Hydrogen–oxygen fuel cells

Ion exchange non-fluorinated membranes were tested in half-cells used as models for hydrogen–oxygen fuel cells. The lower acidity of the membranes allowed us to reduce the chemical stability requirements for the construction and catalytic materials. The maximum energy yield at room temperature was close to 65% at a current density of 40–60 mA cm^–2.Presented at the 3rd International Meeting on Advanced Batteries and Accumulators, 16–20 June 2002, Brno, Czech Republic     

Production of chiral matrices with hybrid silver–thiocholesterol nanosystems and study of their properties

A new type of chiral matrix based on silver–thiocholesterol hybrid nanosystems adsorbed on silica gel has been proposed. The molar ratio of stabilized thiocholesterol (L) ligand and silver (Ag) was found to have little effect on the size of the resulting silver nanoparticles (SNPs). The average diameter of SNPs was 2.7 ± 0.4, 2.2 ± 0.4, and 2.1 ± 0.6 nm upon the ratios Ag: L = 1: 5, Ag: L = 1: 2, and Ag: L = 1: 0.5, respectively. The resulting chiral matrices possess enantioselectivity relative to the 1,1’-binaphthyl-2,2’-diamine (BNDA) and trifluoroanthranyl ethanol (TFAE) optical isomers. The TFAE optical isomers were successfully separated using thin layer chromatography (α = 1.56).     

Comparative characteristics of cathodes with different catalytic systems in hydrogen–oxygen and hydrogen–air fuel cells with proton-conducting polymer electrolyte

The characteristics of low-temperature hydrogen–oxygen (air) fuel cell (FC) with cathodes based on the 50 wt % PtCoCr/C and 40 wt % Pt/CNT catalysts synthesized on XC72 carbon black and carbon nanotubes (CNT) are compared with the characteristics of commercial monoplatinum systems 9100 60 wt % Pt/C and 13100 70% Pt/C HiSPEC. It is shown that the synthesized catalysts exhibit a high mass activity, which is not lower than that of commercial Pt/C catalysts, a high selectivity with respect to the oxygen reduction to water, and a significantly higher stability. The characteristics of PtCoCr/C and Pt/CNT were confirmed by testing in the hydrogen—oxygen FCs. However, when air was used at the cathode, especially in the absence of excessive pressure, a voltage of FC with the cathode based on PtCoCr/XC72 is lower as compared with the commercial systems. Probably, this is associated with the transport limitations in the structure of trimetallic catalyst synthesized on XC72 carbon black due to the absence of mesopores. This drawback was eliminated to a large extent by raising the volume of mesopores as a result of application of mixed support (XC72 + CNT) and the use of only CNT for the synthesis of the monoplatinum catalyst. However, this did not eliminate another drawback, namely, a low platinum utilization coefficient in the cathode active layer as compared with that measured under the model conditions in the 0.5 M Н₂SO₄ solution. Therefore, further research is required to improve the structure of the catalytic systems, which are synthesized both on carbon black and nanotubes, while maintaining their high stability and selectivity.     

TG–DSC–FTIR–MS study of gaseous compounds evolved during thermal decomposition of styrene-butadiene rubber

The thermal decomposition behavior of styrene-butadiene rubber was studied using a system equipped with thermogravimetric analysis, differential thermal analysis, Fourier transform infrared spectroscopy, and mass spectroscopy. Two different experiments were conducted. From these experiments, thermogravimetric analysis results indicated a mass loss of 58 % in the temperature range of ~290–480 °C and a mass loss of 39 % in the temperature range beyond 600 °C. Scanning electron microscopy coupled with energy-dispersive X-ray spectroscopy confirmed the presence of oxides, even at 1,000 °C, accounting for the Zn, Mg, Al, Si, and Ca in the original sample.     

Ab initio study on mechanisms of singlet oxygen reaction with ethylene

The reaction of singlet oxygen with ethylene has been studied at the ab initio level with both HF/3-21G and HF/6-31G basis sets, fully optimizing the geometries of the critical points. The transition state leading to the intermediate peroxirane from the initial reactants is found,Iocated at 81.71 kJ/mol above the dissociation limit. The vibrational analysis is done with two basis sets. From the results it can be seen that the frequencies have not been made an improvement obviously with augmented 6-31G compared to 3-21G basis; it follows that main reason for too high HF/3-21G frequency could mainly be the vibrational anharmonicity. The eigenvector corresponding to the single imaginary vibrational frequency is dominated by the larger O-O distance. The finding of the transition state confirms that the peroxirane minimum can be reachable passing through a peroxirane-like saddle point. In addition , the mechanisms of the reaction forming oxirane are discussed as well.     

Studies on the oxygen sensitivity and microstructure of sol–gel based organic–inorganic hybrid coatings doped with platinum porphyrin dye

Hybrid organic–inorganic nanocomposite coatings were prepared by copolymerizing tetraethylorthosilicate with ethyltriethoxysilane with an acid catalysis process. Oxygen sensor coatings were fabricated by doping the hybrid sol with platinum meso-tetra(pentfluorophenyl) porphyrin. Photophysical properties and oxygen sensitivity of the sensor coatings were studied. The microstructure of the coatings was examined using optical microscopy and scanning electron microscopy. The effect of sol–gel process conditions like precursor silane molar ratio, acid concentration and stirring time of the sol on the oxygen sensitivity and surface microstructure of the sensor coating was studied. Oxygen sensitivity and surface morphology of the coatings were dependent on the sol–gel process parameters.     

Suppression of laminar flames of natural gas–oxygen mixtures with complex obstacles

It has been experimentally shown that a complex obstacle consisting of two confusers oriented in opposite directions of a cylindrical vessel completely prevents the propagation of diluted methane – oxygen flames, i.e., the obstacle is the most effective flame arrester; the theoretical predictions are consistent with the experiments.     

Characterization and electrochemical study of hemoglobin–carbon nanoparticles–polyvinyl alcohol nanoporous hybrid film

A hybrid film is fabricated by casting hemoglobin (Hb)–carbon nanoparticles (CNPs)–polyvinyl alcohol (PVA) suspension on glassy carbon electrode (GCE). The resulting film shows a three-dimensional nanoporous structure. In the hybrid film, the ultraviolet visible (UV–Vis) absorption spectra of Hb keep almost unchanged. The organic–inorganic hybrid material can promote the direct electron transfer of Hb. A pair of well-defined and quasireversible peaks with a formal potential of −0.348 V (vs saturated calomel electrode) is obtained, which is caused by the electrochemical reaction of the Fe(III)/Fe(II) couple of Hb. The electron transfer rate constant (k _s) is estimated to be 3.9 s⁻¹. The immobilized Hb exhibits high stability and excellent electrochemical catalysis to the reduction of oxygen (O₂), hydrogen peroxide (H₂O₂), and nitrite (). The catalytic currents are linear to the concentrations of H₂O₂ and from 1.96 to 112 μM and from 0.2 to 1.8 mM, respectively. Therefore, the hybrid film may be a good matrix for protein immobilization and biosensor fabrication.     

First-principles study of the electronic structures of α-rhombohedral boron codoped with lithium and oxygen

α-Rhombohedral (α-rh) boron, which is the most stable of boron's polymorphs at low temperatures, has p-type semiconductive properties. There have been some attempts to dope the interstitial sites with alkali atoms to create metallic or n-type semiconductive α-rh boron, but this has yet to be achieved. In a previous work, we proposed the codoping of α-rh boron with Li and P or As, and revealed from first principles calculations that B₁₂PLi and B₁₂AsLi could be synthesized and become narrow-gap semiconductors. The band structure suggested that the mobility of electrons might be greater than that of holes. In this paper, based on these prospective results, we selected a new combination of dopants, Li and O, and theoretically studied such compounds as B₁₂OLi and B₁₂O₂Li. The results showed that both of these materials are metallic, while the reaction energies of the Li insertion into B₁₂O and B₁₂O₂ are lower (more unstable) than with B₁₂PLi and B₁₂AsLi. It was proved that the differences in the electronic structures are caused by the dangling bonds of the dopant atoms, O, P and As.     

Computer aided simulation of hydrogen–oxygen (air) fuel cell with regard to the degradation mechanism of platinum catalyst on the cathode

A mathematical model of a hydrogen–oxygen (air) fuel cell that takes into account the phenomena of degradation of the cathodic platinum catalyst is presented. For potential cycling from 0.6 to 1.1 V with a scan rate of 0.1 V/s, depending on the platinum loadings, the following factors are found to prevail in the mechanism of electroactive surface degradation: the coalescence of platinum nanoparticles at large loadings and the platinum dissolution/redeposition and diffusion to the membrane at medium and low loadings. Based on mathematical simulation, the data on the discharge curves are calculated. The observed decrease in the discharge characteristics is attributed to the degradation of the catalyst active surface and the increased transport losses during accelerated stress testing.     

Penetration of methane–oxygen flames through flat obstacles with several openings

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HPIC–UV–ICP–SFMS study of the interaction of cisplatin with guanosine monophosphate

Interaction of cis-[Pt(NH₃)₂Cl₂] (cisplatin) with 5′-guanosine monophosphate (5′-GMP) has been investigated for the first time by on-line coupling of high performance ion chromatography (HPIC) to inductively coupled plasma sector field mass spectrometry (ICP–SFMS). The time-dependent reaction course of the cisplatin-5′-GMP system was followed after incubation under simulated physiological conditions by monitoring the decrease in the concentration of 5′-GMP and the increase in the concentration of formed adducts, on the basis of speciation analysis. Because of the two-step mechanism an intermediate mono adduct was observed together with the major product, the bis adduct cis-[Pt(NH₃)₂(GMP)₂]^2–. The data obtained correlated well with those from earlier studies employing orthogonal techniques such as capillary electrophoresis (CE). Furthermore, HPIC–ICP–SFMS provided unambiguous stoichiometric information about the major GMP-adduct. For this purpose the platinum-to-phosphorus ratio was determined by simultaneously measuring ³¹P and ¹⁹⁵Pt. To separate significant interferences from ¹⁵N¹⁶O⁺, ¹⁴N¹⁶O¹H⁺, ¹²C¹⁸O¹H⁺, and ¹³C¹⁷O¹H⁺ on ³¹P, high-mass resolution (m/Δm = 4500) proved to be mandatory. The P/Pt signal ratio of 2/1 obtained corresponds to the molar ratio in the bis adduct cis-[Pt(NH₃)₂(GMP)₂]^2–.     

Rocket Engine with Continuous Detonation Combustion of the Natural Gas–Oxygen Propellant System

In a demonstrator of a detonation rocket engine (DRE) using the natural gas–oxygen propellant system, a high (270 s) specific impulse at sea level at a low (32 atm) mean combustor pressure was experimentally obtained for the first time. Comparison of these characteristics with the respective ones (263 s and 61 atm) of the well-known Russian RD 170-A liquid-propellant rocket engine using deflagration combustion of the kerosene–oxygen propellant system showed that the specific impulse at sea level in the DRE is close to that in the deflagration-combustion engine but is produced at half as high a mean combustor pressure. This indicates that the energy efficiency of detonation combustion exceeds that of deflagration combustion, and that there is room to improve the weight–size characteristics of the turbopump unit in the DRE.     

Characterization of the physical–mechanical properties of dental resin composites reinforced with novel micro-nano hybrid silica particles: An optimization study

Abstract

In the study, dental composites of color A2 using Bis-GMA/UDMA/TEGDMA resins (ratios 70/10/20), and silica filler (70%wt, 75%wt, and 80%wt) which is a hybrid of two silica types in nano and micro dimensions were made using two different photoinitiators namely BAPO and camphorquinone. The optimum photoinitiator was selected based on the mechanical tests results after which the composites were subjected to the following tests: FTIR to evaluate polymerization degree, microhardness test, UTM, and SEM micrographs were taken to analyze the surface fracture of samples. The results of photoinitiator selection (flexural strength test) is 36.54?MPa, 37.62?MPa, and 75.08?MPa for BAPO?+?camphorquinone, camphorquinone, and BAPO respectively. The results show that the BAPO photoinitiator exhibits better results over camphorquinone and also BAPO/camphorquinone initiator systems. Then after choosing the photoinitiator system composites with different filler contents show higher mechanical strength than existing dental composites. The results of the mechanical tests for the composites with different filler contents synthesized after initiator system selection were significantly higher than the values specified in ISO 4049:2009 (102?MPa over 80?MPa). FTIR results indicate that the degree of conversion in these composite is 25.41%, 37.68, and 40.94% for composites with different filler amounts.     

Development of hydrogen–air fuel cells with membranes based on sulfonated polyheteroarylenes

Proton-conducting membranes based on sulfonated polynaphthoyleneimide (PNI) and polytriazole (PTA) are synthesized that can be used in portable hydrogen–air fuel cells (HAFC). Membrane–electrode assemblies (MEAs) based on sulfonated PNI and PTA membranes in individual HAFC manifested power and voltammetric characteristics exceeding the characteristics of MEA based on the commercial Nafion-212 membrane. Thus, the current density of 320 mA cm^–2 and the power density of 160 mW cm^–2 are obtained at the room temperature with no pressure or gas humidification at the voltage of 0.5 V. Also activity of the oxygen electroreduction Pt–Fe/C (30 wt % of metals in total) catalyst synthesized on the basis of coordination compounds is tested in MEA HAFC. It is shown that the values of power for MEAs with the cathodic Pt–Fe/C catalyst at the voltage of 0.5 V, at the room temperature, without additional pressure and gas humidification considerably exceed the corresponding values for MEAs with the commercial E-TEK 20% Pt/C catalyst.     

Detailed kinetic computations and experiments for the choice of a fuel–oxidiser couple for hybrid propulsion

The choice of a solid reducer for hybrid propulsion is generally based on the quantity of gaseous combustible it can produce (expressed indirectly by the regression rate). For this reason, the studies focus on the use of additives or on the design of grain while the kinetic aspect is rarely of interest despite the chemistry drives the phenomena (chemical induction delay, heat absorption, and chemical composition). One-step mechanisms are first considered in this paper to quantify the effect of operating conditions on high density polyethylene (HDPE), polymethylmethacrylate (PMMA) and hydroxyl termination polybutadiene (HTPB). Then the chemical composition of pyrolysis products is determined for a large range of operating conditions with highly detailed mechanism for HDPE (1014 species and 7541 reactions). The heating rate applied to the reducer is investigated (from 1 K s⁻¹ to 10⁷ K s⁻¹). Ethylene is found to be the major pyrolysis product. The timescale found over 1250 K and 11.11 bar is in agreement with the requirements of hybrid propulsion. The calculated data are compared to experimental ones. Finally, a short combustion study with detailed chemistry (over 700 species and 3000 reactions) is proposed because it impacts directly on the pyrolysis through the generated heat flux. It allows considering the oxidiser decomposition (hydrogen peroxide (H₂O₂) and nitrous oxide (N₂O)). Pure oxygen (O₂) is considered as reference data. The effect of atmosphere (inert or oxidative) on the pyrolysis is shown. The kinetic computations of N₂O combustion give higher flame temperatures than for H₂O₂. Ignition times, below a few milliseconds, are obtained for all the reducers over 1250 K. Finally, the HDPE/H₂O₂ and HTPB/N₂O couples are found to be the most interesting.     

Spectroscopic study of TMOS–TMSM–MMA gels: Previously identification of the networks inside the hybrid material

A 3-(trimethoxy-silyl)propyl methacrylate (TMSM)–methylmethacrylate (MMA)–tetramethyl-orthosilicate (TMOS) hybrid glass, has been prepared using a sol–gel process. In order to study the influence of each of the inorganic matrices, the gels obtained from TMOS and TMSM have been studied separately, the hybrid compound, they have been investigated using Raman spectroscopic, FT-IR and NMR techniques. The networks formed in both TMOS and TMSM gels have been identified. Upon condensation of TMOS a tridimensional array including defect was formed, that results in a certain discontinuity of the material. Nevertheless, the characteristics of this structure have that of molten quartz (glassy silica). By contrast, room temperature condensation of TMSM gave rise to several structurally different species in suspension in the gel. The species have been identified. The insertion of TMSM in an organic network modified its degree of periodicity. The integration of TMOS into a silica network occurred through the formation of rings which link together various silica blocks originated from TMOS. Interpretation of Raman diffusion data shows that the glass still contains non-condensed silanol groups and that low molecular weight cyclic, caged polysilsesquioxanes are formed from condensed TMSM. No organic–inorganic phase separation has been observed. The organic part of the glass has been investigated by Raman Spectroscopy from a microscopic point of view. It has helped understand the competition between condensation and polymerization, and it has been shown that polymerization was not fully completed. This has been confirmed by DSC. Raman spectra have also shown that the inorganic network was mainly three-dimensional. NMR studies confirmed that condensation occurred several times on the active SiO bonds.     

TG–MS analysis of thermal behavior and gaseous emissions during co-combustion of straw with municipal sewage sludge

The thermal behavior and gas product distribution during combustion of straw (wheat straw, corn stalks, and cotton stalks), municipal sewage sludge (MSS), and their blends were investigated by thermogravimetry–mass spectroscopy. The experiments were conducted with various blending ratios and temperatures ranging from 323 to 1,173 K. Addition of MSS decreased the combustion performance of the straw. The reactions between wheat straw and corn stalks with MSS proceeded more easily than that of cotton stalks. Significant interactions were observed between the straw and MSS at the char combustion stage. Gaseous species (CO₂, SO₂, NH₃, HCN, and NO) were mainly produced at temperatures of 523–873 K at which most of the mass loss occurred. Higher MSS proportions in the blends resulted in lower emissions peaks for CO₂, NH₃, HCN, and NO except for SO₂. To ensure combustion performance and mitigate problematic gaseous emissions, the proportion of MSS added to the blends should be <30 mass%.     

Comparison of performances of bioanodes modified with graphene oxide and graphene–platinum hybrid nanoparticles

The performances of graphene oxide (GO) and graphene–platinum hybrid nanoparticles (Gr-Pt hybrid NPs) were compared for biofuel cell (BFC) systems. This is the first study that constitutes these nanomaterials in BFC systems. For this purpose, fabricated bioanodes were combined with laccase modified biocathode in a single cell membraneless BFC. Power and current densities of these systems were calculated as 2.40 μW cm^− 2 and 211.90 μA cm^− 2 for GO based BFC and 4.88 μW cm^− 2 and 246.82 μA cm^− 2, for Gr-Pt hybrid NPs based BFC. As a result, a pioneer study which demonstrates the effective performances of combination of graphene with Pt was conducted.