NanoTiO2-CNT复合膜电极在DMF溶液中对糠醛的异相电催化还原

通过在乙醇中电化学溶解Ti金属阳极合成前驱体Ti(OEt)4和溶胶-凝胶法在Ti表面修饰一层纳米TiO2-碳纳米管(nanoTiO2-CNT)复合膜, 采用循环伏安和电解合成法研究了nanoTiO2-CNT复合膜电极在N, N-二甲基甲酰胺(DMF)中的氧化还原行为以及对糠醛(furfural)还原的电催化活性. 结果发现, nanoTiO2-CNT电极在阴极扫描时有两对氧化还原峰, 可逆半波电位E r1/2 分别为－1.27 V和－2.44 V(vs SCE, 扫描速度100 mV•s-1), 分别对应于TiO2/Ti2O3氧化还原电对的可逆电极过程和TiO2/Ti(OH)3电对的准可逆电极过程；在DMF电解液中nanoTiO2-CNT复合膜中的Ti(IV)/Ti(III)氧化还原电对作为媒质间接电还原糠醛为糠醇, 反应机理为电化学偶联随后化学催化反应(EC′)机理.     

Artificial photosynthesis by using chloroplasts from spinach adsorbed on a nanocrystalline TiO2 electrode for photovoltaic conversion

Photovoltaic conversion has been achieved by use of chloroplasts (photosynthetic organs) from spinach adsorbed on a nanocrystalline TiO₂ film on an indium tin oxide (ITO) glass electrode (chloroplast/TiO₂ electrode). The shape of the absorption spectrum of the chloroplast/TiO₂ electrode is almost the same that of a dispersion of the chloroplasts. Absorption maxima of the chloroplast/TiO₂ electrode observed at 430, 475, and 670 nm were attributed to carotenoid and chlorophyll molecules, suggesting that chloroplasts have been adsorbed by the nanocrystalline TiO₂ film on the ITO electrode. The photocurrent responses of chloroplast/TiO₂ electrodes were measured by using a solution of 0.1 M tetrabutylammonium hexafluorophosphate in acetonitrile as redox electrolyte in the presence or absence of water and 100 mW cm^?2 irradiation. The photocurrent of the chloroplast/TiO₂ electrode was increased by adding water to the redox electrolyte. The photocurrent responses of chloroplast/TiO₂ electrodes irradiated with monochromatic light (680 nm, the absorption band of photosystem II complexed with evolved oxygen) were measured by use of a solution of 0.1 M tetrabutylammonium hexafluorophosphate in acetonitrile as redox electrolyte in the presence or absence of water. A chloroplast/TiO₂ electrode photocurrent was observed only when the redox electrolyte containing water was used, indicating that the oxygen evolved from water by photosystem II in chloroplasts adsorbed by a nanocrystalline TiO₂ film on an ITO electrode irradiated at 680 nm is reduced to water by the catalytic activity of the platinum electrode. The maximum incident photon-to-current conversion efficiency (IPCE) was 0.8 % on irradiation at 670 nm.     

纳米TiO_2膜修饰电极异相电催化还原马来酸

通过电化学合成前驱体和溶胶-凝胶法在Ti表面修饰一层纳米TiO_2膜，SEM， XRD测试表明晶型为锐钛矿型，晶粒平均尺寸为25 nm。采用循环伏安法、循环方波 伏安法和电解合成法研究了纳米TiO_2膜电极在硫酸介质中的氧化还原行为以及对 马来酸（maleic acid）还原的电催化活性。结果表明，纳米TiO_2膜电极在阴极扫 描时有两对可逆氧化还原峰，可逆半波电位E_(1/2)~r分别为-0.53 V和-0.92 V（ sv. SCE，扫描速度0.05 V·s~(-1)），对应于TiO_2/Ti_2O_3和TiO_2/Ti(OH)_3两 个氧化还原电对的可逆电极过程。其中TiO_2/Ti_2O_3电对对马来酸具有异相电催 化还原活性，纳米TiO_2膜中的Ti~(IV)/Ti~(III)氧化还原电对作为媒质间接电还 原马来酸为丁二酸（butane diacid），反应机理为电化学偶联随后化学催化反应 （EC'）机理。     

Three-Dimensional Pinecone-like Binder-Free Pt–TiO2 Nanorods on Ti Mesh Structures: Synthesis,Characterization and Electroactivity towards Ethanol Oxidation

We report here the synthesis of binderless and template-less three-dimensional (3D) pinecone-shaped Pt/TiO₂/Ti mesh structure. The TiO₂ hydrothermally synthesized onto Ti mesh is composed of a mixture of flower-like nanorods and vertically aligned bar-shaped structures, whereas Pt film grown by pulsed laser deposition displays a smooth surface. XRD analyses reveal an average crystallite size of 41.4 nm and 68.5 nm of the TiO₂ nanorods and Pt, respectively. In H₂SO₄ solution, the platinum oxide formation at the Pt/TiO₂/Ti mesh electrode is 180 mV more negative than that at the Pt/Ti mesh electrode, indicating that TiO₂ provides oxygeneous species at lower potentials, which will facilitate the removal of CO-like intermediates and accelerate an ethanol oxidation reaction (EOR). Indeed, the Pt/TiO₂/Ti mesh catalyst exhibits current activity of 1.19 mA towards an EOR at a remarkably superior rate of 4.4 times that of the Pt/Ti mesh electrode (0.27 mA). Moreover, the presence of TiO₂ as a support to Pt delivers a steady-state current of 2.1 mA, with an increment in durability of 6.6 times compared to Pt/Ti mesh (0.32 mA). Pt is chosen here as a benchmark catalyst and we believe that with catalysts that perform better than Pt, such 3D pinecone structures can be useful for a variety of catalytic or photoelectrochemical reactions.     

纳米TiO2膜修饰电极上对硝基苯甲酸异相电催化还原

有机电合成具有对环境友好、反应条件温和副产物少等优点并符合“原子经济性”要求，是一种可持续发展的绿色化学方法，已成为化学研究的重要前沿之一．使用媒质作为氧化剂和还原剂的间接电合成，大多为均相氧化还原电催化过程，把氧化还原催化剂固定在电极表面的异相电催化与均相催化相比具有更为显著的优点．本文采用循环伏安和电解合成法研究了纳米TiO2膜电极在硫酸介质和氢氧化钠介质中的氧化还原行为以及异相电催化还原对硝基苯甲酸的活性，探讨了纳米TiO2膜异相电催化的本质．     

Electrocatalytic evaluation of liquid phase deposited methylene blue/TiO2 hybrid films

Methylene blue (MB)/TiO₂ hybrid thin films were prepared on glassy carbon (GC) electrode surface by the liquid phase deposition (LPD) process. The electrochemical measurements indicated that MB retained its electrochemical activity in the hybrid films. The linear dependence of the reduction peak current for MB upon the scan rate and linear relationship between the middle point potential of MB and pH revealed the surface-confined two-proton two-electron electrochemical characteristics of MB entrapped in hybrid LPD films. Although the electron transfer of K₃[Fe(CN)₆] on GC surface was inhibited by TiO₂ film, the catalytic reduction of K₃[Fe(CN)₆] by MB was observed on the MB/TiO₂ hybrid films. The electrocatalytic activity of hybrid films was also demonstrated as an “artificial peroxidase” for the catalytic reduction of H₂O₂.     

Gold particles supported on self-organized nanotubular TiO2 matrix as highly active catalysts for electrochemical oxidation of glucose

Au/TiO₂/Ti electrode was prepared by a two-step process of anodic oxidation of titanium followed by cathodic electrodeposition of gold on resulted TiO₂. The morphology and surface analysis of Au/TiO₂/Ti electrodes was investigated using scanning electron microscopy and EDAX, respectively. The results indicated that gold particles were homogeneously deposited on the surface of TiO₂ nanotubes. The nanotubular TiO₂ layers consist of individual tubes of about 60–90 nm in diameter, and the electrode surface was covered by gold particles with a diameter of about 100–200 nm which are distributed evenly on the titanium dioxide nanotubes. This nanotubular TiO₂ support provides a high surface area and therefore enhances the electrocatalytic activity of Au/TiO₂/Ti electrode. The electrocatalytic behavior of Au/TiO₂/Ti electrodes in the glucose electro-oxidation was studied by cyclic voltammetry. The results showed that Au/TiO₂/Ti electrodes exhibit a considerably higher electrocatalytic activity toward the glucose oxidation than that of gold electrode.     

Nanoporous Pt Catalyst Modified by Sn Electrodeposition for Electrochemical Oxidation of Formaldehyde

A nanoporous Pt particles‐modified Ti (nanoPt/Ti) electrode was prepared through a simple hydrothermal method using aqueous H₂PtCl₆ as a precursor and formaldehyde as a reduction agent. The nanoPt/Ti electrode was then modified with limited amounts of tin particles generated by cyclic potential scans in the range of ?0.20 to 0.50 V in a 0.01 mol·L^?1 SnCl₂ solution, to synthesize a Sn‐modified nanoporous Pt catalyst (Sn/nanoPt/Ti). Electroactivity of the nanoPt/Ti and Sn/nanoPt/Ti electrodes towards formaldehyde oxidation in a 0.5 mol·L^?1 H₂SO₄ solution was evaluated by cyclic voltammetry and chronoamperometry. Electrooxidation of formaldehyde on the nanoPt/Ti electrode takes place at a potential of 0.45 V and then presents high anodic current densities due to the large real surface area of the nanoPt/Ti electrode. The formaldehyde oxidation rate is dramatically increased on the Sn/nanoPt/Ti electrode at the most negative potentials, where anodic formaldehyde oxidation is completely suppressed on the nanoPt/Ti electrode. Chronoamperogramms (CA) of the Sn/nanoPt/Ti electrode display stable and large quasi‐steady state current densities at more negative potential steps. Amperometric data obtained at a potential step of 100 mV show a linear dependence of the current density for formaldehyde oxidation upon formaldehyde concentration in the range of 0.003 to 0.1 mol·L^?1 with a sensitivity of 59.29 mA·cm^?2 (mol·L^?1)^?1. A detection limit of 0.506 mmol·L^?1 formaldehyde was found. The superior electroactivity of the Sn/nanoPt/Ti electrode for formaldehyde oxidation can be illustrated by a so‐called bifunctional mechanism which is involved in the oxidation of poisoning adsorbed CO species via the surface reaction with OH adsorbed on neighboring Sn sites.     

TCO-free dye solar cells based on Ti back contact electrode by facile printing method

The back contact dye solar cells (BCDSCs), in which the TCO(Transparent Conductive oxide) is omitted, have a potential for use of intact low-cost general substrates such as glass, metal foil and papers. Herein, we introduce a facile manufacturing method of a Ti back contact electrode (Ti BCE) for the BCDSCs. We found that the polylinkers such as poly(butyl titanate) have a strong binding property to make Ti particles connect one with another. A porous Ti film, which consists of Ti particles of ≤ 10? size connected by a small amount of polylinkers, has an excellent low sheet resistance of 10 Ω sq^-1 for an efficient electron collection for DSCs. This Ti BCE can be prepared by using a facile printing method under normal ambient conditions. Conjugating the new back contact electrode technology with the traditional monolithic structure using the carbon counter electrode, we fabricated TCO-less DSCs. These four-layer structurered DSCs consist of a dye-adsorbed nanocrystalline TiO₂ film on a glass substrate, a porous Ti back contact layer, a ZrO₂ spacer layer and a carbon counter electrode in a layered structure. Under AM 1.5 G and 100 mWcm^?2 simulated sunlight illumination, the four-layer structurered DSCs with N719 dyes and I^-/I₃^-redox electrolytes achieved PCEs up to 5.21 %.     

Catalysis of dioxygen reduction at soluble polyaniline modified electrode

A reflux-treatment of soluble polyaniline (SPA) in dimethylformamide (DMF) containing CoCl₂ yields an active catalyst for dioxygen reduction which can be adsorbed on the electrode surface firmly. The catalytic reduction of dioxygen at the glassy carbon (GC) electrode modified by the catalyst was studied with cyclic voltammetry (CV), rotating disk electrode (RDE) and rotating ring-disk electrode (RRDE). The kinetic process of dioxygen reduction at the modified electrode was analyzed with a new RRDE theory dealing with a nondiffusion-controlled process on ring electrode. The rate constants for each scheme of dioxygen reduction were calculated, showing that only 2-electron reduction to H₂O₂ was conducted at the modified electrode. The effect of solution acidity on the electrocatalytic behaviour for dioxygen reduction was investigated. A possibility of initiating catalytic activity for dioxygen reduction was explored with ESCA method.     

Evaluation of in vitro bioactivity and MG63 Oesteoblast cell response for TiO2 coated magnesium alloys

The present investigation reports TiO₂ coating on magnesium alloy AZ31 by sol–gel method via dip coating technique. TiO₂ coated surface was characterized by thin film X-ray diffraction (TF-XRD), Fourier transform infrared red (FT-IR) spectroscopy, scanning electron microscopy (SEM) with energy-dispersive X-ray (EDX) spectroscopy, atomic force microscopy (AFM) and transmission electron microscopy (TEM) techniques. From TF-XRD results, the peaks at 2θ values of 25.14, 32.12, 68.73 and 70.11 confirm the presence of TiO₂. The TiO₂ is crystalline in nature and the crystallite size is about 32.4 nm. SEM-EDX, TEM and AFM show that the coated surface is uniform and nanoporous. FT-IR analysis shows that the peak in the range of 692 cm^?1 is assigned to Ti–O–Ti stretching vibration. Contact angle measurements show that the coating is hydrophilic in nature. Bioactivity of the coating in simulated body fluid (SBF) was also examined, the hydroxyl functionalized surface greatly enhances the hydroxyapatite growth. The potentiodynamic polarization studies prove that the corrosion resistance of the TiO₂ coated surface after immersion in SBF for 7 days is improved dramatically. Cell adhesion studies confirm the increased cell attachment on TiO₂ coated surface when compared to uncoated alloy, due to less amount of Mg ion release from the substrate in the culture medium.     

Electrocatalytic Reduction of Oxygen at Multi‐Walled Carbon Nanotubes and Cobalt Porphyrin Modified Glassy Carbon Electrode

The multi‐walled carbon nanotubes (MWNTs) modified glassy carbon electrode exhibited electrocatalytic activity to the reduction of oxygen in 0.1 M HAc‐NaAc (pH 3.8) buffer solution. Further modification with cobalt porphyrin film on the MWNTs by adsorption, the resulted modified electrode showed more efficient catalytic activity to O₂ reduction. The reduction peak potential of O₂ is shifted much more positively to 0.12 V (vs. Ag/AgCl), and the peak current is increased greatly. Cyclic voltammetry (CV), transmission electron microscopy (TEM), X‐ray photoelectron spectroscopy (XPS) and atomic force microscopy (AFM), were used to characterize the material and the modified film on electrode surface. Electrochemical experiments gave the total number of electron transfer for oxygen reduction as about 3, which indicated a co‐exist process of 2 electrons and 4 electrons for reduction of oxygen at this modified electrode. Meanwhile, the catalytic activities of the multilayer film (MWNTs/CoTMPyP)_n prepared by layer‐by‐layer method were investigated, and the results showed that the peak current of O₂ reduction increased and the peak potential shifted to a positive direction with the increase of layer numbers.     

Modifiying glassy carbon electrode with ferrocene-bridged polysilsesquioxanes

Ferrocene-bridged polysilsesquioxanes film electrodes were prepared via depositing the sols formed by hydrolysis of 1,1′-bis[(2-triethoxylsilyl)ethyl]ferrocene (BTEF) or co-hydrolysis of poly(vinylalcohol) (PVA) with BTEF or tetraethoxysilane (TEOS) with BTEF onto glassy carbon electrode (GCE) surface. The electrochemical behavior of the modified electrodes were characterized by cyclic voltammogram (CV) in aqueous solution. The BTEF film, BTEF/PVA film and BTEF/TEOS film all exhibit a redox wave at E^0’ are 0.504, 0.326, 0.318 V, with the peak potential separation (ΔE) are 0.132, 0.042, 0.028 V, and the value of i_pa/i_pc are 1.8097, 1.007, 1.064 (vs. SCE), respectively. This suggests that BTEF/PVA film and BTEF/TEOS film have a good reversible redox behavior and the redox peak is corresponded to a one-electron reduction and oxidation process. After successive 50 time’s cyclic voltammetric, there is no peak potential shift, and the peak current only decreased 5.58, 4.95%, respectively. BTEF/PVA film has better hydrophilicity and shows a more perfect electrocatalytic activity in the oxidation of H₂A than that of the BTEF/TEOS film. The catalytic peak current has a linear relationship with the concentration of H₂A in the range of 1.0 × 10⁻⁵~1.0 × 10⁻³ M.     

Influence of particle size on the photoactivity of Ti/TiO2 thin film electrodes,and enhanced photoelectrocatalytic degradation of indigo carmine dye

Photoanodes based on Ti/TiO₂ thin films were prepared by the sol–gel method, using either tetraisopropoxide (Ti(OPri)₄) or modified tetraisopropoxide, producing electrodes with different sized nanoparticle coatings, termed nanoporous (20 nm) or nanoparticulated (10 nm) electrodes. The anatase form dominated the composition of the nanoparticulated electrode, which presented a higher surface area, a flat band potential shift of ?160 mV and a 50% improvement in photoactivity, compared to the nanoporous electrode. 100% color removal, and 75% mineralization, of indigo carmine dye were achieved after 15 min of photoelectrocatalytic treatment using a nanoparticulated Ti/TiO₂ electrode operated at a current density of 0.4 mA cm^?2. Our findings indicate that the use of nanoparticulated electrodes, under UV irradiation and with controlled current density, is an efficient alternative for the removal of food dye contaminants during wastewater treatment.     

Boron Nitride Nanosheet Modified Electrode: Preparation and Application to Direct Electrochemistry of Myoglobin

An ionic liquid modified carbon paste electrode (CILE) was prepared with 1‐hexylpyridine hexafluorophosphate (HPPF₆) and used as a substrate electrode. Then hexagonal boron nitride (BN) nanosheet, myoglobin (Mb) and Nafion were fixed on the electrode surface by coating method to get a new‐style chemically modified electrode (Nafion/Mb/BN/CILE). The morphology and crystal phase of BN nanosheet were characterized by SEM, TEM and XRD. UV‐Vis and FT‐IR results showed that Mb retained its original conformation in the composite modified film. In phosphate buffer solutions (PBS) with pH 3.0, cyclic voltammetry (CV) was performed to investigate the direct electrochemical behaviour of Mb. A pair of quasi‐reversible redox reaction peaks was obtained on the CV curve, proving that BN nanosheet had good biocompatibility and could accelerate electron transfer between Mb and electrode surface. Electrocatalytic reduction of trichloroacetic acid (TCA) was investigated, which was further applied to TCA detection. The catalytic reduction peak current at ?0.355 V depended linearly on the TCA concentration in the range of 0.2～30.0 mmol/L with the equation of Ipc (μA)=6.340 C (mmol/L)+0.305 (r=0.998), and the detection limit was 0.05 mmol/L (3 σ).     

Direct electrochemistry and electrocatalysis of horseradish peroxidase immobilized in Nafion-RTIL composite film

The composite film based on Nafion and hydrophobic room-temperature ionic liquid (RTIL) 1-butyl-3-methyl-imidazolium hexafluorophosphate ([bmim] PF₆) was explored. Here, Nafion was used as a binder to form Nafion-ionic liquids composite film and help [bmim] PF₆ effectively adhered on glassy carbon (GC) electrode. X-ray photoelectron spectroscopy (XPS), cyclic voltammtery (CV) and electrochemical impedance spectroscopy (EIS) were used to characterize this composite film, showing that the composite film can effectively adhere on the GC electrode surface through Nafion interacting with [bmim] PF₆ and GC electrode. Meanwhile, doping [bmim] PF₆ in Nafion can also effectively reduce the electron transfer resistance of Nafion. The composite film can be readily used as an immobilization matrix to entrap horseradish peroxidase (HRP). A pair of well-defined redox peaks of HRP was obtained at the HRP/Nafion-[bmim] PF₆ composite film-modified GC electrode through direct electron transfer between the protein and the underlying electrode. HRP can still retain its biological activity and enhance electrochemical reduction towards O₂ and H₂O₂. It is expected that this composite film may find more potential applications in biosensors and biocatalysis.     

掺杂纳米金粒子的火焰氧化TiO2膜的光电化学性质的研究

A nano-Au modified TiO2 electrode was prepared via the oxidation of Ti sheet in flame and subsequent modification with gold nanoparticles. The results of SEM and TEM measurements show that the Au nanoparticles are well dispersed on TiO2 surface. A near 2-fold enhancement in photocurrent was achieved upon the modification with Au nanoparticles. From the results of photocurrent and electrochemical impedance experiments it was found that the flatband potential of nano-Au/TiO2 electrode negatively shifted about 100 mV in 0.5 mol/L Na2SO4 solutions compared with that of bare TiO2 electrode. The improvement of photoelectrochemical performance was explained by the inhibition for charge recombination of photo-induced electrons and holes, and the promotion for interracial charge-transfer kinetics at nano-Au/TiO2 composite film. Such nanometal-semiconductor composite films have the potential application in improving the performance of photoelectrochemical solar cells.     

Simultaneous Determination of Isoproterenol,Acetaminophen and Folic Acid Using a Novel Nanostructure‐Based Electrochemical Sensor

In this study, a carbon paste electrode modified with (E)‐2‐((2‐chlorophenylimino)methyl)benzene‐1,4‐diol (CD) and titanium dioxide nanoparticles (TiO₂) was used to prepare a novel electrochemical sensor. The objective of this novel electrode modification was to seek new electrochemical performances for the detection of isoproterenol (IP) in the presence of acetaminophen (AC) and folic acid (FA). Initially, cyclic voltammetry (CV) was used to investigate the redox properties of this modified electrode at various scan rates. In the following, the mediated oxidation of IP at the modified electrode was described. The results showed an efficient catalytic activity of the electrode for the electrooxidation of IP, which leads to a reduction in its overpotential by more than 235 mV. The value of the electron transfer coefficient (α), catalytic rate constant (k_h) and diffusion coefficient (D) were calculated for IP, using electrochemical approaches. Based on differential pulse voltammetry (DPV), the oxidation of IP exhibited a dynamic range between 0.5 and 1000 µM and a detection limit (3σ) of 0.47 µM. DPV was used for simultaneous determination of IP, AC and FA at the modified electrode. Finally, this method was used for the determination of IP in real samples, using standard addition method.     

Application of Titanium Dioxide Nanowires for the Direct Electrochemistry of Hemoglobin and Electrocatalysis

Titanium dioxide (TiO₂) nanowires were synthesized and used for the realization of direct electrochemistry of hemoglobin (Hb) with carbon ionic liquid electrode (CILE) as the substrate electrode. TiO₂‐Hb composite was casted on the surface of CILE with a chitosan film and spectroscopic results confirmed that Hb retained its native structure in the composite. Direct electron transfer of Hb on the modified electrode was realized with a pair of quasi‐reversible redox waves appeared, indicating that the presence of TiO₂ nanowires could accelerate the electron transfer rate between the electroactive center of Hb and the substrate electrode. Electrochemical behaviors of Hb on the modified electrode were carefully investigated with the values of the electron transfer coefficient (α), the electron transfer number and the heterogeneous electron transfer rate constant (k_s) as 0.58, 0.98 and 1.62 s^‐1. The Hb modified electrode showed excellent electrocatalytic activity to the reduction of trichloroacetic acid and NaNO₂ with wider linear range and lower detection limit, indicating the successful fabrication of a new third‐generation biosensor.     

Electrocatalytic reduction of nitrite on the surface of a glassy carbon electrode modified by palladium(II)-substituted Dawson type heptadecatungstodiphosphate

A palladium(II)-substituted Dawson type heptadecatungstodiphosphate, K₈[P₂W₁₇O₆₁Pd(H₂O)](abbreviated as P₂W₁₇Pd in the following), was used to construct a new kind of chemically modified electrode (CME) by electrodeposition on the surface of a glassy carbon electrode for the first time. This modified electrode was characterized by Fourier transform infrared reflection absorption spectroscopy (FTIRRAS), X-ray photoelectron spectroscopy (XPS) and cyclic voltammetry (CV). FTIRRAS and XPS suggested that the adsorbed species on the electrode surface has the same Dawson type structure as the heteropolyanion in buffer solution. A couple of waves was observed on the P₂W₁₇Pd CME, which was ascribed to the redox process of the palladium center in the heteropolytungstate. After continuous potential scanning for 30 min in a pH 4.0 buffer, 94% of the original coverage remains for the CME. The P₂W₁₇Pd CME had high electrocatalytic activity for nitrite reduction and exhibited good reproducibility and stability. The catalytic peak current was found to be linear with the nitrite concentration in the range of 1 ∼ 50 mmol/L, with a correlation coefficient of 0.994. The effect of solution pH on the catalytic activity of the CME for nitrite reduction was also investigated. Received: 20 May 1998 / Revised: 7 September 1998 / Accepted: 15 September 1998