Synthesis of catalytic filamentous carbon on a nickel/graphite catalyst and a study of the resulting carbon-carbon composite materials in microbial fuel cells

The carbon-carbon composite materials obtained via the synthesis of catalytic filamentous carbon (CFC) on a Ni/graphite supported catalyst in the process of the pyrolysis of C₃–C₄ alkanes in the presence of hydrogen were systematically studied. The effects of the following conditions on the catalytic activity expressed as the yield of carbon (g CFC)/(g Ni) and on the character of CFC synthesis on graphite rods were studied: procedures for supporting Ni(II) compounds (impregnation and homogeneous precipitation), the concentrations of impregnating compouds (nickel nitrate, urea, and ethyl alcohol) in solution, graphite treatment (oxidation) conditions before supporting Ni(II) compounds, and the pyrolysis temperature of C₃–C₄ alkanes in the range of 400–600°C. Optimum conditions for preparing CFC/graphite composite materials, which are promising for use as electrodes in microbial fuel cells (MFCs), were chosen. The electrochemical characteristics of an MFC designed with the use of a CFC/graphite electrode (anode) and Gluconobacter oxydans glycerol-oxidizing bacteria were studied. The morphology of the surfaces of graphite, synthesized CFC, and also bacterial cells adhered to the anode was studied by scanning electron microscopy.     

Electroless Ni–P coated on graphite as catalyst for the electro-oxidation of dextrose in alkali solution

Graphite particles were coated with Ni–P by electroless deposition using a conventional bath consisting of a nickel salt and hypophosphite. After 15 min of electroless deposition, the graphite particles were covered with 10 wt% nickel and 0.7–1.0 wt% phosphorus as analysed by wet chemical method. Surface morphology was studied by scanning electron microscopy (SEM). Electrochemical characterisation for the catalytic activity was done by cyclic voltammetry. Pure Ni powder and electroless Ni–P coated on graphite were used as catalysts for the electro-oxidation of dextrose (1.8 × 10⁻³ to 4.5 × 10⁻³ M) in 0.1 M KOH solution. Comparative studies revealed that electroless Ni–P coated on graphite particles acted as a better catalyst than pure Ni powder for catalytic reaction.     

Silver and palladium nanoparticles-containing products of the low-temperature wave conversion of an energetic material: Catalytic activity in piperylene hydrogenation

The hydrogenation of 1,3-pentadiene into pentenes over the commercial 0.5% Pd/Al₂O₃ catalyst and over a new catalyst containing 1.0% Pd and 3.7% Ag (μ-catalyst) has been investigated. The new catalyst has been prepared via the flameless wave conversion of cyclotrimethylenetrinitramine in a porous composite. The catalytic properties of the new composite in the hydrogenation reaction depend on the hydrogen/1,3-pentadiene ratio and on the catalyst activation temperature. The reaction conditions for selective 1,3-pentadiene hydrogenation have been optimized. The pentenes yield as a function of temperature passes through a maximum at any H₂/C₅H₈ ratio between 1 and 2. The 2-pentene/1-pentene ratio in the reaction products increases as the temperature is raised.     

Electrochemical behavior of Ni(II) incorporated in zeolite Y-modified carbon electrode: application for electrocatalytic oxidation of methanol in alkaline solution

Nickel ions were incorporated in NaY zeolite according to cation exchange mechanism. Then NiY zeolite was used as modifier for preparation of modified carbon paste electrode. The electrochemical behavior of NiY-modified carbon paste electrode (NiY/CPE) was studied in alkaline solution using cyclic voltammetry method. Ability of different electrodes containing NiY/CPE, Ni-NiY/CPE, Ni-NaY/CPE, and Ni/CPE for electrocatalytic oxidation of methanol was compared (three last electrodes prepared by open circuit accumulation of Ni(II) ions on the surface of NiY/CPE, NaY/CPE, and bare CPE, respectively). Results show that Ni-NiY/CPE is best catalyst for the electrochemical oxidation of methanol in alkaline solution and both process of earlier Ni ion incorporation through cation exchange in NaY zeolite and open circuit accumulation of Ni ion on the surface of electrode are essential to have good catalyst. Effect of graphite–zeolite ratio on electrocatalytic current was studied and 3:1 ratio of graphite–zeolite was selected as optimum ratio for preparing electrode. Ni-NiY/CPE has very good stability toward the methanol oxidation in concentration range of 0.005 to 0.5 M. Finally, using chronoamperometric method, the catalytic rate constant (k) for methanol was found to be 1.56 × 10⁴ cm³ mol⁻¹ s⁻¹.     

Screen-printed sensor for batch and flow injection potentiometric chromium(VI) monitoring

A disposable screen-printed electrode was designed and evaluated for direct detection of chromium(VI) in batch and flow analysis. The carbon screen-printed electrode was modified with a graphite–epoxy composite. The optimal graphite–epoxy matrix contains 37.5% graphite powder, 12.5% diphenylcarbohydrazide, a selective compound for chromium(VI), and 50% epoxy resin. The principal analytical parameters of the potentiometric response in batch and flow analysis were optimized and calculated. The screen-printed sensor exhibits a response time of 20 ± 1 s. In flow analysis, the analytical frequency of sampling is 70 injections per hour using 0.1 M NaNO₃ solution at pH 3 as the carrier, a flow rate of 2.5 mL·min⁻¹, and an injection sample volume of 0.50 mL. The sensor shows potentiometric responses that are very selective for chromium(VI) ions and optimal detection limits in both static mode (2.1 × 10⁻⁷ M) and online analysis (9.4 × 10⁻⁷ M). The disposable potentiometric sensor was employed to determine toxicity levels of chromium(VI) in mineral, tap, and river waters by flow-injection potentiometry and batch potentiometry. Chromium(VI) determination was also carried out with successful results in leachates from municipal solid waste landfills.     

Preparation, characterization and catalyst application of ternary interpenetrating networks of poly 4-methyl vinyl pyridinium hydroxide-SiO2-Al2O3

In this work, Al₂O₃ was mixed with SiO₂ and poly 4-vinylpyridine by the sol-gel method in order to make a composite which is used as a heterogeneous basic catalyst for Knoevenagel condensation reaction. The physical and chemical properties of the composite catalyst were investigated by XRD, FT-IR, TG, BET and SEM techniques. The catalytic performance of each material was determined for the Knoevenagel condensation reaction between carbonyl compound and malononitrile. The reactions were performed in solvent-free conditions and the product was obtained in high yield and purity after a simple work-up. The effects of the amount of catalyst, amount of monomer for the synthesis of composite and recyclability of the heterogeneous composite were investigated. The composite catalyst used for this synthetically useful transformation showed considerable level of reusability besides very good activity.     

The fractal dimension as estimator of the fractional content of metal matrix composite materials

Electrochemical techniques are applied to estimate the fractal dimension value of electroactive surface structures. However, the fractal dimension value is an abstract concept, which sometimes is hard to understand. Herein, this abstract concept is used to calculate the fractional content of the nickel/graphite–polypropylene hybrid composite material, putting into practice this concept in the study of composite materials.     

Platinum–polytyramine composite material with improved performances for methanol oxidation

Polytyramine (PTy) is shown to be a possible alternative to other conducting polymers as a support material for fuel cell electrocatalysts such as platinum. In this work, a Pt–PTy composite was prepared via potentiodynamic deposition of polytyramine on graphite substrate, followed by the electrochemical deposition of Pt nanoparticles. The material obtained by this straightforward method exhibited, for platinum loadings as low as ca. 0.12 mg cm⁻², a specific electrochemically active surface area of the electrocatalyst of ca. 54 m² g⁻¹, together with a good electrocatalytic activity for methanol oxidation in acidic media, thus ensuring better efficiency of Pt utilization. The system Pt–PTy appears to be worthy of development for methanol fuel cell applications also because the results suggested that, when deposited as small particles in a PTy matrix, platinum is less sensitive to fouling during CH₃OH oxidation.     

Synthesis,characterization, and catalytic activity in the <Emphasis Type="Italic">n</Emphasis>-heptane conversion over Pt/In–Al<Subscript>2</Subscript>O<Subscript>3</Subscript> sol–gel prepared catalysts

Platinum catalysts supported on indium-doped alumina were prepared by the sol–gel method. The method allows the incorporation of In³⁺ in the alumina network. The indium-doped alumina supports showed narrow pore size distribution (5.4–4.0 nm) and high specific surface areas (258–280 m²/g). The ²⁷Al NMR-MAS spectroscopy identified aluminum in tetrahedral, pentahedral, and octahedral coordination; however, the intensity of the signal assigned to aluminum in pentahedral coordination diminishes with the increase of the content of indium. Total acidity determined by ammonia thermodesorption diminishes strongly in Pt/In–Al₂O₃ catalysts, suggesting a selective deposit of platinum over the acid sites of the support. The effect of the support in the platinum catalytic activity was evaluated in the n-heptane dehydrocyclization reaction. The selectivity patterns for such reaction were modified substantially in the doped Pt/In–Al₂O₃ catalysts, in comparison with the Pt-In/Al₂O₃–I coimpregnated reference catalyst. As an important result, the formation of benzene was suppressed totally over the indium-doped alumina sol–gel supports with a high content (3 wt%) of indium.     

Organic–Inorganic Hybrid Catalysts Based on Ordered Porous Structures for Carbon–Carbon Bond Forming Reactions

Two types of organic–inorganic hybrid base catalysts are prepared. Organic-functionalized molecular sieves (OFMSs); in particular, “amine-immobilized porous silicates” are designed based on common idea to immobilize catalytic active sites on silicate surface. Silicate–organic composite materials (SOCMs), such as “ordered porous silicate–quaternary ammonium composite materials”, are the precursors of ordered porous silicates obtained during the synthesis. Both the OFMS and the SOCM are used as the catalysts for Knoevenagel condensation and Michael addition reactions. Among the OFMSs, there is clear tendency that the use of molecular sieve with larger pore volume and/or surface area gives the product in higher yield. Aminopropylsilyl (AP)-tethered mesoporous silicate such as AP-MCM-41 gives the Knoevenagel condensation product in high yield under mild conditions. No loss of activity is observed after repeated use for three times. The SOCMs are also active for the same reaction. The OFMSs are effective when the supports have large pore volume and/or surface area and the reaction is carried out in polar solvents ethanol and DMF. However, the activity of the OFMSs is considerably low in a non-polar solvent such as benzene. In contrast, the SOCMs are remarkably active in benzene. The organic cation–MCM-41 composite is more active than the composite of an organic cation and a microporous silicate such as zeolite beta and ZSM-12. In the SOCM catalysts, (SiO)₃SiO⁻(⁺NR₄) moieties located at the accessible sites are considered to play some important roles. The active species are absent in the liquid phase after the reaction. The recycle of the catalyst was possible without significant loss of activity when the substrates are enough reactive. The mechanism of the reaction over SOCM catalyst is discussed.     

Catalytic and physicochemical properties of Pt/α-GeO<Subscript>2</Subscript> systems in reaction of selective hydrogenation of α,β-unsaturated aldehydes in a gas phase

Hydrogenation of crotonaldehyde in a gas phase over Pt/α-GeO₂ catalysts was investigated. The systems were characterized by BET, XRD, TPR, TEM, ToF-SIMS, and FTIR methods. The optimum pretreatment parameters were studied. The best catalytic performance shows the catalyst 5 wt % Pt/α-GeO₂ (69% selectivity to crotyl alcohol at 200 μmol s⁻¹ g _Pt ⁻¹ activity and 10% conversion of crotonaldehyde). Lower loaded catalysts (2 and 1 wt % Pt) show lower, but also promising activity and selectivity. This good catalytic performance was related to the physicochemical properties of the catalyst. GeO₂ in the presence of Pt undergoes a partial surface reduction at temperatures higher than 100°C probably leading to the creation of the active Pt-Ge centers responsible for high selectivity to crotyl alcohol. Reduction at a temperature≥200°C deactivates the catalytic systems due to the formation of inactive PtGe alloys. Published in Russian in Kinetika i Kataliz, 2007, Vol. 48, No. 4, pp. 600–605. This article was submitted by the authors in English.     

Determining the orientations of BrF3 and FeBr3 molecules in graphite fluoride matrices using the XANES and EXAFS polarization dependences

Synchrotron radiation was used to measure the EXAFS and XANES polarization dependences for intercalation compounds of graphite fluoride. An approach is developed which allows one to analyze the orientation of molecules of arbitrary shapes using XANES and EXAFS data. Analyzing the orientation dependences of BrK XANES spectra for the T-shaped BrF₃ molecules, we determined possible combinations and admissible ranges of angles between the normal to the graphite fluoride matrix planes and the Br−F bond directions (α=52–90°, β=27–82°) and between the normal to the matrix planes and the molecular planes (γ=27–53°). The average orientation angles obtained by the combined analysis of the EXAFS and XANES data are as follows: α=62±1.5°, β=58±1.5°, γ=45±1.5°. The interatomic distances Br−F, Br−Br, and Fe−Br are determined. It is established that thermal treatment, which recovers the X-ray diffraction pattern from the unfilled matrix, does not affect the predominant orientation of the BrF₃ molecules. This suggests that the thermally treated graphite fluoride matrix contains thin layers of ordered molecules. The absence of the polarization dependence of the spectra of FeBr₃ in graphite fluoride allows the assumption that the molecular planes are oriented with respect to the normal to the matrix planes at a “magic” angle of 35°. Institute of Inorganic Chemistry, Siberian Branch, Russian Academy of Sciences. Translated fromZhurnal Strukturnoi Khimii, Vol. 36, No. 6, pp. 1020–1029, November–December, 1995. Translated by I. Izvekova     

Preparing graphene oxide–copper composite material from spent lithium ion batteries and catalytic performance analysis

The wide use of lithium ion batteries (LIBs) has created much waste, which has become a global issue. It is vital to recycle waste LIBs considering their environmental risks and resource characteristics. Anode graphite from spent LIBs still possess a complete layer structure and contain some oxygen-containing groups between layers, which can be reused to prepare high value-added products. Given the intrinsic defect structure of anode graphite, copper foils in LIB anode electrodes, and excellent properties of graphene, graphene oxide–copper composite material was prepared in this work. Anode graphite was firstly purified to remove organic impurities by calcination and remove lithium. Purified graphite was used to prepare graphene oxide–copper composite material after oxidation to graphite oxide, ultrasonic exfoliation to graphene oxide (GO), and Cu²⁺ adsorption. Compared with natural graphite, preparing graphite oxide using anode graphite consumed 40% less concentrated H₂SO₄ and 28.6% less KMnO₄. Cu²⁺ was well adsorbed by 1.0 mg L^?1 stable GO suspension at pH 5.3 for 120 min. Graphene oxide–copper composite material could be successfully obtained after 6 h absorption, 3 h bonding between GO and Cu²⁺ with 3/100 of GO/CuSO₄ mass ratio. Compared to CuO, graphene oxide–copper composite material had better catalytic photodegradation performance on methylene blue, and the electric field further improved the photodegradation efficiency of the composite material.     

Catecholase biomimetic catalytic activity of copper(II) complexes with 2-methyl-3-amino-(3H)-quinazolin-4-one

The oxidation of catechol by molecular oxygen in the presence of a catalytic amount of copper(II) complex with 2-methyl-3-amino-(3H)quinazoline-4-one (MAQ) and various anions (Cl⁻, Br⁻, ClO ₄ ⁻ , SCN⁻, NO ₃ ⁻ and SO ₄ ^– ) was studied. The catecholase biomimetic catalytic activity of the copper(II) complexes has been determined spectrophotometrically by monitoring the oxidative transformation of catechol to the corresponding light absorbing o-quinone (Q). The rate of the catalytic oxidation reaction was investigated and correlated with the catalyst structure, time, concentration of catalyst and substrate and finally solvent effects. Addition of pyridine or Et₃N showed a dramatic effect on the rate of oxidation reaction. Kinetic investigations demonstrate that the rate of oxidation reaction has a first order dependence with respect to the catalyst and catechol concentration and obeying Michaelis–Menten Kinetics. It was shown that the catalytic activity depends on the coordination environment of the catalyst created by the nature of counter anions bound to copper(II) ion in the complex molecule and follows the order: Cl⁻ > NO ₃ ⁻ > Br⁻ > SO ₄ ^– > SCN⁻ > ClO ₄ ⁻ . To further elucidate the catalytic activity of the complexes, their electrochemical properties were investigated and the catecholase mimetic activity has been correlated with the redox potential of the Cu²⁺/Cu⁺ couple in the complexes.     

Synthesis of highly ordered mesoporous CeO<Subscript>2</Subscript> and low temperature CO oxidation over Pd/mesoporous CeO<Subscript>2</Subscript>

Highly ordered mesoporous cerium dioxide (meso-CeO₂) was successfully synthesized using a facile solvent-free infiltration method from a mesoporous silica template, KIT-6. The meso-CeO₂ material, thus obtained, exhibited well-defined mesostructure and high surface area (153 m² g⁻¹). The physicochemical properties of meso-CeO₂ material and Pd-supported on meso-CeO₂ (Pd/meso-CeO₂) were characterized by electron microscopy, X-ray diffraction, N₂ adsorption–desorption, and temperature-programmed experiments. The Pd/meso-CeO₂ catalyst exhibited excellent catalytic activity for CO oxidation compared with those of other Pd/CeO₂ catalysts which were prepared using nanocrystalline CeO₂ and bulk-CeO₂ as the supports. Moreover, a hydrogen pretreatment of the Pd/meso-CeO₂ catalyst resulted in a remarkable increase of catalytic activity (T ₁₀₀ = 52 °C).     

Preparation and properties of a new composite photocatalyst based on nanosized titanium dioxide

The use of photocatalysts supported on adsorbents is receiving substantial attention. Supporting TiO₂ with zeolites is found to be one of the best solutions to increase the efficiency of TiO₂-based photocatalysts. This work was focused on simple preparation of a TiO₂/Na-ZSM-5 composite catalyst by the solid state dispersion (SSD) method and its modification with an organic photosensitizer — polythiophene (PT). Using the XRD diffractometry, structure of the new composite catalyst was proved. Beside this composite catalyst, mechanical mixtures of TiO₂-based catalysts with Na-ZSM-5 zeolite were prepared. The efficiency of all five available photocatalysts (TiO₂, TiO₂-PT, mechanical mixture of TiO₂ + Na-ZSM-5, mechanical mixture of TiO₂-PT + Na-ZSM-5, and the modified SSD-PT composite) on photodegradation of 4-chlorophenol was compared. By measuring the formation of chloride ions and decreasing the 4-chlorophenol concentration at two different initial concentrations of 4-chlorophenol in the basic aqueous solution, the photoefficiency and adsorption properties of our photocatalysts were determined. Presented at the 35th International Conference of the Slovak Society of Chemical Engineering, Tatranské Matliare, 26–30 May 2008.     

Selective catalytic reduction of NO with CO on Pt/W–Ce–Zr catalysts

Various Pt catalysts (Pt/ZrO₂, Pt/CeO₂, Pt/CeZrO, Pt/WO₃/ZrO₂ and Pt/WO₃/CeZrO) were prepared and characterized, and their catalytic reduction reactions of NO by CO, with or without the presence of excess oxygen, were investigated. The results of temperature-programmed experiments showed that CO could be easily oxidized over Pt/CeO₂ and Pt/CeZrO while the introduction of WO₃ into the catalyst (Pt/WO₃/CeZrO) inhibited the reduction of catalyst surface; NO could not dissociate over those catalysts in oxidized state but after CO reduction at a low temperature, NO dissociation took place only over Pt/CeO₂ and Pt/CeZrO catalysts. For NO + CO reaction, those easily reduced catalysts Pt/CeO₂ and Pt/CeZrO exhibited better catalytic performances, and NO could be rapidly converted below 350 °C. For the reaction with the presence of excess O₂, the NO conversions were significantly inhibited, but better NO conversions were obtained over the tungstate-contained catalysts when compared with Pt/CeO₂ and Pt/CeZrO. The higher activities of Pt/W–Ce–Zr catalysts were attributed to their high acidities.     

Influence of the nickel content on the electrocatalytic activity of thin nanostructured Co–Te–Ni–O films

The influence of nickel addition in Co–Te–O catalytic films, obtained by vacuum co-evaporation of Co, Ni, and TeO₂ on electrocatalytic activity toward oxygen reactions in alkaline media has been investigated. Bifunctional gas-diffusion oxygen electrodes were prepared by direct deposition of catalyst films on gas-diffusion membranes consisting of hydrophobized carbon blacks. The method used allows the deposition of nanostructured films consisting of intertwined nanowires with high surface area. Thus, obtained electrodes with different atomic ratio R _(Co+Ni)/Te of the catalyst, fresh and thermally treated at 100 °C temperatures were electrochemically tested by means of cyclic voltammetry and steady-state voltammetry. It has been shown that the partial replacement of Co with about 30 at.% Ni leads to the increase in the film catalytic activity toward oxygen evolution reaction.     

Characterization and catalytic performance of sol–gel derived Cu/SiO<Subscript>2</Subscript> catalysts for hydrogenolysis of diethyl oxalate to ethylene glycol

A series of Cu/SiO₂ catalysts with copper loadings ranging from 17.8 to 42.2 wt% were prepared by the sol–gel method and evaluated for the hydrogenolysis of diethyl oxalate to ethylene glycol. The physicochemical properties of these catalysts were systematically characterized by means of different techniques. It is found that copper loadings have great influence on the catalytic performance; the catalyst with a copper loading of 37.8 wt% exhibited the best activity and ethyl glycol selectivity. The sol–gel derived catalyst was superior in catalytic performance to the catalyst prepared by the deposition precipitation method, a result due to the presence of finely dispersed copper phyllosilicate.     

Development of nano IrO<Subscript>2</Subscript> composite-reinforced nickel–phosphorous electrodes for hydrogen evolution reaction

Electroless and electroplated nickel electrodes are extensively used for hydrogen evolution reaction (HER). In the present work, TiO₂-supported IrO₂ mixed oxide composite was prepared and used to reinforce Ni–P electroless plates to be used as catalytic electrodes for HER. The electrodes exhibited high electrocatalytic activity when the electrodes were used for HER. All the parameters including particle size of the catalyst, surface roughness, and surface active sites were studied. The particle size of the IrO₂ catalyst in the mixed oxide was found to have high influence on the catalytic activity of the electrodes. Low overpotential as low as 70 mV at a current density of 200 mA cm⁻² was achieved with the mixed oxide-reinforced Ni–P electrodes.