Mixed oxide semiconductors based on bismuth for photoelectrochemical applications

The structural and photoelectrochemical properties of mixed oxide semiconductor films of Bi-Nb-M-O (M = Al, Fe, Ga, In) were studied in order to explore their use as photoanodes in photoelectrochemical cells. These films were prepared on AISI/SAE 304 stainless steel plates by sol–gel dip-coating. The films were characterized by scanning electron microscopy—energy dispersive spectroscopy (SEM-EDS), X-ray diffraction (XRD), and X-ray photoelectron spectroscopy (XPS), and their photoelectrochemical properties were studied by open circuit potential (OCP) measurements, linear sweep voltammetry (LSV), and cyclic voltammetry (CV). SEM micrographs show homogeneous and rough films with agglomerates on the surface. EDS analyses show that the films are composed of Bi, Nb, and M, and the agglomerates are mainly composed of Bi. XRD analyses show a predominant crystalline phase of bismuth(III) oxide (Bi₂O₃) and a secondary phase composed of Bi-M mixed oxides. It is noteworthy that there was no identified niobium-based crystalline phase. XPS results reveal that the films are composed by Bi(III), Nb(V), and M(III). CV results show that the electrochemical behavior is attributed only to the semiconductor films which indicate a good coating of the stainless steel support. OCP measurements show that all the films have n-type semiconductor properties and exhibited photoresponse to the visible light irradiation. LSV results show that the application of a potential higher than +0.1 V enhances the photocurrent which can be attributed to an improved charge carrier separation. The results indicate that these materials can be used in photoelectrochemical cells.     

Crystal structure, spin polarization, solid-state electrochemistry, and high n-type carrier mobility of a paramagnetic semiconductor: vanadyl tetrakis(thiadiazole)porphyrazine

We report the synthesis, crystal structure, and magnetic, electrochemical, and carrier-transport properties of vanadyl tetrakis(thiadiazole)porphyrazine (abbreviated as VOTTDPz) with S = ?. X-ray crystal analysis reveals two polymorphs, the α and β forms; the former consists of a 1D regular π stacking, while the latter forms a 2D π network. Molecular orbital calculations suggest a V(4+)(d(1)) ground state and a characteristic spin polarization on the whole molecular skeleton. The temperature dependence of the paramagnetic susceptibility of the α form clearly indicates a ferromagnetic interaction with a positive Weiss constant of θ = 2.4 K, which is well-explained by McConnell's type I mechanism. VOTTDPz forms amorphous thin films with a flat and smooth surface, and their cyclic voltammogram curves indicate a one-electron reduction process, which is highly electrochromic, because of a reduction of the porphyrazine π ring. Thin-film field-effect transistors of VOTTDPz with ionic-liquid gate dielectrics exhibit n-type performance, with a high mobility of μ = 2.8 × 10(-2) cm(2) V(-1) s(-1) and an on/off ratio of 10(4), even though the thin films are amorphous.     

Electrochemistry and electrocatalysis of hemoglobin in Nafion/nano-CaCO3 film on a new ionic liquid BPPF6 modified carbon paste electrode

Room temperature ionic liquid N-butylpyridinium hexafluorophosphate (BPPF6) was used as a binder to construct a new carbon ionic liquid electrode (CILE), which exhibited enhanced electrochemical behavior as compared with the traditional carbon paste electrode with paraffin. By using the CILE as the basal electrode, hemoglobin (Hb) was immobilized on the surface of the CILE with nano-CaCO3 and Nafion film step by step. The Hb molecule in the film kept its native structure and showed good electrochemical behavior. In pH 7.0 Britton-Robinson (B-R) buffer solution, a pair of well-defined, quasi-reversible cyclic voltammetric peaks appeared with cathodic and anodic peak potentials located at -0.444 and -0.285 V (vs SCE), respectively, and the formal potential (E degrees') was at -0.365 V, which was the characteristic of Hb Fe(III)/Fe(II) redox couples. The formal potential of Hb shifted linearly to the increase of buffer pH with a slope of -50.6 mV pH-1, indicating that one electron transferred was accompanied with one proton transportation. Ultraviolet-visible (UV-vis) and Fourier transform infrared (FT-IR) spectroscopy studies showed that Hb immobilized in the Nafion/nano-CaCO3 film still remained its native arrangement. The Hb modified electrode showed an excellent electrocatalytic behavior to the reduction of H2O2, trichloroacetic acid (TCA), and NaNO2.     

Electrochemical generation of free nitric oxide from nitrite catalyzed by iron meso-tetrakis(4-N-methylpyridiniumyl)porphyrin

Electrochemical generation of free nitric oxide (NO) from nitrite (NO(2)(-)) catalyzed by iron meso-tetrakis(4-N-methylpyridiniumyl)porphyrin, [Fe(III)(TMPyP)](5+), has been developed in this study. To obtain free NO, a cathodic electrolysis and an anodic electrolysis were performed in two connected flow electrolytic cells in sequence. The flow electrolytic cell upstream was used for cathodic electrolysis, where the solution of [Fe(III)(TMPyP)](5+) and NO(2)(-) was reduced at -0.25 V (vs Ag/AgCl) into [Fe(II)(NO(2)(-))(2)(TMPyP)](2+) and [Fe(II)(NO)(TMPyP)](4+) in sequence. The flow electrolytic cell downstream was utilized for anodic electrolysis, where [Fe(II)(NO)(TMPyP)](4+) formed from the upstream cell was oxidized at +0.40 V (vs Ag/AgCl) into [Fe(III)(TMPyP)](5+) and free NO. Finally, NO was bubbled out from anodic electrolyte by argon gas. The mechanism and the optimum conditions for electrochemical generation of NO from NO(2)(-) catalyzed by [Fe(III)(TMPyP)](5+) were studied in detail by voltammetric and spectroelectrochemical methods.     

Direct Synthesis of High Purity Silicon Wires by Electrorefining in Molten KF-NaF Eutectic

The electrochemical synthesis silicon wires by electrorefining metallurgical grade silicon in thermally dried and pre-electrolyzed molten KF-NaF eutectic were studied at temperatures 800-900 oC using cyclic voltammetry and ac impedance. One oxidation peak at -0.14 V could be attributed to the reaction of Si to Si⁴⁺. A cathodic peak occurred at -0.56 V in the cyclic voltammogram and one response semicircle in the ac impedance spectrum was observed, supporting a one-step electrochemical reduction process of Si⁴⁺→Si. The electrochemical reaction of silicon was controlled by the diffusion process. The purity of electrorefined silicon wires was up to 99.999% by ICP-MS analysis.     

Copper-dioxygen adducts and the side-on peroxo dicopper(II)/bis(mu-oxo) dicopper(III) equilibrium: Significant ligand electronic effects

The variation of ligand para substituents on pyridyl donor groups of tridentate amine copper(I) complexes was carried out in order to probe electronic effects on the equilibrium between mu-eta2:eta2-(side-on)-peroxo [Cu(II)2(O2(2-))]2+ and bis(mu-oxo) [Cu(III)2(O(2-))2] species formed upon reaction with O2. [Cu(I)(R-PYAN)(MeCN)n]B(C6F5)4 (R-PYAN = N-[2-(4-R-pyridin-2-yl)-ethyl]-N,N',N'-trimethyl-propane-1,3-diamine, R = NMe2, OMe, H, and Cl) (1R) vary over a narrow range in their Cu(II)/Cu(I) redox potentials (E(1/2) vs Fe(cp)2(+/0) = -0.40 V for 1(NMe2), -0.38 V for 1(OMe), -0.33 V for 1H, and -0.32 V for 1Cl) and in C-O stretching frequencies of their carbonyl adducts, 1R-CO: nu(C-O) = 2080, 2086, 2088, and 2090 cm(-1) for R = NMe2, OMe, H, and Cl, respectively. However, within this range of electronic properties for 1R, dioxygen reactivity is significantly affected. The reaction of 1Cl or 1H with O2 at -78 degrees C in CH2Cl2 gives UV-vis and resonance Raman spectra indicative of a mu-eta2:eta2-(side-on)-peroxo dicopper(II) adduct (2R). Compound 1(OMe) reacts with O2, yielding equilibrium mixtures of side-on peroxo (2(OMe)) and bis(mu-oxo) (3(OMe)) species. Oxygenation of 1(NMe2) leads to the sole generation of the bis(mu-oxo) dicopper(III) complex (3(NMe2)). A solvent effect was also observed; in acetone or THF, increased ratios of bis(mu-oxo) relative to side-on peroxo complex are observed. Thus, the equilibrium between a dicopper side-on peroxo and bis(mu-oxo) species can be tuned by ligand design-specifically, more electron donating ligands favor the formation of the latter isomer, and the peroxo/bis(mu-oxo) equilibrium can be shifted from one extreme to the other within the same ligand system. Observations concerning the reactivity of the dioxygen adducts 2H and 3(NMe2) toward external substrates are also presented.     

Identification of iron(III) oxides and hydroxy-oxides by voltammetry of immobilised microparticles

In this paper, we propose the use of an electroanalytical technique based on the direct oxidation or reduction of the electroactive components of the sample on the surface of the working electrode, called voltammetry of immobilised microparticles (VMPs). The sample is easily deposited on the electrode by abrasion and then the electrode is transferred to the electrochemical cell where the square wave potential scan is performed. Electroactive species showed peaks whose peak potential is related to the standard formal potentials. We applied this technique to the identification of iron oxides and hydroxy-oxides in cosmetics. To characterise and identify the iron(III) oxides and hydroxy-oxides VMP was performed in two different media: oxalic acid and hydrochloric acid, that is, a complexing and a slightly complexing media. Two electrode processes were observed. They were influenced by the media and the synthesis procedure of the oxides. The reduction peak at negative potentials (−0.50 V in hydrochloric acid and −0.60 V in oxalic acid) is related to the direct reduction of the iron(III) oxide and it does not appear in the case of the more reactive phases (hydroxy-oxides). The peak at positive potentials (0.90 V in hydrochloric acid and 0.60 V in oxalic acid) involves the reduction of iron(III) in solution. The same electrode process were observed for binary mixtures but the peak potentials are shifted from the pure components peak potentials. This allowed us to distinguish between their mixtures. Finally, VMP was used to characterise iron oxides in cosmetic powders.     

Iron tetraanthracenotetraazaporphyrins: synthesis, structural characterization, ligand binding properties, and unexpected selectivity of a bis-"bowl" tetraazaporphyrin

The synthesis and characterization, by optical spectroscopy, mass spectrometry, superconducting quantum interference device (SQUID) magnetometry, and single-crystal X-ray diffraction, of six iron complexes of tetraanthracenotetraazaporphyrin (TATAP) are reported. Eight benzo groups, flanking the macrocycle periphery, form a nonpolar "bowl" on each face of the porphyrazine and prevent mu-oxo dimer formation. Fe(TATAP) readily binds THF, a variety of neutral nitrogenous axial ligands, and carbon monoxide. The equilibrium binding constants for the first two are higher than those of analogous porphyrins while those of the latter are smaller. We attribute these differences to the higher pi acidity of the porphyrazine ligand. Fe(TATAP) also shows different relative magnitudes of the successive equilibrium binding constants, K1 and K2, for hindered nitrogenous ligands when compared to those of porphyrin analogues. Surprisingly, Fe(TATAP), in toluene solution, shows no affinity for O2 when exposed to 1 atm partial pressure of O2 at 25 degrees C. These results are explained in terms of an unusually positive iron(III/II) redox potential when coordinated by the TATAP ligand.     

Photocurrent generation in layer-by-layer assembled dendrimers with ruthenium tris-bipyridine peripheral groups and a viologen-like core

The photophysical and photoelectrochemical properties of first- and second-generation dendrimers with ruthenium tris-bipyridine peripheral groups and a tri-viologen like core (Ru3V3 and Ru6V3) were investigated in solution and when embedded within assembled films. The stepwise assembly of these dendrimers on quartz and ITO surfaces utilizing the layer-by-layer approach was investigated. The amount of the assembled dendrimers was found to increase on going to the higher generation dendrimer. This dendrimer generation effect was evident from the UV-vis, atomic force microscopy, and electrochemical measurements of the dendrimers in either solution phase or when embedded in films. The anodic and cathodic photocurrent generation was seen upon visible light irradiation, with higher photocurrents for Ru6V3 than Ru3V3. This observation was attributed to better light-harvesting properties, thicker films, and slower charge recombination processes in Ru6V3 when compared to Ru3V3.     

Synthesis and two-electron redox behavior of diazuleno[2,1-a:1,2-c]naphthalenes

The Diels-Alder reaction of di-2-azulenylacetylene with tetraphenylcyclopentadienone afforded 7,8,9,10-tetraphenyldiazuleno[2,1-a:1,2-c]naphthalene in one pot via autoxidation of the presumed 1,2-di-2-azulenylbenzene derivative. In contrast, a similar reaction of bis(1-methoxycarbonyl-2-azulenyl)acetylene with tetraphenylcyclopentadienone gave the 1,2-di-2-azulenylbenzene derivative. The following cyclodehydrogenation reaction of the benzene derivative with iron(III) chloride afforded diazuleno[2,1-a:1,2-c]naphthalene 6,11-bismethoxycarbonyl derivative. The redox behavior of these novel diazuleno[2,1-a:1,2-c]naphthalenes was examined by cyclic voltammetry (CV). These compounds exhibited two-step oxidation waves at +0.22 to +0.71 V upon CV, which revealed the formation of a radical cation and dication stabilized by the fused two azulene rings under the electrochemical oxidation conditions. Since the 1,2-di-2-azulenylbenzene derivative was oxidized at higher oxidation potentials (+0.83 and +1.86 V), the fusion of the two azulene rings to naphthalene increased electron-donating properties because of the formation of a closed-shell dicationic structure. Formation of the radical cation was characterized by UV-vis spectroscopy under the electrochemical oxidation conditions, although no evidence was obtained for the presumed dication under the conditions of the UV-vis spectroscopy measurement.     

辅酶Ⅰ在苯并咪唑修饰银电极上的还原反应

辅酶Ⅰ在苯并咪唑修饰银电极上的还原反应李根喜,陈洪渊,朱德煦（南京大学生物化学系,生物医药技术国家重点实验室,化学系,南京,２１００９３）关键词ＮＡＤ~＋,苯并咪唑,化学修饰电极还原态烟酰胺辅酶Ⅰ（ＮＡＤＨ）的氧化反应已进行了大量研究。但有关氧化态辅?..     

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.     

Indirect Voltammetric Determination of Iron at Parts-Per-Million Levels Using Either Ferron or BPDS

Abstract

The electrochemical behavior of ferron and BPDS (bathophenanthrolinedisulfonic acid) in 0.5 M HAc/NaAc at pH 4.7 is studied by cyclic voltammetry at a glassy carbon electrode. Ferron shows a very sharp oxidation peak at + 0.74 V vs SCE while BPDS shows a sharp reduction peak at - 1.03 V. The heights of the peaks are shown to be inversely proportional to the iron (III) and iron (II) concentration of the solution, respectively. Linear calibration plots are obtained between 5 and 60 ppm of iron (III) for ferron and 0 to 60 ppm of iron (II) for BPDS using, initially, 4.00 mM solution of each reagent. A simple and fast procedure was developed for the analysis of iron content in pharmaceutical samples. The results are comparable with those found by spectrophotometry.     

Electroactive layer-by-layer films of heme protein-coated polystyrene latex beads with poly(styrene sulfonate)

In this work, a novel two-step construction strategy for protein layer-by-layer assembly films was proposed. In the first step, positively charged hemoglobin (Hb) or myoglobin (Mb) at pH 5.0 was adsorbed on the negatively charged surface of 500 nm diameter-sized polystyrene (PS) latex beads, forming core-shell structured PS-protein particles. In the next step, the PS-protein particles were further assembled layer by layer with oppositely charged poly(styrene sulfonate)(PSS) on various solid surfaces under suitable conditions. Cyclic voltammetry (CV), quartz crystal microbalance (QCM), and UV-vis spectroscopy were used to monitor the growth of {(PS-protein)/PSS}(n) films. The stable {(PS-protein)/PSS}(n) films modified on pyrolytic graphite (PG) electrodes demonstrated good electroactivity in protein-free buffer, which was originated from protein heme Fe(III)/Fe(II) redox couples, and the electroactivity extended to six (PS-protein)/PSS bilayers. UV-vis spectroscopy showed that Hb and Mb in the films retained their near-native structure in the medium pH range. {(PS-protein)/PSS}(n) films catalyzed electrochemical reduction of oxygen, hydrogen peroxide, trichloroacetic acid (TCA) and nitrite with a significant lowering of overpotential, and displayed better catalytic activity than corresponding cast PS-protein films.     

基于三联吡啶衍生物的Fe~(2+)/Fe~(3+)化学比色敏感器

合成和表征了一种新的化合物(E)-4-′(4-(2-(2-萘)乙烯基)苯基)-2,2′:6′,2″-三联吡啶L.用Fe2+或Fe3+来滴定时,L的溶液(三氯甲烷和乙醇的体积比为1∶20)颜色分别从无色变成洋红色和橙红色,相应的紫外可见吸收光谱都在374和574 nm出现特征吸收峰.此外,即使存在其它过量金属阳离子时,L对Fe2+或Fe3+离子仍然表现出很强的敏感性和选择性.另外,还研究了L对Fe2+或Fe3+离子及两者共同存在时的线性检测浓度范围和最低检测极限(LOD).     

Mechanism of nitrate electroreduction on Pt(100)

Kinetics and mechanism of nitrate anion reduction on the Pt(100) electrode in perchloric and sulfuric acid solutions are studied. Analysis of the results of electrochemical measurements (combination of potentiostatic treatment and cyclic voltammetry) and the data of in situ IR spectroscopy allow suggesting the following scheme of the nitrate reduction process on Pt(100) differing from that in the literature. If the potential of 0.85 V is chosen as the starting potential for a clean flame-annealed electrode surface and negativegoing (cathodic) potential sweep is applied, then an NO adlayer with the coverage of about 0.5 monolayer is formed on Pt(100) in the nitrate solution already at 0.6 V. The further decrease in the potential results in NO reduction to hydroxylamine or/and ammonia, desorbing products vacate the adsorption sites for nitrate and hydrogen adatoms. At E < 0.1 V, adsorbed hydrogen is mostly present on the surface. During positive-going (anodic) potential sweep, the process of nitrate reduction starts after partial hydrogen desorption, the cathodic peak of nitrate reduction to hydroxylamine or ammonia is observed at 0.32 V on cyclic voltammograms. The process of nitrate anion reduction continues up to 0.7 V; at higher potentials, the surface redox process with participation of hydroxylamine or ammonia (the anodic peak at 0.78 V) and nitrate (the cathodic peak at 0.74 V is due to nitrate reduction to NO on the vacant adsorption sites) occurs.     

Chelate adsorption for trace voltammetric measurements of iron(III)

Summary A very sensitive electrochemical stripping procedure for trace measurements of iron(III) is described. The chelate of iron with Solochrome Violet RS is adsorbed on the hanging mercury drop electrode, and the reduction current of the accumulated chelate is measured by voltammetry. The adsorption and redox behaviours are explored by cyclic voltammetry. The height of the chelate peak, which is about 0.28 V more negative than the peak of the free dye, is shown to be proportional to the iron concentration. Optimal experimental conditions include a preconcentration potential of –0.40 V, solution pH of 5.1 and a linear scan mode. The sharp chelate peak, associated with the effective interfacial accumulation, coupled with the flat baseline, facilitates measurements at the nanomolar and submicromolar concentration levels using short preconcentration times. The limit of detection after 1 min preconcentration is 0.04 gl^–1 (7 × 10^–10 M), and the relative standard deviation at the 10^–7 M level is 4.7%. The effects of possible interferences, due to coexisting metal ions or organic surfactants, are evaluated. The ability of measuring iron(III) in the presence of iron(II) is illustrated. Actual analyses of sea and tap waters are reported.

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Chelat-Adsorption für voltammetrische Spurenanalyse von Eisen(III)

     

Growth of ultrathin films of cadmium telluride and tellurium as studied by electrochemical atomic force microscopy

Time dependent, cathodic electrodeposition of ultrathin CdTe and Te films has been studied in 50 mM H(2)SO(4) + 1 mM CdSO(4) + 0.1 mM TeO(2) solutions at room temperature under potential control using electrochemical atomic force microscopy (EC-AFM). The films were also characterized electrochemically and with X-ray diffraction. The growth mechanism and the composition of the films depends on the applied potentials. Island-like growth mode was observed for CdTe films when the deposition potential was -0.35 V (SHE). At a more positive deposition potential of 0.138 V (SHE), Cd was not co-deposited into the film but affected the dynamic growth mode of the deposit. At this voltage smooth Te films were obtained. Depending on the applied potential, Cd acts either as a co-deposition element for CdTe film growth, or as a mediator for layer-by-layer growth of Te films.     

Electrochemical and spectral studies on the reductive nitrosylation of water-soluble iron porphyrin

The reaction of iron(III) (meso-tetrakis(N-methylpyridinium-4-yl)porphyrin (Fe(III)TMPyP) with nitric oxide (NO) was studied by electronic absorption spectroscopy, ESR, and electrochemical and spectroelectrochemical techniques in aqueous solutions with pH from 2.2 to 12.0. Fe(III)TMPyP has been found to undergo a reductive nitrosylation in all pHs, and the product of nitric oxide binding to the porphyrin has been determined as iron(II) porphyrin nitrosyl complex ([Fe(II)(NO)TMPyP]). The rate of the reductive nitrosylation exhibits a tendency to get faster with increase in pH. An intermediate species was observed around neutral pH by spectroelectrochemical technique and was proposed to be the iron(II) nitrosyl complex of the mu-oxo dimeric form of FeTMPyP, which is known to be a predominant in neutral solutions.     

Iron complexes of new pentadentate ligands containing the 1,4,7-triazacyclononane-1,4-diacetate motif. spectroscopic, electro-, and photochemical studies

Three new pentadentate, pendent arm macrocycles containing the 1,4,7-triazacyclononane-1,4-diacetate motif have been synthesized, and their coordination chemistry with Fe(III) has been investigated. Eight new octahedral Fe(III) complexes containing chloro, azido, or mu-oxo ligands have been synthesized, five of which have been characterized by X-ray crystallography. Spectroscopic characterization of these octahedral Fe(III) complexes by UV-vis, IR, electrochemistry, EPR, magnetic susceptibility, and zero-field M?ssbauer measurements firmly establishes the high-spin state of the iron in all complexes. Electrochemistry studies of the azido-Fe(III) complexes show that they can be reversibly oxidized to the corresponding Fe(IV) species at -20 degrees C, and Fe(II), Fe(III), and Fe(IV) species show characteristic IR and UV-vis profiles. Photolysis of one of the azido complexes was studied as a function of temperature (room temperature vs 77 K) and wavelength (480, 419, and 330 nm). Photoreduction to a high-spin Fe(II) species occurs under all conditions, which is proposed to be the dominant photochemical pathway generally available to high-spin ferric azido complexes.