Electrochemical characteristics of poly(ophenylendiamine) film electrodes in phosphatic solution

The electrochemical characteristics of poly(o-phenylendiamine) (POPD) film modified electrodes have been investigated using different electrochemical techniques.The main interest is focused on the effect of potential and film thickness on the electrode process.Good agreement has been found for the apparent diffusion coefficient estimated by chronocoulometry and impedance spec-troscopy.The charge transfer process within POPD films is diffusion processes at negative and positive overpotentials and electron hopping mechanism at formal potential.The POPD film conductivity of the oxidized state is better than that of the reduced state.For all electrode processes,the H+ may penetrate the film/electrolyte interface and take part in charge transfer or protonation-deprotonation of phenazine rings.     

Dependence of the photoelectrochemical performance of sensitised ZnO on the crystalline orientation in electrodeposited ZnO thin films

The influence of the crystal orientation in porous crystalline films of ZnO electrodeposited on the photoelectrochemical characteristics of the films is studied. For differently oriented ZnO thin films following removal of the respective structure-directing agent (SDA) and adsorption of a sensitiser, time-resolved photocurrent measurements, intensity modulated photocurrent spectroscopy (IMPS), intensity modulated photovoltage spectroscopy (IMVS) and current-voltage curves were measured in acetonitrile-based electrolytes containing I(3)(-)/I(-) as the redox electrolyte. The crystal orientation has a significant influence on the charge transport across such films and hence is reflected in the observed electrode kinetics. Films originally grown in the presence of, e.g., Coumarin 343 as a SDA, showed a significantly faster response to illumination. Increased electron diffusion coefficients and diffusion lengths were calculated from the results of IMPS and IMVS, caused by a faster electron movement in the films. Implications of these findings on further improvements of sensitised ZnO films prepared by electrochemical deposition are discussed.     

Potential-dependent recombination kinetics of photogenerated electrons in n- and p-type GaN photoelectrodes studied by time-resolved IR absorption spectroscopy

Recombination kinetics of photogenerated electrons in n-type and p-type GaN photoelectrodes active for H(2) and O(2) evolution, respectively, from water was examined by time-resolved IR absorption (TR-IR) spectroscopy. Illumination of a GaN film with UV pulse (355 nm and 6 ns in duration) gives transient interference spectra in both transmittance and reflection modes. Simulation shows that the interference spectra are caused by photogenerated electrons. We observed that recombination in the microsecond region is greatly affected by the applied potentials, the lifetime becoming longer at negative and positive potentials for n- and p-type GaN electrodes, respectively. There is a good correlation between potential dependence of the steady-state reaction efficiency and that of the number of surviving electrons in the millisecond region. We also performed potential jump measurement to examine the shift in Fermi level by photogenerated charge carriers. In the case of n-type GaN, the electrode potential jumps to the negative side by accumulation of electrons in the bulk. However, in the case of p-type GaN, the electrode potential first jumps to the negative side within 20 μs and gradually shifts to the positive side in a few milliseconds, while the number of charge carriers is constant at >0.2 ms. This two-step process is ascribed to electron transport from the bulk to the surface of GaN, because the electrode potential is sensitive to the number of electrons in the bulk. The results confirm that TR-IR combined with potential jump measurement provides useful information for understanding the behavior of charge carriers in photoelectrochemical systems.     

锆表面氧化膜的光电化学研究

用光电化学方法研究了金属锆的表面初始氧化膜和线性电势扫描形成阳极氧化膜．光电流作用谱上的阳极和阴极光电流取决于电极电势,而与成膜和测量溶液基本无关．光电流作用谱和瞬态光电流响应说明锆表面氧化膜为双层结构,内层为ＺｒＯ＿２外层为ＺｒＯ＿２·（Ｈ＿２Ｏ）＿ｎ．光电流可以来自内、外层的光生载流子和基底金属的内光注入电子迁移至电极／溶液界面与溶液中的氧化还原对反应,光电流作用谱的分析给出了三个过程的光学间能值,分别为４．５ｅＶ、３．０ｅＶ和２．０ｅＶ．     

Self-propagating fabrication of 3D porous MXene-rGO film electrode for high-performance supercapacitors

2D MXene nanosheets with metallic conductivity and high pseudo-capacitance are promising electrode materials for supercapacitors.Especially,MXene films can be directly used as electrodes for flexible supercapacitors.However,they suffer from sluggish ion transport due to self-restacking,causing limited electrochemical performance.Herein,a flexible 3D porous MXene film is fabricated by incorporating graphene oxide(GO) into MXene film followed by self-propagating reduction.The self-propagating process is facile and effective,which can be accomplished in 1.25 s and result in 3D porous framework by releasing substantial gas instantaneously.As the 3D porous structure provides massive ion-accessible active sites and promotes fast ion transport,the MXene-rGO films exhibit superior capacitance and rate performance.With the rGO content of 20%,the MXene-rGO-20 film delivers a high capacitance of 329.9 F g^-1 at 5 mV s^-1 in 3 M H2 SO4 electrolyte and remains 260.1 F g^-1 at 1,000 mV s^-1 as well as good flexibility.Furthermore,the initial capacitance is retained above 90% after 40,000 cycles at 100 A g^-1,revealing good cycle stability.This work not only provides a high-performance flexible electrode for supercapacitors,but also proposes an efficient and time-saving strategy for constructing 3D structure from 2D materials.     

Electrochemical behavior of poly(ferrocenyldimethylsilane-b-dimethylsiloxane) films

The electrochemical behavior of poly(ferrocenyldimethylsilane-b-dimethylsiloxane) (PFDMS-b-PDMS) films deposited on a glassy carbon electrode was investigated by means of cyclic voltammetry (CV). The influences of the solvent, film thickness, temperature, and PDMS block length in PFDMS-b-PDMS on the electrode process were discussed. It was found that in 0.1 M aqueous LiClO(4) the electrochemical processes of the films on a glassy carbon electrode were complex and have a low rate of electron transport and mass diffusion. The kinetic parameters obtained indicated that the electrode process was controlled by both the electrode reaction and mass diffusion.     

Fast electron transport in metal organic vapor deposition grown dye-sensitized ZnO nanorod solar cells

The electron transport in dye-sensitized solar cells with a MOCVD (metal organic vapor deposition)-grown ZnO nanorod array (ZnO-N) or a mesoporous film prepared from ZnO colloids (ZnO-C) as the working electrode was compared. The electrodes were of similar thickness (2 mum) and sensitized with zinc(II) meso-tetrakis(3-carboxyphenyl)porphyrin, while the electrolyte was I(-)/I(3)(-) in 3-methoxypropionitrile. Electron transport in the ZnO-C cells was comparable with that found for colloidal TiO(2) films (transport time approximately 10 ms) and was light intensity dependent. Electron transport in solar cells with ZnO-N electrodes was about 2 orders of magnitude faster ( approximately 30 mus). Thus, the morphology of the working ZnO electrode plays a key role for the electron transport properties.     

Textile electrodes as substrates for the electrodeposition of porous ZnO

Metal-coated polyamide threads and filaments were chosen as substrate electrodes to deposit highly porous ZnO films for photovoltaic application. The films were electrodeposited at 70 degrees C from oxygen-saturated aqueous zinc salt solutions containing EosinY as a structure directing agent. The current density during deposition was increased compared with planar electrodes by enhanced diffusion at the filaments operating as cylindrical microelectrodes. Analysis by scanning electron microscopy showed an influence of geometrical constraints within the textiles and the hydrodynamic flow rate in the deposition solution on the film morphology. Photoelectrochemical characterization of sensitized films revealed the feasibility of the presented approach and indicated further steps needed for electrode optimization.     

Mechanistic study of the electrodeposition of nanoporous self-assembled ZnO/Eosin Y hybrid thin films: effect of eosin concentration

ZnO films prepared by one-step electrodeposition in the presence of dissolved eosin molecules present an internal nanoporous hybrid structure resulting from self-assembling processes occurring in solution between ZnO and eosin components. This study aims to better understand the underlying growth mechanism, which is still unexplained. The films were deposited by cathodic electrodeposition from an oxygen-saturated aqueous zinc chloride solution. The effects of the addition of 10 to 100 micromol.L(-1) eosin Y, as a sodium salt, on the growth rate and film properties, were systematically studied while all other parameters remained constant (concentrations of zinc salt and supporting electrolyte, applied potential of -1.4 V versus the mercurous sulfate electrode (MSE), temperature of 70 degrees C, rotating disk electrode at 300 rotations per min, and a glass-coated tin oxide electrode). It is shown that the addition of eosin provokes the formation of a nanoporous "cauliflower" structure whose nodule size and composition depend on the eosin concentration in the bath. The growth rate of the hybrid films increases markedly with the eosin concentration. The ZnO and eosin contents of the films are determined for each concentration by chemical analysis. Comparing with thickness determinations, it is shown that the total porosity increases up to 60-65% in volume fraction toward an eosin concentration of 100 micromol.L(-1). The empty pore volume fraction increases up to about 30% at an eosin concentration of about 20 micromol.L(-1) and then decreases. These correlations have been precisely established for the first time. It is shown that the global composition is fixed by the relative rate of deposition for zinc oxide, which is constant, and for the relative rate of eosin inclusion, which is proportional to the concentration in solution. This is explained on the basis of different steps in the growth mechanism, in particular, a diffusion effect limitation for both oxygen and eosin. This variation explains part of the increase in the growth rate. Another contribution is related by the structural effect on the nanoscale leading to the formation of the interpenetrated porous network. Competition between empty and eosin-filled parts of the pore network is evidenced. The formation of the porous network structure could be governed by a diffusion-limited aggregation mechanism. The system may represent a reference case of competing reactions in the electrochemical self-assembly of hybrid nanostructures.     

TiO2/ZnO薄膜电极中光生电子的传输及其在太阳电池中的应用

制备了TiO2纳米颗粒和ZnO纳米棒混合的多孔薄膜电极, 利用瞬态光电压技术研究了染料敏化TiO2/ZnO薄膜中光生载流子的传输特性. 实验结果表明, ZnO纳米棒增加了薄膜中自由电子扩散速率, 减小了复合几率, 改善了能量转换效率.     

纳米ZnO薄膜的制备及其可见光催化降解甲基橙

采用溶胶-凝胶方法制备ZnO透明溶胶, 在铝箔上涂膜后经500 ℃处理制得具有可见光响应的纳米ZnO薄膜光催化剂. 以甲基橙模拟有机污染物, 在可见光下研究了薄膜的降解性能, 结果表明, 用一片有效面积为200 cm2的ZnO/Al薄膜作为催化剂, 甲基橙的降解率达到96.3％, 比ZnO负载在玻璃上制得的ZnO/glass薄膜催化剂活性高得多. 采用扫描电镜与原子力显微镜对ZnO/Al薄膜制备条件进行了表征, 结果发现多孔ZnO/Al薄膜比致密ZnO/Al薄膜具有更高的活性, 实验制备的具有高活性的ZnO/Al薄膜颗粒平均直径为52.2 nm. 采用本方法制备的ZnO/Al薄膜是一种具有应用前景的, 能在可见光下降解有机物的有效光催化剂.     

Long-Range Transport in an Assembly of ZnO Quantum Dots: The Effects of Quantum Confinement,Coulomb Repulsion and Structural Disorder

We have studied the storage and long-range transport of electrons in a porous assembly of weakly coupled ZnO quantum dots permeated with an aqueous and a propylene carbonate electrolyte solution. The number of electrons per ZnO quantum dot is controlled by the electrochemical potential of the assembly; the charge of the electrons is compensated by ions present in the pores. We show with optical and electrical measurements that the injected electrons occupy the S, P, and D type conduction electron levels of the quantum dots; electron storage in surface states is not important. With this method of three-dimensional charge compensation, up to ten electrons per quantum-dot can be stored if the assembly is permeated with an aqueous electrolyte. The screening of the electron charge is less effective in the case of an assembly permeated with a propylene carbonate electrolyte solution. Long-range electron transport is studied with a transistor set-up. In the case of ZnO assemblies permeated with an aqueous electrolyte, two quantum regimes are observed corresponding to multiple tunnelling between the S orbitals (at a low occupation) and P orbitals (at a higher occupation). In a ZnO quantum-dot assembly permeated with a propylene carbonate electrolyte solution, there is a strong overlap between these two regimes.     

Hydrophobic silica sol-gel films for biphasic electrodes and porotrodes

Hydrophobic sol-gel films from methyltrimethoxysilane (MTMOS) are deposited onto glass and tin-doped indium oxide (ITO) coated glass substrates. Uniform and microporous films of ca. 200 nm thickness are obtained and investigated by scanning electron microscopy and by electrochemical techniques. From cyclic voltammograms for the oxidation of ferrocenedimethanol in aqueous 0.1 M KNO3 apparent diffusion coefficients and free volume data for processes within the film are derived and it is demonstrated that the film morphology can be controlled by the deposition timing. Two novel types of biphasic electrodes for observing liquid/liquid ion transfer reactions are introduced: (i) an ITO electrode coated with a hydrophobic sol-gel film and (ii) a hydrophobic sol-gel film on glass sputter-coated with 20 nm porous gold (porotrode). For the t-butylferrocene redox system deposited in the form of an organic liquid, very low and morphology dependent current responses are observed on modified ITO electrodes. However, the porotrode system allows biphasic electrode reactions to be driven with high efficiency and with no significant morphology effect of the hydrophobic sol-gel film. This type of nanofilm-modified electrode system will be of interest for biphasic sensor developments.     

利用强度调制光电流/光电压谱研究碳点/KOH电解液界面的动力学行为

通过强度调制光电流谱(IMPS)和强度调制光电压谱(IMVS)技术研究在光电分解水制氢体系中碳点光阳极与KOH电解液界面的动力学行为。结果表明,光强在30–90 m W·cm~(-2)范围内,界面的电子传输时间(τ_d)、电子寿命(τ_n)、电子扩散系数(D_n)、电子扩散长度(L_n)均没有变化;当光强增加到110和130 m W·cm~(-2)时,τ_d和τ_n延长,而D_n减小。实验表明,不同于Ti O_2/电解液等界面,碳点光电极/电解液界面中碳点电极存在的缺陷少,因此电子主要以无陷阱限制扩散方式传输为主。且在30–130 m W·cm~(-2)的光强范围内,与τ_d和τ_n相关的载流子收集效率(η_(cc))相近。     

TiO2 photoanodes prepared by cathodic electrophoretic deposition in 2-propanol: effect of the electric field and deposition time

This paper evaluates the influence of electric field and deposition time applied on cathodic electrophoretic formation of TiO₂ films in organic medium (2-propanol). The film morphology was tracked by measuring the deposited mass and film thickness. The variation in film porosity was correlated with the apparition of surface states distribution in the cyclic voltammetric characterization in the dark, due to grain boundaries defects generated in the contact of the TiO₂ particles. The open-circuit voltage decay curves showed that there is no formation of deep energy states inside the band gap of the TiO₂. The photopotential of the films increased until a critical thickness but the photocurrents showed to be dependent on operational variables, due to the fact that anodic polarization in thin films increases the electric field generated by the illumination at the ITO/TiO₂ interface, favoring the transport of the photogenerated electrons to the rear contact.     

Electroactive planar waveguide studies of Ru(bpy)3(2+) intercalated in a thin clay film: I. Transport and electrochemical phenomena

Electroactive planar waveguide (EAPW) instrumentation was used to perform potential modulated absorbance (PMA) experiments at indium tin oxide (ITO) electrodes coated with 0-, 300-, 800-, and 1200-nm-thick SWy-1 montmorillonite clay. PMA experiments performed at low potential modulation monitor mass transport events within 100 nm of the ITO surface and, thus, when used in conjunction with cyclic voltammetry (CV), can elucidate charge transport mechanisms. The data show that at very thin films electron transfer is controlled by electron hopping (sensitive to the anion species in the electrolyte) in an adsorbed Ru(bpy)(3)(2+) layer. As the thickness of the clay film grows, electron transfer may become controlled by mass transfer of Ru(bpy)(3)(2+) within the clay film to and from the electrode surface, a mechanism that is affected by the swelling of the film. Film swelling is controlled by the cation of the electrolyte. Films loaded with Ru(bpy)(3)(2+) while being subjected to evanescent wave stimulation demonstrate a large hydrophobic layer. The growth of the hydrophobic layer is attributed to the formation of Ru(bpy)(3)(2+*), which has negative charge located at the periphery of the molecule enhancing clay/complex repulsion. The results suggest that the structure of the film and the mechanism of charge transport can be rationally controlled. Simultaneous measurements of the ingress of Ru(bpy)(3)(2+) into the clay film by CV and PMA provide a means to determine the diffusion coefficient of the complex.     

The effect of hydrothermal growth temperature on preparation and photoelectrochemical performance of ZnO nanorod array films

Highly oriented ZnO nanorod arrays with controlled diameter and length, narrow size distribution and high orientation consistency have been successfully prepared on ITO substrates at different growth temperatures by using a simple hydrothermal method. XRD results indicate that the nanorods are high-quality single crystals growing along [001] direction with a high consistent orientation perpendicular to the substrate. SEM images show that the nanorods have average diameters of about 30-70 nm by changing growth temperature. The thin films consisting of ZnO nanorods with controlled orientation onto ITO substrates allow a more efficient transport and collection of photogenerated electrons through a designed path. For a sandwich-type cell, the relatively high overall solar energy conversion efficiency reaches about 2.4% when the growth temperature is at 95 °C.     

Photoinduced charge transfer in ZnO/Cu(2)O heterostructure films studied by surface photovoltage technique

ZnO/Cu(2)O heterostructure films were prepared by a two-step electrodeposition method in aqueous solution on fluorine-doped tin oxide (FTO) substrates. Scanning electron microscopy (SEM), X-ray powder diffraction (XRD) and UV-vis transmission measurements were utilized to characterize the films. Surface photovoltage (SPV) technique was used to investigate the process of photoinduced charge transfer. The results show that there is an electric field located at the interface between ZnO and Cu(2)O film and the photoinduced electrons in Cu(2)O film inject into ZnO under the effect of interfacial electric field with visible light irradiation. While under ultraviolet light illumination, the photoinduced electrons in Cu(2)O film accumulate at the surface of Cu(2)O film instead of injecting into ZnO under the action of surface built-in electric field of Cu(2)O film. The work function measurements confirm that the direction of interfacial electric field is from ZnO to Cu(2)O. These results are help to future design of high performance heterostructure photovoltaic devices.     

Experimental evidence of a UV light-induced long-range electric field in nanostructured TiO2 thin films in contact with aqueous electrolytes

Nanostructured TiO(2) thin-film electrodes of controlled thickness were obtained by immobilization of TiO(2) powder (Degussa P25) on SnO(2):F (FTO)-coated glasses by electrophoresis. The photocurrent-potential characteristics of the electrodes in contact with an indifferent aqueous electrolyte, for both front--and backside UV illumination, show the existence of a macroscopic electric field in the electrode region near the FTO substrate. This electric field, which is only photoinduced in the presence of water (it does not appear in TiO(2) dye-sensitized solar cells under visible illumination), apparently disappears when an efficient hole scavenger, like methanol, is added to the aqueous electrolyte. It is attributed to a nonhomogeneous spatial accumulation of photogenerated holes at surface-bound OH radicals resulting from the photooxidation of chemisorbed water molecules. The influence of film thickness and UV illumination mode (front- and backside) on the photoinduced electric field is analyzed by solving the transport equations for diffusion and drift of electrons.     

碳点修饰多孔ZnO纳米棒增强光催化性能

Porous ZnO nanorods that displayed excellent photocatalytic degradation of organic pollutants (RhB and phenol) were prepared via a solvent thermal method followed by surface modification with carbon dots (C-dots) using a deposition method. The photocatalysts were characterized using X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), and ultraviolet-visible (UV-Vis) spectroscopy. The degradation of the organic pollutants using the nanorods was tested under Xe-light illumination and was enhanced following C-dot modification. Nanorods that were modified by the C-dots at a mass fraction of 1.2% (CZn1.2) exhibited the highest photocatalytic activity for the degradation of RhB, which was 2.5 times of the pure porous ZnO nanorods. Additionally, the modified nanorods with strangely oxidation ability could catalyze the degradation of phenol by open-rings reaction under Xe-light illumination. The improved photocatalytic activity was attributed to the effective separation of the photogenerated electrons and holes, in which the C-dots served as the receptor of the photogenerated electrons.