. (IF 4.396) Pub Date : 2018-03-29
    Qingyang Li, Wei Li, Maozhong An

    It is demonstrated that the oxides and corrosion product layers not only endured the attack from aggressive environments, but also provided an additional photogenerated cathode protection to electrogalvanized steel in simulated seawater under simulated sunlight illumination. The corrosion product layer, which is composed of ZnO, Zn(OH)2, Zn2(OH)2CO3 and Zn5(OH)8Cl2·H2O provided approximately 30% better corrosion protection to zinc coating under sunlight illumination than the situation in darkness according to the Stern−Geary resistance results. The responsible mechanism is due to the fact that the ZnO layer could produce photoelectrons which are transferred directly to the substrate, thereby providing a cathodic protection to electrogalvanized steel under sunlight illumination.

    更新日期:2018-03-30
  • Cavities between the double walls of nanotubes: Evidence of oxygen evolution beneath an anion-contaminated layer
    Electrochem. Commun. (IF 4.396) Pub Date : 2018-03-22
    Mengshi Yu, Chen Li, Yibei Yang, Sunkai Xu, Kun Zhang, Huimin Cui, Xufei Zhu

    The mechanisms of formation of porous anodic alumina and anodic TiO2 nanotubes (ATNTs) have attracted increasing attention due to the wide range of application of these materials. The field-assisted dissolution and field-assisted ejection theories are widely supported, despite the fact that many experimental results raise difficult questions. The oxygen bubble mould theory can explain experimental phenomena that contradict the field-assisted dissolution theory, but is controversial as there is a lack of evidence of oxygen evolution. In this work, cavities between the double walls of ATNTs obtained in electrolytes containing NH4F and H3PO4 provide direct evidence of oxygen bubbles resulting in pore formation. Oxygen evolution proceeds at the interface between the anion-contaminated layer and the barrier oxide layer. Small oxygen bubbles that cannot rupture the anion-contaminated layer flow upward with the barrier oxide, resulting in cavities between the double walls of the nanotubes.

    更新日期:2018-03-22
  • Quantifying the turnover frequency for ethanol electro-oxidation on polycrystalline Pt in acid and alkaline media
    Electrochem. Commun. (IF 4.396) Pub Date : 2018-03-17
    Loriz F. Sallum, Ernesto R. Gonzalez, Andressa Mota-Lima

    The turnover frequency (TOF) is conventionally used to measure activity in catalysis but is rarely used in electro-catalysis, which uses the value of the interfacial current instead. Herein, a procedure to quantify the TOF for the ethanol oxidation reaction (EOR) in electro-catalysis is proposed and compared with the value observed in catalysis (Sapi et al., Nano Lett., 14 (2014) 6727). The intrinsic TOF in an alkaline medium is 9.23 molecules site−1·s−1, which is three times larger than the value obtained in an acidic medium, explaining the major differences observed between the interfacial currents recorded during cyclic voltammetry and chronoamperometry in the two media. In the future this methodology will be extended to single crystal surfaces and nanoparticles, assisting the development of electro-catalysts on a more fundamental theoretical basis.

    更新日期:2018-03-18
  • Evidence for the production of hydroxyl radicals at boron-doped diamond electrodes with different sp3/sp2 ratios and its relationship with the electro-oxidation of aniline
    Electrochem. Commun. (IF 4.396) Pub Date : 2018-03-15
    L. Carolina Espinoza, Adolfo Henríquez, David Contreras, Ricardo Salazar

    In this work, the electrochemical production of hydroxyl radicals on boron-doped diamond (BDD) electrodes with different sp3/sp2 ratios was studied, together with the relationship between the level of production of hydroxyl radicals and the degradation and mineralization of aniline, taken as a model organic compound. A higher sp3/sp2 ratio on the BDD surface produces a greater number of hydroxyl radicals, as previously stated; however, for the first time the difference in the production of hydroxyl radicals for different levels of sp2-impurities on BDD surface was established and its importance in determining the nature of the BDD surface (semi-active or inactive) is demonstrated. The results are of great relevance in interpreting the real effect of conductive diamond electrochemical oxidation on the treatment of organic wastes described in the literature.

    更新日期:2018-03-15
  • An all-solid-state Li-organic battery with quinone-based polymer cathode and composite polymer electrolyte
    Electrochem. Commun. (IF 4.396) Pub Date : 2018-03-14
    Wenfei Wei, Long Li, Lei Zhang, Jianhe Hong, Gang He
    更新日期:2018-03-14
  • Kinetics of oxygen reaction and discharge/charging overvoltages of Li-O2 battery with aprotic electrolytes
    Electrochem. Commun. (IF 4.396) Pub Date : 2018-03-12
    Оleg V. Коrchagin, Vera А. Bogdanovskaya, Оleg V. Tripachev, Viktor V. Emets
    更新日期:2018-03-13
  • A rechargeable Mg2+/Li+ hybrid battery based on sheet-like MoSe2/C nanocomposites cathode
    Electrochem. Commun. (IF 4.396) Pub Date : 2018-03-10
    Jing-Jing Fan, Shou-Yu Shen, Yuan Chen, Li-Na Wu, Jun Peng, Xin-Xing Peng, Chen-Guang Shi, Ling Huang, Wen-Feng Lin, Shi-Gang Sun
    更新日期:2018-03-10
  • Electrochemical synthesis of photoactive carbon-carbide structure on silicon in molten salt
    Electrochem. Commun. (IF 4.396) Pub Date : 2018-03-06
    Eimutis Juzeliūnas, Derek J. Fray, Putinas Kalinauskas, Ignas Valsiūnas, Gediminas Niaura, Algis Selskis, Vitalija Jasulaitienė

    Carbon-carbide coatings on silicon with a distinctively developed surface were electrochemically synthesized in molten CaCl2 using Si-SiO2 precursor and a graphite anode. Energy-dispersive X-ray spectroscopy showed approximately one quarter of the structure (in at.%) was composed of carbon. X-ray diffraction identified crystalline phases of graphite, silicon carbide and carbonate. X-ray photoelectron spectroscopy identified the carbide/carbon concentration ratio varied from 0.2 in the external region of the structure to 0.7 at the silicon substrate boundary. Mott-Schottky analysis showed p-type semiconductivity of the structure with high density of charge carriers N > 1016 cm−3. The surfaces absorbed over 90% of white light in a broad region of wavelengths from 400 nm to 1100 nm. The obtained composite is promising for application as an antireflection and protective coating or a photoelectrode.

    更新日期:2018-03-06
  • In situ monitoring of the localized corrosion of 304 stainless steel in FeCl3 solution using a joint electrochemical noise and scanning reference electrode technique
    Electrochem. Commun. (IF 4.396) Pub Date : 2018-03-02
    Cheng Wang, Yangzhi Cai, Chenqing Ye, Shigang Dong, Xinshuo Cai, Yanhui Cao, Changjian Lin

    Electrochemical noise (ECN) has been adopted as a powerful method of studying early-stage corrosion, but there is a lack of direct in situ evidence to prove the correlation between ECN data and visual corrosion behavior. The advanced scanning reference electrode technique (SRET) assisted by electrochemical scanning tunneling microscopy (ECSTM) can detect local active sites of micro corrosion and follow their initiation and development, and can provide experimental evidence of localized corrosion at the same time as the system is monitored by ECN. To further understand the localized corrosion mechanism of metals, an in situ strategy (ECN/SRET) was developed and used to detect rapid initialization of active corrosion sites, and follow the evolution of pitting corrosion. It is expected that the ECN/SRET combination will prove to be a powerful tool for in-depth studies of localized corrosion.

    更新日期:2018-03-02
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  • A non-conventional way to modulate the capacitive process on carbon cloth by mechanical stretching
    Electrochem. Commun. (IF 4.396) Pub Date : 2018-02-27
    Haixia Zhang, Cuihua An, Aiting Yuan, Qibo Deng, Jiangli Ning

    This work investigates the in situ capacitive charging/discharging process of a carbon cloth surface under an external mechanical strain in order to understand the strain-modulated electrochemistry of an amorphous material. Our work first quantifies the electrochemical change in capacitive potential, E, in response to an applied linear strain, ε. The experimental data show that tensile strain could positively shift the capacitive potential. More importantly, the discharging time, a significant representative parameter of the energy storage performance of a material, is shortened when mechanically stretched. This phenomenon suggests that the specific capacitance is strain-dependent, and tensile strain decreases the specific capacitance of carbon cloth. This dependence could be attributed to a change in the surface free energy of carbon cloth when it is mechanically stretched. External mechanical work can modulate the typical capacitive process on not only metal or metal-oxide surfaces with specific lattice structures but also the surfaces of amorphous materials.

    更新日期:2018-02-28
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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