Influence of surface inhomogeneities of boron doped CVD-diamond electrodes on reversible charge transfer reactions

The electrochemical behaviour of reversible charge transfer reactions on boron doped diamond (BDD) was studied by cyclic voltammetry and electrochemical impedance spectroscopy using rotating disc electrodes under defined convection. Diamond films of 5 m thickness with doping levels of 200, 3000 and 6000 ppm were prepared by hot filament chemical vapour deposition on niobium substrate. The electrochemical measurements were carried out on BDD electrodes in deaerated 0.5 M Na₂SO₄ + 5 mM K₃[Fe(CN)₆]/K₄[Fe(CN)₆] solution at rotation frequencies 0 < f _rot < 4000 rpm. Comparative measurements were carried out on an active Pt electrode. The BDD electrodes exhibit distinct irreversibilities indicated by a larger peak potential difference in the cyclic voltammograms, lower diffusion limiting current densities and an additional impedance element at high frequencies. Mechanical polishing with carbon fleece and SiC paper strongly affects the irreversible behaviour of the BDD electrodes. The experimental results are explained by a partial blocking of the diamond surface with reversible charge transfer at active sites. The impedance spectra are analysed quantitatively using a transport impedance model for reversible reactions on partially blocked electrode surfaces.     

Preparation and electrochemical performances of ZnO nanowires as anode materials for Ni/Zn secondary battery

ZnO nanowires were synthesized by a hydrothermal route without any substrate or template. Structure analyses through XRD, SEM, TEM and HRTEM indicated that ZnO nanowires had high purity and perfect crystallinity, and grew along [0 0 0 1]. The diameter was 50-80 nm, the length was about several micrometers and length-diameter ratio was more than 100. As electrode materials of Ni/Zn batteries, ZnO nanowires showed the obviously improved cycle stability, average discharge capacity of 609 mAh g⁻¹, higher discharge voltage/lower charge voltage. Slow rate cyclic voltammetry showed that electrochemical activity of ZnO nanowires was superior to that of the conventional ZnO. The improvements of electrochemical performance were ascribed to the unique nanowire structure. During the charging/discharging cycles, nanowires were broke, grew in diameter, and changed into nanorods. Nanowires lying parallel to the anodes could suppress the growth of dendrite clusters perpendicular to the anodes.     

Defect engineering in semiconducting oxides: Control of ZnO surface potential via temperature and oxygen pressure

The technological usefulness of a semiconductor often depends on the types, concentrations, charges, spatial distributions, and mobilities of the atomic‐scale defects it contains. For semiconducting metal oxides, defect engineering is relatively new and involves complex transport and reaction networks. Surface‐based methods hold special promise in nanostructures where surface‐to‐volume ratios are high. This work uses photoreflectance augmented by X‐ray photoelectron spectroscopy to show that the surface potential V_S for Zn‐terminated ZnO(0001) can be manipulated over a significant range 54.97–79.08 kJ/mol (0.57–0.82 eV) via temperature and the partial pressure of O₂. A defect transport model implies this variation in V_S should affect the injection rate of oxygen interstitials by a factor of three. Such injection plays an important role in controlling the concentrations of oxygen vacancies deep in the bulk, which often prove troublesome as trapping centers in photocatalysis and photovoltaics and as parasitic emitters in light‐emitting devices. © 2015 American Institute of Chemical Engineers AIChE J, 62: 500–507, 2016     

Highly sensitive characteristic of surface enhanced Raman scattering for CuO/Au core/shell nanowires substrate

In this paper, we report a facile process to fabricate CuO/Au core/shell nanowires, where CuO core and Au shell were prepared by thermal oxidation and sputtering, respectively. The as-prepared CuO/Au nanowires are highly sensitive surface-enhanced-Raman-scattering (SERS) substrates, which can detect methylene blue down to a very low concentration of 10^?13 M. The major advantages of SERS substrates based on CuO/Au core/shell nanowires compared with others SERS substrates are the high sensitivity, uniformity, and purity due to the absence of any organic surfactants in the synthesis process.     

Theoretical study of charge transfer mechanism in fullerene-phenyl-phenothiazine compound: A real-space analysis

Quantum chemistry methods as well as two-dimensional (2D) and three-dimensional (3D) real-space analysis have been conducted to study the photo-induced intramolecular charge-transfer (ICT) and excited state properties of fullerene-phenylphenothiazine, which has recently been developed for solar cells. Firstly, we obtained the energy levels and spatial distributions of HOMO/LUMO, energy gap (ΔEH-L) and excitation energies on the basis of quantum chemistry study. Secondly, two-dimensional (2D) and three-dimensional (3D) real-space analysis were used to visualize the CT process and to reveal the nature of the excited states. In the above analyses, the 2D real-space analysis of the transition density matrix provided information about the electron-hole coherence, and the 3D real-space analysis of charge difference density enabled the visualization of the orientation and result of the ICT. The results of real-space analysis directly indicate that some states are ICT states, and others belong to locally excited states. Moreover, according to the generalized Mulliken Hush theory, we calculated the electronic coupling matrix elements and predict that electron transfer for some ICT states more easily takes place than that for some locally excited states.     

Identification of inductive behavior for polyaniline via electrochemical impedance spectroscopy

Polyaniline (PANI) film electrodeposited in HCl medium using cyclic voltammetry (CV) with an upper potential limit of 0.90 V, exhibited an inductive behavior. PANI films deposited with different conditions were subjected to various applied potentials and the impedance characteristics were recorded through electrochemical impedance spectroscopy (EIS). The impedance results clearly reveal the existence of inductive behavior to PANI. Inductive behavior was observed for PANI films deposited with conditions which favor benzoquinone/hydroquinone (BQ/HQ) formation and further evidenced by X-ray photoelectron spectroscopy (XPS). A comparative analysis of the EIS and XPS results of PANI films prepared under similar conditions with the upper potential limits of 0.75 and 0.90 V, respectively, clearly documented that the presence of BQ/HQ, the degradation product of PANI, formed during the electrochemical polymerization at the upper potential limits causes inductive behavior to PANI.     

Significantly enhanced charge transfer efficiency and surface reaction on NiP2/g-C3N4 heterojunction for photocatalytic hydrogen evolution

In this work, a novel NiP₂/g-C₃N₄ heterojunction via homogeneous precipitation method assisted by thermal phosphorization reaction was designed and constructed, and the optimized sample showed the excellent photocatalytic H₂ evolution activity under visible-light irradiation, which was nearly 112 times higher than that of pristine g-C₃N₄ sample. Experimental characterizations and DFT calculations demonstrated that the NiP₂ nanoparticles covered on the g-C₃N₄ surface can form a built-in electric field at the interface to accelerate the transfer of photoexcited electrons from g-C₃N₄ to NiP₂, crucial for hindering the recombination of electron-hole pairs. Moreover, the energy barrier of hydrogen evolution reaction can also vastly reduce when combined NiP₂ and g-C₃N₄ to construct NiP₂/g-C₃N₄ heterojunction. This work represents a method through combing experimental and theoretical tools to thoroughly investigate the mechanism of photocatalytic process.     

Mass transport and charge transfer rates for Co/Co redox couple in a thin-layer cell

Recently, the complex Co(dtb)₃ⁿ⁺ (dtb = 4,4 di tert-butyl-2,2′ bipyridine) in methoxypropionitrile (MPN) solvent has been proposed as an alternative redox mediator in the thin-layer dye sensitized solar cells. The electrochemical properties of this new mediator as a function of temperature were investigated by mean of symmetric golden electrodes thin-layer cell, using three electro-analytical techniques: electrochemical impedance spectroscopy (EIS), slow scan cyclic voltammetry (SCCV) and chronoamperometry (CA). Our study pointed out that, at room temperature, both the electron transfer rate k° = 1.24 10⁻⁴ cm s⁻¹ as well as the diffusion coefficient D = 5.85 × 10⁻⁷ cm s⁻¹ are rather low. Raising the temperature has a beneficial effect, increasing more than 6 times the standard rate constant of electron transfer and more than 3 times the ionic diffusion coefficient at 80 °C. However, for all the studied temperatures, the slow mass transport of Co^(III)/Co^(II) species still remains the rate determining step. Viscosity measurements have demonstrated that the ionic mass transport in MPN follows the Stokes’ law and the Walden product is constant, in the temperature range investigated.     

A comparison of charge transport behavior in functionalized and non-functionalized poly 3,4-(ethylenedioxythiophene) films

Poly 3,4-(ethylenedioxythiophene) (PEDOT) films electropolymerized from an aqueous micellar solution containing sodium dioctyl sulfosuccinate and the monomer were functionalized with 1-fluoro-2-nitro-4-azidobenzene (FNAB) molecules by a photochemical nitrene insertion reaction. The variation in redox activity and the changes in the charge transfer and diffusion (through bulk) behavior of the functionalized and the non-functionalized PEDOT films have been followed by electrochemical impedance spectroscopy and cyclic voltammetry. While the functionalized film allows a reversible insertion and extraction of guest cations and anions, the non-functionalized film is capable of exchanging only anions. The higher level of oxidation attained in the functionalized film is also reflected in the longer diffusion length (l_D) observed for the ions in this film. In both films the barrier to charge transfer is resistive rather than capacitive. Both charge transfer and diffusion resistance (R_CT and R_D) are lower for the functionalized film, a consequence of a higher surface roughness and a more nodular morphology and therefore higher optical contrast and faster color-bleach kinetics are achieved in this film. For the functionalized and the non-functionalized films, both R_CT and R_D are greatly enhanced during reduction than for oxidation. In particular, in the low frequency regime, the hindered diffusion-controlled extraction of anions from the bulk of the film is also evident from the larger R_D as compared to R_CT and the difference in their magnitudes is more pronounced for the functionalized film thus confirming that functionalization is a useful method for controlling the redox response of conducting polymer films.     

Effects of charge density on water splitting at cation-exchange membrane surface in the over-limiting current region

To determine the correlation between surface properties and concentration polarization (CP) behaviors, cation exchange membranes with varying fixed charge densities were prepared and characterized by using several electrochemical analyses such as chronopotentiometry, zeta potential, and current-voltage measurements. Results showed that CP behavior depended mainly on surface charge density. With higher surface charge density, stronger electroconvection was observed, suggesting that an increase in the surface charge density increased the concentration of the counter ions at the membrane surface. As such, the electric field around the membrane surface was strengthened at a current over the limiting current density. Water splitting was also proportional to the surface charge density. This result was consistent with the classical electric field-enhanced water splitting theory, indicating that water splitting increased due to increases in the electric field and prepolarization of water molecules at the membrane-solution interface of the cation-exchange membrane. This paper is dedicated to Professor Hyun-Ku Rhee on the occasion of his retirement from Seoul National University.     

Electrochemical impedance spectroscopy study of a surface confined redox reaction: The reduction of azobenzene on mercury in the absence of diffusion

The kinetics of azobenzene reduction on mercury electrodes in the absence of diffussional mass transport is studied by electrochemical impedance spectroscopy (EIS) in acetic acid/acetate buffered solutions at different pH values. Cyclic voltammetry experiments confirm the absence of diffusion effects and provide the values of the surface equilibrium potential. The analysis of the impedance frequency spectrums at every potential within the faradaic region conforms well the model and provides the global rate constant of the process, k_f. The potential dependence of k_f suggests the existence of an EE mechanism, with two electron transfers controlling the overall rate. The kinetic parameters of every step are obtained and their pH dependences clarify the role played by the protonation steps.     

Hydrocarbon absorption in tetrachloroaluminate catalysts effects of catalyst cation, hydrocarbon polarity and charge transfers via molecular modeling

Absorption levels were obtained for five hydrocarbons of increasing polarity in three tetrachloroaluminate catalysts of increasing cation size. Obtained absorption levels were found to correlate with cation size and hydrocarbon polarity. Molecular modeling was used to calculate charge transfers from absorbed hydrocarbons to the catalysts. Obtained charge transfers were also found to correlate with hydrocarbon absorption levels. Lastly, polarities calculated for absorbed free-radicals suggest a mechanism for previous findings. In the previous effort, resid conversion was found to go through a maximum with increasing hydrogen tetrachloroaluminate contents in a sodium tetrachloroaluminate catalyst.     

Impact of tailoring of the defect states and the band gap towards extreme photocatalytic performance and photo-induced conductivity in cobalt doped ZnO QD

Due to the advantages of tuning the electronic structure and reducing charge carrier recombination, metal doping into semiconductor metal oxides has been considered an efficient method for enhancing photocatalytic activity and photo-induced conductivity. In this paper, we focus on the effect of cobalt doping on the photocatalytic performance and photo-induced conductivity of ZnO QD. It was found that after Co doping, the photocatalytic activity of ZnO QD was remarkably higher than that of undoped ZnO QD when measured with methylene blue (MB) dye. The study showed that the complete degradation of the dye using 5 mol% cobalt doped ZnO QD occurred in just 6 min, which is 4 times faster than that of undoped ZnO QD. The extent of dye mineralization was supported by chemical oxygen demand (COD) study, which revealed that the dye was almost entirely mineralized. Furthermore, the photoconductivity and photosensitivity of 5 mol% doped Co doped ZnO QD were increased by 20 and 7 times, respectively, over that of undoped ZnO QD. The outstanding boost in photocatalytic activity and photoconductivity is caused by the tunable band gap mediated photo response, which increases light harvesting and thus the generation of a large number of electron hole pairs. Another possible explanation is that sub-energy levels formed between the conduction and valence bands act as a trap for electrons and holes, promoting charge separation by limiting photogenerated charge carrier recombination.     

Gold-thickness-dependent Schottky barrier height for charge transfer in metal-assisted chemical etching of silicon

Large-area, vertically aligned silicon nanowires with a uniform diameter along the height direction were fabricated by combining in situ-formed anodic aluminum oxide template and metal-assisted chemical etching. The etching rate of the Si catalyzed using a thick Au mesh is much faster than that catalyzed using a thin one, which is suggested to be induced by the charge transport process. The thick Au mesh in contact with the Si produces a low Au/Si Schottky barrier height, facilitating the injection of electronic holes from the Au to the Si, thus resulting in a high etching rate.     

Covalently tethered comb‐like polymer brushes on hydrogen‐terminated Si (100) surface via consecutive aqueous atom transfer radical polymerization of methacrylates

The hydrogen‐terminated Si (100) (Si? H surface) was functionalized by coupling with 4‐vinylbenzyl chloride (VBC) to form a Si? VBC surface, which serves as macroinitiators for the surface‐initiated aqueous atom transfer radical polymerization (ATRP) of 2‐hydroxyethyl methacrylate (HEMA) and poly(ethylene glycol)methacrylate (PEGMA) to prepare Si? VBC? g? PHEMA and Si? VBC? g? PPEGMA substrates, respectively. The ellipsometric results revealed that the surface‐initiated ATRP of both PHEMA and PPEGMA brushes proceeded in a controlled fashion. By adjusting the monomer concentration, an eccentric polymer thickness dependence on the initial monomer concentration [M]₀ was observed for both HEMA and PEGMA, i.e., in the dilute regime, the thickness of the polymer film increases with the increase in [M]₀; however, beyond critical [M]₀, the thickness deceases gradually with the further increase. Such an eccentricity was tentatively correlated to the counteractive combination of the increase in [M]₀ and decrease in the apparent polymerization rate constant. Both Si? VBC? g? PHEMA and Si? VBC? g? PPEGMA substrates were esterified for the subsequent surface‐initiated ATRP, resulting in corresponding comb‐like brushes. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 2590–2599, 2006     

Facet engineered TiO2 hollow sphere for the visible-light-mediated degradation of antibiotics via ligand-to-metal charge transfer

Efficient removal of tetracycline (TC) under visible-light irradiation over TiO₂-based photocatalysts remains a challenge based on the fact that the reported photocatalytic systems still suffer from weak visible-light absorption and/or inefficient charge separation. Herein, we constructed {101} and {001} facets co-exposed TiO₂ hollow sphere (001-HT) via a gentle NaF treatment, in which the hollow mesoporous feature can trap incident light for a long time to improve photons efficiently. Meanwhile, the as-formed facet heterojunction significantly facilitates the charge separation. As a result, the 001-HT exhibits a high removal rate (~90.1%) of TC under visible-light irradiation, beyond the values of many reported TiO₂-based photocatalysts. Most importantly, we further expound the ligand-to-metal charge transfer mechanism towards TiO₂-assisted degradation of TC under visible-light irradiation, which effectively clarifies the confusion about the origin of pure TiO₂ visible-light activity towards TC degradation because both TiO₂ and TC do not exhibit any visible-light catalytic activity. Therefore, this work provides a new insight in revealing the mechanism of visible-light-mediated TC degradation over pure TiO₂ photocatalyst.     

Grafting polymer brushes on graphene oxide for controlling surface charge states and templated synthesis of metal nanoparticles

In this article, poly[(dimethylamino)ethyl methacrylate] (PDMAEMA) brushes were grafted onto graphene oxide (GO) sheet via noncovalent modification of pyrene terminated initiator and subsequent in situ surface‐initiated atom transfer radical polymerization (SI‐ATRP). The results of zeta‐potentials, dispersivity measurement as well as the permeability of cationic and anionic redox‐active probe molecules reveal that the as‐prepared GO/PDMAEMA composite exhibits zwitterionicity because of the presence of phenol hydroxyl, carboxyl, and amine groups and the charging state can be manipulated by controlling pH values. Furthermore, by ion exchange and in situ reduction, palladium and gold nanoparticles were successfully uploaded and the catalytic property of the uniformly distributed Pd‐Au nanoparticles on GO sheet was investigated. These results reported in this work may open primarily toward constructing a bridge among GO, charged polymer and metal nanoparticles and secondarily to represent a new strategy for uniformly depositing inorganic nanoparticles. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Evaluation of red mud as surface treatment for carbon steel prior painting

Red mud (RM) is the waste product of the Bayer process for obtaining alumina from bauxite. The alkaline nature of RM suspensions together with the presence of Fe³⁺ species point towards the possibility of using RM as a good corrosion inhibitor for carbon steel. Based on this idea, the possible use of RM suspensions as pre-treatment for carbon steel was studied by recording the electrode potential and the electrochemical impedance spectroscopy (EIS) evolution with immersion time. Different parameters regarding the steel surface finishing (grinding, pickling or degreasing) and RM suspension condition (stirred or steady, decanted or filtered) have been considered in the study; the passivation was obtained when ground samples were immersed in decanted RM suspensions and subjected to continuous stirring. The influence of chlorides and pH were analysed by potentiometric titration. The obtained results indicate that treated samples depassivate at lower Cl⁻/OH⁻ ratio than untreated ones. Regarding the pH parameter, treated samples remain passive at lower pH values than the untreated ones. Finally, some treated and untreated samples were painted and subjected to cathodic polarisation experiments, including an artificial defect in the coating. The comparative study was done using EIS technique; the impedance diagrams would indicate an effective passivation of the steel surface for treated samples.     

Dielectric properties evaluation of NiFe2O4/MWCNTs nanohybrid for microwave applications prepared via novel one step synthesis

NiFe₂O₄/MWCNTs nanohybrids were synthesized via novel one step ultrasonication assisted method using ortho-xylene as a dispersive medium with varying MWCNTs concentration (0.0%, 1.0%, 1.5%, 2.0% and 2.5%). The nanohybrids were characterized by X-Ray Diffraction (XRD), Scanning Electron Microscope (SEM), Fourier Transform Infrared Spectroscopy (FT-IR) and Impedance Analyzer techniques. XRD indexed patterns confirmed the formation of NiFe₂O₄/MWCNTs nanohybrid. The SEM images showed the decoration of nickel ferrite nanoparticles on MWCNTs. The FTIR results show two absorption bands. The Cole-Cole plots of impedance show the resistance was only due to the grain boundary contribution. The dielectric properties were found to be increasing with increasing MWCNTs concentration. For 2.5% MWCNTs concentration, dielectric constant and loss 1.06×10⁵, 1.99×10⁶ were achieved as compared to pure nickel ferrite 6.17×10³, 3.87×10⁴, respectively. Such increase in the dielectric properties renders its application at high frequency     

Enhanced cyclability and surface characteristics of lithium batteries by Li-Mg co-deposition and addition of HF acid in electrolyte

The effect of Mg(ClO₄)₂ and HF acid in 1 M LiPF₆/EC + DEC + DME electrolyte on the cycle behaviors and the surface characteristics of the lithium electrode were investigated. The morphology of the electrode is greatly improved using Li-Mg co-deposition and HF acid, and results in the enhancement of the cyclability observed by electrochemical measurement. The scanning electron microscopy images of the electrode surface show densely deposited lithium-magnesium alloy particles with a hemispherical shape on the entire surface of the electrode. The improved coulombic efficiency was attributed to the synergistic effect due to the formation of Li-Mg alloy and LiF caused by Li-Mg co-deposition and HF to the electrolyte, respectively.