Lack of nano size effect on electrochemistry of dopamine at a gold nanoparticle modified indium tin oxide electrode

Nanometer sized materials have been shown to possess excellent chemical and electrochemical catalytic properties. In this work, a gold nanoparticle (AuNP) modified indium tin oxide (ITO) electrode was employed for investigating its electro-catalytic property. AuNP was deposited on the 3-aminopropyltriethoxysilane (APTES) modified ITO electrode by self-assembly, and was characterized by scanning electron microscopy and cyclic voltammetry. Although the electrochemical reaction of dopamine was very sluggish on the ITO/APTES electrode, it was significantly enhanced after AuNP deposition. The cyclic voltammogram exhibited apparent dependence on the surface coverage of 11 nm AuNPs, which could be rationalized by different modes of mass diffusion. Among the different sizes of AuNP investigated, the lowest anodic peak potential was observed on 11 nm AuNP. However, the potential was still about 50 mV more positive than that obtained on a bulk gold electrode of similar geometry. It is therefore concluded that there is no nanometer size effect of AuNP modified ITO on the electrochemistry of dopamine.     

ITO在NaOH溶液中阳极与阴极极化过程的电化学行为

通过循环伏安法等方法研究了氧化铟锡(ITO)透明导电薄膜的电化学行为. 获得了ITO薄膜在NaOH溶液中阴极和阳极极化处理前后的循环伏安曲线. 采用透射光谱, 方块电阻测试, 扫描电子显微镜(SEM), 能量色散X射线荧光光谱(EDS)与X射线衍射(XRD)表征ITO薄膜经电化学处理后的反应产物. 结果表明, ITO薄膜在阳极处理后(约为+1.5 V(vs SCE))保持了稳定的成分和结构. 但经阴极处理后(约为-1.5 V(vs SCE))发生了严重的电化学腐蚀, 可见光透射率大幅下降, 方块电阻增加一个数量级. 经SEM、EDS和XRD表征分析, 证明阴极处理过程使ITO薄膜中的In3+还原成了In单质.     

Photoelectrochemical sensing for hydroquinone based on gold nanoparticle-modified indium tin oxide glass electrode

Gold nanoparticles (GNPs) were deposited directly onto the surface of indium tin oxide (ITO) thin film-coated glass by electrochemical method. It was used as a photoanode in a photoelectrochemical (PEC) cell for sensitive detection of hydroquinone (HQ) at an applied bias potential of 0.15 V vs. saturated calomel electrode. This heterostructure showed dramatically enhanced PEC properties due to the introduction of the Au/ITO interface. Under the irradiation, the marked photocurrent response was observed at the GNPs/ITO photoelectrode compared with bare ITO electrode. The anodic photocurrent could be further largely enhanced by HQ. A new PEC strategy for sensitive detection of HQ at a relative low potential was developed. The linear range for HQ determination was 0.25 to 150 μM, with a detection limit of 0.1 μM. The sensitivity on the GNPs/ITO electrode at the irradiation was ~ 3.3 times higher than that in dark. These results demonstrate that the simple GNPs/ITO electrodes have great potential for PEC analysis application.     

电泳沉积制备ZnO-C60和ZnO-MWCNT合涂层电极及其光电性质

在氧化铟锡( ITO)导电玻璃表面电泳沉积制备ZnO-C60和ZnO-MWCNT复合涂层电极,经后续热处理增强其结合强度,通过SEM观察2种电极复合涂层的表面形貌,并使用CHI 705电化学分析仪和PMI-E电致化学发光系统测定其光电性质.结果表明,ZnO-C60复合涂层电极具有较高的稳定性,在可见光辐照下,该电极显示...     

Surface Modifications and Optoelectronic Characterization of TiO2‐Nanoparticles: Design of New Photo‐Electronic Materials

TiO₂ nanoparticles are of great current interest for applications in photo‐electronic materials including light‐energy conversion, artificial photosynthetic systems as well as photocatalysis. The success of these applications relies on the exciton recombination dynamics and visible‐light sensitivity of the TiO₂ nanomaterials. Thus, in order to develop the highly efficient photo‐electronic materials absorbing visible light, different low dimensional TiO₂ nanostructures such as nanodiscs, nanofibers and nanochains were synthesized, and thereafter their surfaces were modified by incorporating with Sn‐porphyrins and heteropoly acid. The optoelectronic properties of the surface‐modified nanomaterials were investigated with regard to the optical properties and the surface exciton dynamics by using both steady‐state and ultrafast time‐resolved laser spectroscopic techniques including single nanoparticle photoluminescence technique. These results were correlated with the photo‐electronic properties including photocatalytic activities and solar cell efficiencies, indicating that the electron transfer mechanism in the modified nanostructures may be similar to the “Z‐scheme” of the plant photosynthetic system so that both photocatalytic activity and solar cell efficiencies were synergistically enhanced by using two color illumination.     

Electrochemical Performance of Free-Standing and Flexible Graphene and TiO2 Composites with Different Conductive Polymers as Electrodes for Supercapacitors

The advantage of using composite electrode materials for energy storage is, to a large extent, the synergistic role of their components. Our work focuses on the investigation of the interactions of each phase, exploring the patterns found with the change of materials to provide theoretical or experimental foundations for future study. Here, conductive polymers (CPs), including polyaniline (PANi), polypyrrole (PPy), and polythiophene (PTh), as well as reduced graphene oxide (rGO), and TiO₂ with the different crystalline phases of anatase and rutile were applied to form a series of free-standing and flexible binary or ternary composite electrodes. The electrochemical behaviors of these composite electrodes are presented. The results indicate that the synergistic improvement in electrochemical performance is due to the incorporation of the different components. CPs significantly increase the current density of these composite films and contribute their pseudocapacitance to improve the specific capacitance, but lead to a decline in cycle stability. After introducing TiO₂, both the specific capacitance and the cycle-stability of rGO-TiO₂-CP were synergistically improved. A CP can magnify the pseudocapacitance behavior of any of the TiO₂ crystalline phases, and interactions vary with the specific CP and the specific TiO₂ crystalline phase employed. The synergistic effects of the as-prepared composites were theoretically predicted and explored.     

Co对NiOxHy薄膜电致变色性能的影响

本文利用阴极化电沉积法在抛光镍极及ＩＴＯ玻璃表面制备了含Ｃｏ量为１６．２％的ＮｉＯｘＨｙ薄膜,薄膜厚度分别为４２ｎｍ、２１ｎｍ,采用透射光谱以及线性电位扫描、交流阻抗和阳极稳态极化曲线等测试技术,考察了Ｃｏ对ＮｉＯｘＨｙ薄膜电致变色性能的影响,光谱测试范围为３００￣２５００ｎｍ。结果发现：Ｃｏ能降低薄膜着色态在可见光区及部分近红外区的透过率,通过电压调节不仅可以调光而且可望能够控温;同时Ｃｏ还能降     

ZnO/TiO2复合涂层电极的制备及其光电性能

以氧化铟锡导电玻璃为基材,采用电泳沉积法制备负载型ZnO/TiO2复合涂层,经450℃后续烧结处理后,采用XRD、SEM、EDX和UV-Vis DRS对ZnO/TiO2复合涂层进行表征;在pH=7.00的磷酸盐缓冲溶液中,分别测试ZnO/TiO2复合涂层电极在紫外灯和100 W白炽灯辐照下的电化学阻抗谱、Tafel极化曲线和循环伏安等电化学性质。结果表明:ZnO以200~300 nm晶粒分散于复合涂层中,质量百分比为0.74%;ZnO/TiO2复合涂层在可见光区有一定的吸收;在可见光辐照下ZnO/TiO2复合涂层电极具有较好的光电活性,并对水的分解具有较强的光电催化活性。     

Cr(Ⅵ)-氯代苯酚共存污染体系中的光反应与光催化反应研究

Cr(Ⅵ)-4CP(4-氯苯酚)共存污染体系中Cr(Ⅵ)离子的紫外光致还原主要是由于Cr(Ⅵ)与4CP光解产物之间的氧化还原反应而引起的。Cr(Ⅵ)离子还原受光强和体系酸度影响较大,还原速率呈零级反应。随体系pH值增大,Cr(Ⅵ)离子还原速率下降。中性条件下,光反应结束后有沉淀产物生成,这对于采用光化学方法消除环境污染提供了很有意义的结果。4CP存在对Cr(Ⅵ)离子在TiO₂表面的暗态吸附没有影响。Cr(Ⅵ)-4CP-TiO₂体系中Cr(Ⅵ)离子的紫外光致还原主要包括了两种反应:Cr(Ⅵ)与4CP之间的均相反应以及Cr(Ⅵ)离子在TiO₂表面的光催化还原反应。一定波长紫外光下,排除Cr(Ⅵ)-4CP-TiO₂体系中的均相反应,使得4CP对Cr(Ⅵ)离子光催化还原反应的促进作用得以证实。     

MnO2/TiN heterogeneous nanostructure design for electrochemical energy storage

MnO(2)/TiN nanotubes are fabricated using facile deposition techniques to maximize the surface area of the electroactive material for use in electrochemical capacitors. Atomic layer deposition is used to deposit conformal nanotubes within an anodic aluminium oxide template. After template removal, the inner and outer surfaces of the TiN nanotubes are exposed for electrochemical deposition of manganese oxide. Electron microscopy shows that the MnO(2) is deposited on both the inside and outside of TiN nanotubes, forming the MnO(2)/TiN nanotubes. Cyclic voltammetry and galvanostatic charge-discharge curves are used to characterize the electrochemical properties of the MnO(2)/TiN nanotubes. Due to the close proximity of MnO(2) with the highly conductive TiN as well as the overall high surface area, the nanotubes show very high specific capacitance (662 F g(-1) reported at 45 A g(-1)) as a supercapacitor electrode material. The highly conductive and mechanically stable TiN greatly enhances the flow of electrons to the MnO(2) material, while the high aspect ratio nanostructure of TiN creates a large surface area for short diffusion paths for cations thus improving high power. Combining the favourable structural, electrical and energy properties of MnO(2) and TiN into one system allows for a promising electrode material for supercapacitors.     

Detection of aniline at boron-doped diamond electrodes with cathodic stripping voltammetry

Boron-doped diamond (BDD) electrodes were used to investigate the possibility of detecting aniline by linear-sweep cathodic stripping voltammetry. It was found that the dimeric species (p-aminodiphenylamine and benzidine) formed by anodic oxidation of aniline during the accumulation period are involved in electrochemically reversible redox processes and, in acidic media, the shape of the stripping voltammetric response is suitable for aniline detection in the micromolar concentration range. The low background current of conductive diamond is an advantage compared to other electrode materials and allows a detection limit of 1 μM. Weak adsorption properties and the extreme electrochemical stability are additional advantages of BDD and it was found that, even after long-time measurements, the electrode surface can regain its initial activity by an anodic polarization in the potential region of water decomposition.     

Water‐Splitting Catalysis and Solar Fuel Devices: Artificial Leaves on the Move

The development of new energy materials that can be utilized to make renewable and clean fuels from abundant and easily accessible resources is among the most challenging and demanding tasks in science today. Solar‐powered catalytic water‐splitting processes can be exploited as a source of electrons and protons to make clean renewable fuels, such as hydrogen, and in the sequestration of CO₂ and its conversion into low‐carbon energy carriers. Recently, there have been tremendous efforts to build up a stand‐alone solar‐to‐fuel conversion device, the “artificial leaf”, using light and water as raw materials. An overview of the recent progress in electrochemical and photo‐electrocatalytic water splitting devices is presented, using both molecular water oxidation complexes (WOCs) and nano‐structured assemblies to develop an artificial photosynthetic system.     

Reduction of 2,3,5-triphenyl-2H-tetrazolium chloride in the presence of polyelectrolytes containing 4-styrenesulfonate moieties

The redox behavior of 2,3,5-triphenyl-2H-tetrazolium chloride (TTC) in the presence of different polyelectrolytes such as poly(sodium 4-styrenesulfonate) (PSS), poly(sodium 4-styrenesulfonate-co-sodium maleate) at two different comonomer compositions (P(SS(1)-co-MA(1)) and P(SS(3)-co-MA(1))), poly(sodium acrylate-co-sodium maleate) (P(AA(1)-co-MA(1))), and poly(sodium acrylate) (PAA) is studied. Due to aromatic-aromatic interactions, the polyelectrolytes containing benzene sulfonate groups produce a decrease on the reduction rate of TTC in the presence of ascorbic acid (ASC) and a shift of the anodic and cathodic peaks to higher negative potentials for the electrochemical reaction of TTC. As an important conclusion, these effects are a function of the linear aromatic density of the polyelectrolytes.     

基底材料对脉冲电流法制备的聚苯胺膜性能的影响

本文采用脉冲电流法(PGM)在不同的基底材料表面沉积PANI, 通过平均电位\|时间曲线及扫描电子显微镜(SEM)等方法研究了基底材料对PGM法制备PANI的影响; 并采用循环伏安(CV)和电化学阻抗谱(EIS)研究了不同电极材料表面PANI的电化学性能.     

Enhanced electrochemical activity of redox-labels in multi-layered protein films on indium tin oxide nanoparticle-based electrode

Facile electrical communication between redox-active labeling molecules and electrode is essential in the electrochemical detection of bio-affinity reactions. In this report, nanometer-sized indium tin oxide (ITO) particles were employed in the fabrication of porous thick film electrodes to enhance the otherwise impeded electrochemical activity of redox labels in multi-layered protein films, and to enable quantitative detection of avidin/biotin binding interaction. To carry out the affinity reaction, avidin immobilized on an ITO electrode was reacted with mouse IgG labeled with both biotin and ruthenium Tris-(2,2′-bipyridine) (Ru-bipy). The binding reaction between avidin and biotin was detected by the catalytic voltammetry of Ru-bipy in an oxalate-containing electrolyte. On sputtered ITO thin film electrode, although a single layer of Ru-bipy labeled avidin exhibited substantial anodic current, attaching the label to the outer IgG layer of the avidin/biotin-IgG binding pair resulted in almost complete loss of the signal. However, electrochemical current was recovered on ITO film electrodes prepared from nanometer-sized particles. The surface of the nanoparticle structured electrode was found by scanning electron microscopy to be very porous, and had twice as much surface binding capacity for avidin as the sputtered electrode. The results were rationalized by the assumption of different packing density of avidin inner layer on the two surfaces, and consequently different electron transfer distance between the electrode and Ru-bipy on the IgG outer layer. A linear relationship between electrochemical current and IgG concentration was obtained in the range of 40-4000 nmol L⁻¹ on the nanoparticle-based electrode. The approach can be employed in the electrochemical detection of immunoassays using non-enzymatic redox labels.     

Efficient charge injection from the S2 photoexcited state of special-pair mimic porphyrin assemblies anchored on a titanium-modified ITO anode

A novel surface fabrication methodology has been accomplished, aimed at efficient anodic photocurrent generation by a photoexcited porphyrin on an ITO (indium-tin oxide) electrode. The ITO electrode was submitted to a surface sol-gel process with titanium n-butoxide in order to deposit a titanium monolayer. Subsequently, porphyrins were assembled as monolayers on the titanium-treated ITO surface via phosphonate, isophthalate, and thiolate groups. Slipped-cofacial porphyrin dimers, the so-called artificial special pair at the photoreaction center, were organized through imidazolyl-to-zinc complementary coordination of imidazolylporphyrinatozinc(II) units, which were covalently immobilized by ring-closing olefin metathesis of allyl side chains. The modified surfaces were analyzed by means of X-ray photoelectron spectroscopy. Photoirradiation of the porphyrin dimer generated a large anodic photocurrent in aqueous electrolyte solution containing hydroquinone as an electron sacrificer, due to the small reorganization energy of the dimer. The use of different linker groups led to significant differences in the efficiencies of anodic photocurrent generation. The apparent flat-band potentials evaluated from the photocurrent properties at various pH values and under biased conditions imply that the band structure of the ITO electrode is modified by the anchoring species. The quantum yield for the anodic photocurrent generation by photoexcitation at the Soret band is increased to 15 %, a surprisingly high value without a redox cascade structure on the ITO electrode surface, while excitation at the Q band is not so significant. Extensive exploration of the photocurrent properties has revealed that hot injection of the photoexcited electron from the S2 level into the conduction band of the ITO electrode takes place before internal conversion to the S1* state, through the strong electronic communication of the phosphonyl anchor with the sol-gel-modified ITO surface.     

Photoresponsive Molecular Memory Films Composed of Sequentially Assembled Heterolayers Containing Ruthenium Complexes

Photoresponsive molecular memory films were fabricated by a layer‐by‐layer (LbL) assembling of two dinuclear Ru complexes with tetrapodal phosphonate anchors, containing either 2,3,5,6‐tetra(2‐pyridyl)pyrazine or 1,2,4,5‐tetra(2‐pyridyl)benzene as a bridging ligand (Ru‐NP and Ru‐CP, respectively), using zirconium phosphonate to link the layers. Various types of multilayer homo‐ and heterostructures were constructed. In the multilayer heterofilms such as ITO||(Ru‐NP)_m|(Ru‐CP)_n, the difference in redox potentials between Ru‐NP and Ru‐CP layers was approximately 0.7 V, which induced a potential gradient determined by the sequence of the layers. In the ITO||(Ru‐NP)_m|(Ru‐CP)_n multilayer heterofilms, the direct electron transfer (ET) from the outer Ru‐CP layers to the ITO were observed to be blocked for m>2, and charge trapping in the outer Ru‐CP layers became evident from the appearance of an intervalence charge transfer (IVCT) band at 1140 nm from the formation of the mixed‐valent state of Ru‐CP units, resulting from the reductive ET mediation of the inner Ru‐NP layers. Therefore, the charging/discharging (“1”and “0”) states in the outer Ru‐CP layers could be addressed and interconverted by applying potential pulses between ?0.5 and +0.7 V. The two states could be read out by the direction of the photocurrent (anodic or cathodic). The molecular heterolayer films thus represent a typical example of a photoresponsive memory device; that is, the writing process may be achieved by the applied potential (?0.5 or +0.7 V), while the readout process is achieved by measuring the direction of the photocurrent (anodic or cathodic). Sequence‐sensitive multilayer heterofilms, using redox‐active complexes as building blocks, thus demonstrate great potential for the design of molecular functional devices.     

Electrochemical Synthesis of Shape-controlled Cu−Ni Nanocomposite and its Application for Nonenzymatic Glucose Sensing at Nanomolar Level

The electrodeposition method was firstly applied to obtain uniform cube-shaped copper nanoparticles on conductive glass (ITO), and then a layer of tiny nickel nanoparticles. A bimetallic composite electrode (Cu−Ni/ITO), characterized by TEM, XPS and XRD, was prepared to construct the non-enzyme electrochemical glucose sensor with high catalytic activity. The catalytic performance of Cu−Ni/ITO had been greatly improved, probably due to the synergistic bimetallic catalysis effect. The electrode had a satisfactory linear response in the range of 2.5×10⁻⁷ M to 2.6×10⁻³ M, with detection limit as low as 67 nM. Besides, Cu−Ni/ITO had good anti-interference ability and reproducibility, indicating the promising application for glucose detection in practical samples.     

Thylakoid membrane–based photobioelectrochemical systems: Achievements,limitations, and perspectives

During the few past decades, intensive efforts have been focused toward optimizing ‘wiring’ of thylakoid membranes (TMs) to conductive surfaces for their further application for light-energy conversion and production of an electron flow. This review summarizes recent progress and current state of photobioelectrodes and systems based on TMs. We consider various electrode materials and surface modifications, mediators and setup designs reported until now and compare achieved current and power outputs. Finally, we discuss further potentially valuable applications and perspectives of TM-based bioelectrochemical systems.     

Nanostructure in energy conversion

Nanostructured and nanosized materials are widely applied to tackle the pressing challenges associated with energy conversion. In this conceptual review, rather than highlighting separate examples, we aim to give a general overview about where and how nanostructure design can be beneficial in the three major research fields(photo)thermal chemical energy conversion, electrochemical energy conversion, and solar energy conversion. It will be shown that in many cases the design of catalytically active nanostructures is the main task and that especially for catalysts nanostructure and activity are inseparably linked to each other. Moreover, electrochemical and photochemical processes are complicated by the overlap of multiple processes that all need to be optimized, including in particular light absorption, charge migration,recombination and trapping events and surface processes. It will also be shown how the development of materials for new challenges can often be based on our knowledge on existing materials for related applications.