Copper doped manganese dioxide as counter electrode for dye-sensitized solar cells

Many materials have been tried as the counter electrode (CE) material as a substitute to the noble metal Pt in dye-sensitized solar cells (DSSCs). The CE property is critical to the operation of a DSSC as it catalyzes the reduction of I₃^- ions and retrieves the electrons from the photoanode. Here we have explored the application of manganese dioxide (MnO₂) and copper-doped manganese dioxide (Cu-MnO₂) nanoparticles as CE candidates for DSSCs mainly as low-cost alternatives to Pt. A simple hydrothermal method was followed to synthesize α-MnO2 and Cu-MnO2 nanoparticles at a temperature of 140 °C for 14 h. The nanoparticles were characterized to prove its electrocatalytic abilities for DSSCs. DSSC devices fabricated with 10 wt% Cu-MnO₂ as CE showed the best V_OC of 781 mV, I_SC of 3.69 mA/cm², FF of 0.50, and %PCE of 1.7 whereas Pt as CE showed V_OC of 780 mV, I_SC of 14.8 mA/cm², FF of 0.43, and %PCE of 5.83 under 0.85 Sun. The low-cost feature of using Cu-MnO₂ is encouraging to further study the factors that can improve the efficiency of DSSCs with alternative CEs to conventional Pt electrodes.     

Characteristics of the hydrogen ion-sensitive field effect transistors with sol-gel-derived lead titanate gate

The sol-gel-derived lead titanate (PbTiO₃) membrane has been successfully applied as a pH sensitive layer to form the PbTiO₃ gate ion-sensitive field-effect transistor (ISFET). There exhibit the excellent quasi-Nernstian response of 56-59 mV pH⁻¹, good surface adsorption and anticorrosion characteristics via the C-V measurement of the EIS structure. At a specific pH concentration, the output and transfer characteristics are very similar to the behaviours of MOSFETs, and the ISFET model can be derived by the modified MOSFET model. As it operated in the nonsaturation region, there exhibits a linear pH response of about 56-59 mV pH⁻¹. On the other hand, as it operated in the saturation region, the pH response and linearity can be controlled by adjusting the V_GS values, e.g. the pH responses of −4.2, −24.8 and −31.3 μA pH⁻¹ and the correlation coefficients of 0.9491, 0.9995 and 0.9996 at V_GS=1, 3 and 5 V can be obtained, respectively. Besides, in order to get the best pH response and the minimized leakage current, the heat treatment temperature of the PbTiO₃ membrane must be limited between 350 and 450 °C.     

Potentiometric NOx sensor based on stabilized zirconia and NiCr2O4 sensing electrode operating at high temperatures

The two types of electrochemical sensors using stabilized zirconia and the oxide sensing electrode (SE) were developed for NO_x detection at high temperatures. For the mixed-potential-type sensor, NiCr₂O₄ was found to give fairly excellent NO_x sensing characteristics in air among several spinel-type oxides tested. This NO_x sensor provided a linear correlation between EMF and the logarithm of NO or NO₂ concentration in the range 25–436 ppm and in the temperature range 550–650°C. With fixed bias voltage being applied between the SE (oxide) and the counter (Pt) electrode (CE), the EMF between SE and the reference (Pt) electrode (RE) was measured as a sensing signal. The NiCr₂O₄-attached tubular device was found to provide selective response to NO over NO₂ if SE was polarized at +175 mV versus RE. It was also found that this device gave selective response to NO₂ over NO, if SE was polarized at −250 mV versus CE. The new design of the planar device was proposed to avoid the cross-sensitivities to the others gases usually coexisting in car exhausts.     

Analysis of a quasi-reversible two-electron cyclic voltammetric wave for an organometallic ir(III)/ir(I) couple at platinum and mercury electrodes

^*CpIr(η-C₆Me₆)^2+/0 (^*Cpη⁵-C₅Me₅) displays Nernstian two-electron voltammetry at a Hg electrode, but quasi-reversible charge transfer kinetics at solid electrodes. Cyclic voltammetry (CV) peak shapes and separations change drastically from one solvent to another at Pt, ΔE_p values being as small as 170 mV in acetone and as large as 350 mV in CH₃CN (v = 0.03 V/s). These variations arise from changes in the relative E° values of the one-electron Ir(III)/Ir(II) and Ir(II)/Ir(I) couples, and from changes in charge-transfer rates. It is concluded that the Ir(II)/Ir(I) couple has a significantly lower charge-transfer rate than the Ir(III)/Ir(II) couple at platinum electrodes. The sensitivity of the CV curves to the relative E° values allows the approximate determination of the individual E° values for each one-electron process. In contrast, Nernstian conditions allow only the average of the two one-electron E° potentials to be determined. Solvents with higher solvating power are shown to facilitate the thermodynamics of the two-electron transfer process by moving E°₂ positive with respect to E°₁. Possible reasons for the abnormally slow charge transfer rates at Pt electrodes are discussed.     

Interfacial energetics of electrodeposited cadmium selenide in acetonitrile

The open circuit voltage, E_V, was used to estimate the barrier height of thin film CdSe electrodeposited from aqueous selenosulfite solution in contact with various redox couples in acetonitrile. Films that were heat treated in air or oxygen had E_V values that increased approximately linearly with the formal redox potential, E°, in the range −520 mV < E° < +100 mV (SCE) to a maximum of E_v≅ 600 mV. For +100 < E° < +1300 mV, E_v is constant due to Fermi level pinning, a behavior present in single crystal CdSe. Cyclic voltammetry of thin film CdSe in the dark and the light gave useful qualitative information, but E_V values determined from the difference in the anodic peak positions on illuminated CdSe and Pt were smaller than those determined from direct measurement of the open circuit voltage. For redox potentials more negative than the flatband potential (E_FB), all films formed ohmic junctions, which are characterized by reversible electrochemical behavior in the dark and the light. Films that were annealed in the absence of oxygen behaved electrochemically as degenerate semiconductors, since there was no rectification in the dark, even for redox potentials quite positive of E_FB.     

Optimization of ammonia-sensitive metal-oxide-semiconductor structures with platinum gates

Ammonia gas-sensitive MOS capacitors with platinum as a thin active metal gate have been studied. The influence of parameters such as the thickness and area of the platinum film on the ammonia sensitivity was investigated. Thicknesses of about 10 to 30 nm of platinum were found to be favourable for a large response to small ammonia concentrations. It was further observed that with aluminium as a thick contact material, the response to ammonia was independent of the area of the platinum film. Theoretical and experimental C(V curves were compared to elucidate the mechanism behnd the ammonia sensitivity. it is concluded that the sensitivity arises from the thin catalytic Pt film.     

Nouveau diagramme de phase pour le système (1 − x)V2O5 · xPbO dans le domaine x < 23

Phase diagram of the system (1 − x)V₂O₅ · xPbO is revised in the rich V₂O₅ region (x < 0.66). Two new eutectic compositions are evidenced: x = 0.4975 (15) (T_E1 = 478°C) and x = 0.5035 (15) (T_E2 = 480°C). Some melting points are also refined.     

Thermodynamics of solid-state connected ion-sensitive membrane electrodes: The silver-silver chloride system: Part I. Standard potential EM0 at 25, 50, and 75°C

Standard potentials E_M⁰ at 25, 50 and 75°C of all-solid-state silver-silver chloride ring membrane electrodes (Schott) with pressed-in silver foil have been measured with respect to the Pt, H₂ electrode by means of a cell without transference (see also [1]) applied earlier by Bates and Bower who measured standard potentials E⁰ of corresponding electrodes of the 2nd kind. The data evaluated by the extended Debye-Hückel theory can directly be compared with the reported 2nd kind electrode data. Identical thermodynamic behavior of both electrode types is observed; small differences (<1.5 mV) of standard potentials and their temperature dependence are discussed on the basis of different states of electrode materials orignating from different electrode preparation and are applied to calculate thermodynamic data of membrane electrodes referred to those of electrodes of the 2nd kind. The results and contradictory literature data are discussed. A brief characterization of membrane and 2nd kind electrodes is given.     

Selective hydroisomerization of n-dodecane over platinum supported on zeolites

In this study, in order to develop catalysts for the selective isomerization of higher paraffin, the hydroisomerization reaction of n-dodecane was performed as a model reaction. Pt/ZSM-48, Pt/HZSM-5, Pt/HY, and Pt/SAPO-11 were examined for the selective hydroisomerization of n-dodecane. The catalysts were characterized via X-ray powder diffraction, N₂ adsorption, and the temperature-programmed desorption of ammonia. Among the catalysts studied, the Pt/HZSM-48 catalyst exhibited the best isomerization selectivity in the hydroisomerization reaction of n-dodecane, which is attributed to the moderate acid sites and medium-sized pores present in the HZSM-48. The highest iso-dodecane yield was obtained at a reaction temperature of 280 °C in the Pt/HZSM-48 catalyst. The optimal selectivity of the n-dodecane hydroisomerization over the Pt/SAPO-11 catalyst was obtained at approximately 300 °C, which was slightly higher than that of the Pt/HZSM-48 catalyst.     

Über die Phasenbreite von V2O5 im Temperaturbereich von 450°C bis 620°C

About the Homogeneity Range of V₂O₅ in the Temperature Range of 450°C to 620°C The influence of the deposition temperature T₁ on the homogeneity range of V₂O₅-crystalls was investigated by using a solid electrolyte cell. The deviation x in V₂O_5–x from the stoichiometric composition was obtained with: x = 0.0066 at T₁ = 450°C up to x = 0.0326 at T₁ = 620°C.     

Investigations on the determination of NO with galvanic ZrO2 solid electrolyte cells

In order to demonstrate the usefulness of gassymmetrical galvanic ZrO₂ solid electrolyte cells for the determination of NO, cell tensions caused by catalytically different active electrodes and thereby different oxygen partial pressures in N₂/NO mixtures with a low oxygen concentration (<50 vol.-ppm) were measured in the temperature range of 500 to 800°C. Separate investigations demonstrated that the catalytic activity of Pt decreases with increasing sinter temperature (1000 to 1300°C), but is higher than the activity of perovskite type oxides La_1?xSr_xMeO₃ (x=0.1.... 0.5; Me=Co, Mn, Fe, Cr). The activity of the perovskites decreases in the order Co>Mn ≈ Fe>Cr. Between different Pt electrodes changes of cell tension were measured when alternating between pure and NO containing nitrogen (e.g. 19.7 mV with 0.4 vol.-% NO). Cells with a Pt electrode and a perovskite electrode produce higher changes of the cell tension, but without going to zero in pure nitrogen due to own oxygen potentials of the mixed oxides.     

Chloride interference with non-stoichiometric copper sulphide copper(II)-selective electrodes: Part 3. New equation for the electrode response

A general equation for the electrode potential response under metastable equilibrium conditions is derived for the non-stoichiometric copper sulphide electrodes immersed in solutions containing Cu(II) and Cu(I) and the interfering chloride ions. The theoretically predicted “anomalous” slopes (S_II = δ E/δ) log C_Cu(II) of the calibration curves, greater than 29.6 mV at 25° C, were confirmed experimentally in concentrated chloride solutions. The inapplicability of the Nicolsky equation for the electrodes at equilibrium is discussed on the basis of the theory presented. The new relationship (Eqn. 13) can be adapted for other ion-selective electrodes for which the exchange reactions with the solution species are fast enough and mass transport is not inhibited.     

Elektromotorisches Verhalten von Glaselektroden in flüssigem Ammoniak

Glass electrodes behaving as protodes or alkali cation electrodes in aqueous systems respond to the protonated solvent in liquid ammonia at — 38°C and can be used to measure the activity of NH₄⁺. Deviations in the response to the activity of NH₄⁺ are shown to be due to an alkali metal function (alkaline error) of the glass electrodes. The selectivity of glass electrodes for different alkali metal cations changes drastically from water to liquid ammonia.     

Incident investigation on thermal instability of an intermediate using adiabatic calorimeter

Thermal instability is a loss of thermal control which liberates high amount of energy and pressure. An incident took place during drying of an intermediate having amino alcohol functional group in agitated nutsche filter dryer at plant scale. During our investigation using advanced reactive system screening tool (ARSST), thermal decomposition was observed. Onset temperature of decomposition (T _o) is at 85 °C, adiabatic temperature rise due to decomposition (ΔT _ad) is 215 °C, maximum temperature attained due to decomposition (T _max) is 300 °C, maximum self-heat rate (dT/dt)_max is 6,215 °C min^?1, and maximum rate of pressure rise (dP/dt)_max is 1,442 psi min^?1 obtained from ARSST experiments. T _D24 value is 75 °C which was estimated experimentally. The correlations of these results were utilized to identify the root cause of this incident and necessary control measures were taken accordingly.     

Preparation and comparison of Proteus vulgaris and Proteus mirabilis bacterial electrodes for the determination of DL-phenylalanine

Bacterial electrodes for DL-phenylalanine were prepared by immobilizing the bacteria Proteus vulgaris and Proteus mirabilis on an ammonia gas-sensor. The response of the Proteus vulgaris bacterial electrode, when 10 mg of the bacteria was used, had a linear range between 3.0 × 10⁻⁴ and 1.0 × 10⁻² M DL-phenylalanine with a response slope of 43 mV/decade in pH 7.0, 0.1 M phosphate buffer solution at 30°C, while the response of the Proteus mirabilis bacterial electrode, when 3 mg of the bacteria was used, had a linear range between 3.0 × 10⁻⁴ and 3.0 × 10⁻² M DL-phenylalanine with a response slope of 49 mV/decade in pH 7.2, 0.1 M phosphate buffer solution at 30°C. The most important interferents were urea and l-asparagine, and inorganic salts reacted as an inhibitor. The Proteus vulgaris bacterial electrode could be used directly for the determination of DL-phenylalanine in nearly the same linear range during 3 days. On the other hand, the Proteus mirabilis bacterial electrode could be used continuously during 7 days in the above linear range.     

On the oxidation behaviour of monolithic TiB2 and Al2O3-TiB2 and Si3N4-TiB2 composites

In view of the susceptibility of TiB₂ to oxidation, the thermal stability of monolithic TiB₂ and of Al₂O₃-30 vol% TiB₂ and Si₃N₄-20 vol% TiB₂ composites was investigated. The temperature at which TiB₂ ceramic starts to oxidize is about 400°C, oxidation kinetics being controlled by diffusion up toT≈900°C and in the first stage of the oxidation at 1000°C and 1100°C (up to 800 min and 500 min respectively), and by a linear law at higher temperatures and for longer periods. Weight gains in the Al₂O₃-TiB₂ composite can be detected only at temperatures above ≈700°C and the rate governing step of the oxidation reaction is characterized by a one-dimensional diffusion mechanism atT=700°C andT=800°C and by two-dimensional diffusion at higher temperatures. Concerning the Si₃N₄-TiB₂ composite, three different oxidation behaviours related to the temperature were observed, i.e. up to ≈1000°C the reaction detected regards only the second phase; at ≈1000<T<≈1200°C, the diffusion of O₂ or N₂ through an oxide layer is proposed as the rate-governing step; atT〉=1200°C, a linear kinetic indicates the formation of a non protective scale.     

Differential thermal analysis- studies on the crystallization of strontium tungstate from sodium tungstate melts

The kinetics of strontium tungstate crystallization from sodium tungstate melts in platinum crucibles were studied by differential thermal analysis at crystallization temperaturesT ₀=800, 900 and 1000° by continuous cooling at ratesR _T=40, 120 and 200° per hour. Heterogeneous nuclei that first formed on the metal platinate particles in the solution during the induction periods (t) grew to small crystallites (¯l). The main crystal growth started after the development of some excess solute concentration (Δ¯C) at the end of the induction temperatures (¯T). For the first 80% crystallization, the average crystal lengths (l _τ ) varied with the growth time (τ) according to the relation \(l_\tau ^2 = (\bar l)^2 + + 4\bar k_{D_1 } M\Delta \bar C\) where \(\bar k_{D1} \) is the diffusion rate constant at temperatures nearT, andM is the metal salt molecular weight. The initial growth rates and the ratiosl _τ ² /τ depended onΔ¯C instead ofR _T The last 20% growth was controlled only by the rate of development of the excess solute concentration.     

A promising amendment for water splitters: Boosted oxygen evolution at a platinum,titanium oxide and manganese oxide hybrid catalyst

A hybrid catalyst composed of a platinum thin layer and modified with manganese oxide (MnOx) is recommended for the oxygen evolution reaction (OER). The Pt layer of the catalyst was physically sputtered onto a TiOx-coated Si substrate (this TiOx layer was sputtered inbetween the Si substrate and Pt layer to improve their adhesion and prevent their mutual diffusion). On top of the Pt layer, another thin TiOx layer (∼60 nm) was spun before the electrochemical deposition of MnOx. The investigation focused primarily to evaluate the impact of the catalyst’s annealing in oxygen atmosphere on its catalytic activity toward OER. Interestingly, before the modification with MnOx, a large catalytic enhancement both in activity (∼228 mV negative shift at 20 mA cm⁻² if compared to conventional bare Pt catalysts) and stability was achieved at the catalyst annealed at 600 °C toward OER in 0.5 M KOH. Surprisingly, the addition of MnOx to the catalyst synergized a boosted activity amplifying the negative shift to 470 mV at the same current density. Bunch of materials and electrochemical techniques were combined to reveal important remarks about the catalyst’s morphology, structure, composition and intrinsic activity which was attributed to electronic rather than geometric factors.     

High performance heteroaromatic poly(azo-ester)s and their miscible blends: Thermomechanical and conductivity profile

An interesting type of thermally stable and processable poly(azo-ester)s (PAEs) have been synthesized through the polycondensation of a novel diol—(E)-1-(5-(3-hydroxypyridylazo)thiocarbamoyl-aminonaphthyl)-3-(3-hydroxypyridylazo)thiourea, and various diacid chlorides. The dihydroxy compound containing azo group (?N=N?) was prepared via multi-step procedure in which the coupling of bisthiourea compound with diazonium chloride (in alkali) yielded the desired monomer. The polymeric materials were characterized in terms of FTIR, ¹H NMR, solubility, solution viscosity, molecular weight, electrical conductivity, glass transition and thermal degradation temperatures. PAEs possessed high inherent viscosity 1.19–1.23 dL/g and molar mass (8.3–8.5) × 10⁴. The polymers were thermally stable in the range 531–541°C (10% gravimetric loss T ₁₀) having T _g′ = 258–266°C. PAEs were, thus, melt blended with polyaniline resulting in high performance materials that potentially combined the fine thermal properties and processability of poly(azo-ester)s with electrical characteristics of polyaniline. The miscible blends exhibited good heat stability (T ₁₀ = 525–527°C, T _g = 246–252°C) and mechanical strength (61.81–63.19 MPa) compared with several polyaniline-based blends. FESEM showed nano-level homogeneity of the microstructure liable for better electrical conductivity (3.2–4.2 S/cm).     

V<Subscript>3</Subscript>O<Subscript>7</Subscript> · H<Subscript>2</Subscript>O oxide nanostructures: Synthesis and study

Nanorods of orthorhombic V₃O₇ · H₂O with the parameters a = 16.805 Å, b = 9.428 Å, and c = 3.660 Å are prepared under hydrothermal conditions (T = 180–190°C, τ = 30–40 h) from the V₂O₅ · nH₂O/H₂C₂O₄ · 2H₂O composite. The particle diameter is 40–70 nm, and the length is several micrometers. The IR spectra, electric conductivity, and thermal properties of the nanorod powder are studied. In air V₃O₇ · H₂O begins to decompose at temperatures above 150°C, and at 350°C nanobelts V₂O₅ 40–100 nm wide and 40 µm long are formed. A mechanism of nanostructure formation is suggested.