Methanol-resistant cathodic oxygen reduction catalysts for methanol fuel cells

Efforts were made to simplify the structure of Ru-based catalysts, and to tailor industrially practicable methanol insensitive oxygen reduction catalysts both by thermolysis of Ru-carbonyls in organic solvents and by modified preparation techniques of Ru colloids. Selective catalysis was found to be essentially independent of the chalcogene (Se) used which, however, is a crucial factor for facilitating efficient electron transfer. All preparations contained Ru-metal particles of nm size, the surfaces of which were modified by carbonyl and carbido-carbonyl complexes or carbon compounds. The role of carbon as ligand to Ru clusters stabilizing the Ru interface against oxidation and in promoting catalytic electron exchange via nonbonding Ru d-states is theoretically analysed in a model calculation. An analogy is drawn to a biological Fe – only hydrogenase centre in order to discuss projected key experiments for optimizing reduction catalysis: the stabilization of small, inherently unstable catalytic metal clusters by CO or CN and their linking via electron bridges such as S and Se to electron reservoirs (metal colloids).     

Non-catalyzed cathodic oxygen reduction at graphite granules in microbial fuel cells

Oxygen is the most sustainable electron acceptor currently available for microbial fuel cell (MFC) cathodes. However, its high overpotential for reduction to water limits the current that can be produced. Several materials and catalysts have previously been investigated in order to facilitate oxygen reduction at the cathode surface. This study shows that significant stable currents can be delivered by using a non-catalyzed cathode made of granular graphite. Power outputs up to 21 W m⁻³ (cathode total volume) or 50 W m⁻³ (cathode liquid volume) were attained in a continuous MFC fed with acetate. These values are higher than those obtained in several other studies using catalyzed graphite in various forms. The presence of nanoscale pores on granular graphite provides a high surface area for oxygen reduction. The current generated with this cathode can sustain an anodic volume specific COD removal rate of 1.46 kg_COD m⁻³ d⁻¹, which is higher than that of a conventional aerobic process. This study demonstrates that microbial fuel cells can be operated efficiently using high surface graphite as cathode material. This implies that research on microbial fuel cell cathodes should not only focus on catalysts, but also on high surface area materials.     

An investigation of cathodic oxygen reduction beneath an intact organic coating on mild steel and its relevance to cathodic disbonding

An epoxy-coated mild steel panel was coupled with bare mild steel to characterise the cathodic reaction underneath the paint and study the short term change in properties of the coating under cathodic polarisation. It showed that the cathodic reaction obeys the Tafel law and is not controlled by either the high coating resistance or oxygen transport through the coating.     

Substrate effect on oxygen reduction electrocatalysis

The oxygen reduction reaction (ORR) was investigated on carbon (XC-72) supported platinum nanoparticles, generated via the carbonyl chemical route and on oxide composites supported platinum generated via the UV-photo-deposition technique in sulfuric acid medium. The behavior of Pt/C was examined using a careful dosing of the catalyst loading spanning the range from 4.3 to 131 μg cm⁻². The ORR electrochemical response of Pt/C (in line with recent literature data) is put into contrast with the Pt/oxide-composite systems. Our results point out that it is possible to use smaller amounts of catalyst for the ORR when platinum atoms interact with the oxide (anatase) surface of the substrate composite. Evidence of the incipient metal-substrate interaction is discussed in the light of the results of XRD experiments.     

Determination of the oxygen reduction products on ASTM A516 steel during cathodic protection

The electrochemistry of steel in aerobic and anaerobic aqueous alkaline solutions was studied with or without forced convection to investigate the cathodic processes occurring on steel exposed by defects in polymer coated steel pipe. The results are relevant to the mechanistic understanding of the effect of cathodic protection on the disbonding of fusion bonded epoxy (FBE) coatings on steel. Moderate (pH9.8) and strongly (pH14) alkaline aqueous solutions were used to simulate the water layers at the cathodically polarized steel surface on the soil-side of buried pipe. A rotating gold ring and steel disc electrode (RRDE) in alkaline aqueous electrolyte equilibrated with 1atm oxygen over solution was used to measure the rotation rate dependent current for the electroreduction of oxygen, O2, on an ASTM A516 steel disc and the resulting peroxide generation, which was determined by monitoring the oxidation current on the gold ring. An appreciable fraction of the oxygen reduction current on the steel disk gave rise to peroxide generation over a wide range of potentials, from –0.2 to –0.9V vs SCE in 1M KOH. The observation of peroxide generation is noteworthy, because oxidizing agents, such as peroxide and its decomposition products, superoxide and hydroxy radical, can degrade the polymers used for coating pipelines. As result, oxidative degradation of polymer or interfacial compounds may be a cause of the accelerated disbonding observed for protective coatings on steel pipelines under cathodic protection.     

Ruthenium selenide catalysts for cathodic oxygen reduction in direct methanol fuel cells

The oxygen reduction reaction in sulphuric acid on commercial carbon supported platinum and ruthenium catalysts as well as on a home-made carbon supported ruthenium selenide catalysts (RuSe _x /C) was investigated. The RuSe _x /C catalysts were synthesised using similar procedures to those found in the literature. A dependency of H₂O₂ formation on the selenium content was found using the thin-film rotating ring disc electrode technique, namely that the H₂O₂ formation in the typical operation range of a Direct Methanol Fuel Cell (0.7–0.4 V) on Pt/C is below 1% and 1–4% on Ru/C and RuSe _x /C catalysts. Finally for comparing the intrinsic activities of the catalysts the electrochemically active surface areas were determined in-situ by means of copper underpotential deposition. Our results indicate a comparable activity of the present RuSe _x /C catalyst to commercial Pt/C if the activities are related to the electrochemical active areas.     

The effect of pH on oxygen and hydrogen peroxide reduction on polycrystalline Pt electrode

Oxygen reduction (ORR) and hydrogen peroxide reduction (HPRR) reactions were studied on polycrystalline Pt by the rotating disc electrode technique in sulphate solutions over the entire pH range. Initial potentials for both ORR and HPRR coincide with the potential region of PtOH formation and shift negatively with the increase of the pH of the solution. For pHs lower than 3.0 and higher than 10.0, the ORR takes place through 4e-series pathways from acid and alkaline solutions, respectively. For 3.0 < pH < 6.0, the overall number of electrons exchanged depends on the potential and falls below 4 for ORR and below two for HPRR. This indicates that both reactions occur in a limited extent due to the changes of the local pH in the course of these reactions which gives rise to the double wave in the polarization curves (as observed for ORR for pH 3.5 and pH 4.0 and for HPRR for pH 4.0). The change of the Tafel slopes with potential indicate the change in reaction pathway from one that takes place in acid – to one that takes place in alkaline solution.     

Microstructure effect of carbon nanofiber on electrocatalytic oxygen reduction reaction

Carbon nanofibers (CNFs) with controlled microstructures, i.e. platelet CNF (p-CNF), fish-bone CNF (f-CNF) and tube CNF (t-CNF), are synthesized, and their behaviors in electrocatalytic oxygen reduction reaction (ORR) in acid media are investigated in this paper. The physico-chemical properties of the CNFs are characterized by high resolution transmission electron microscope (HRTEM), N₂ adsorption–desorption and Raman spectrum. Cyclic voltammetry experiments show that the CNFs have higher ORR activities than graphite. The p-CNF, which has the highest ratio of edge atoms to basal atoms, demonstrates the most positive ORR onset potential and ORR peak potential. The f-CNF, which has the largest amounts of ORR active sites, exhibits the highest ORR peak current. The t-CNF demonstrates the most negative ORR onset potential, negative ORR peak potential, and the least ORR peak current, which is a result of the fewest catalytic active sites. Furthermore, the microstructures of CNFs can impact the reaction process. The ORR on p-CNF or f-CNF is controlled by diffusion, while the ORR on t-CNF is jointly controlled by surface reaction and diffusion.     

The effect of surface coverage by adsorbed oxygen on the kinetics of oxygen reduction at oxide free platinum

The kinetics of oxygen reduction was studied at prereduced platinum electrodes in oxygen saturated perchloric acid solutions using potentiostatic transients and steady-state techniques. The steady-state experiments show that the reduction at potentials cathodic to 1·0 V is characterized by ∂V/∂ log i = −60, and ∂V/∂ pH = −100m V. These parameters are compatible with the previously proposed mechanism in which the first charge transfer step is rate determining under Temkin conditions of adsorption by reaction intermediates. In transients too (when the electrode potential was increased from a low level where the coverage with oxygen is virtually zero to any potential between 0·8 and 1·0 V) the initial current i_i, is controlled by the first charge transfer step but now under Langmuirian conditions of adsorption. This accounts for the observed slope ∂V/∂ log i_i of −120 mV. From the steady state and the initial currents the change in the heat of adsorption of reaction intermediates with coverage is found to be 20 kcal/equiv.     

Anodic behaviour of arsenopyrite and cathodic reduction of ferrate(VI) and oxygen in alkaline solutions

This paper presents the results of an electrochemical study of the anodic characteristics of arsenopyrite in strongly alkaline solutions and of the cathodic reduction of ferrate(VI) and of dissolved oxygen at an arsenopyrite surface at potentials which are relevant to the oxidation reactions. Cyclic voltammetry at both arsenopyrite disc and arsenopyrite disc/platinum ring electrodes has shown that arsenic(III) is the main product of the anodic process at potentials in the region of the rest potential during oxidation by either ferrate(VI) or oxygen. Evidence for partial passivation of both the anodic and cathodic reactions has been obtained from potentiostatic current–time transients. The initial stage of oxidation by ferrate(VI) has been shown to be mass-transport controlled and this is also true of the oxidation by oxygen in dilute solutions of sodium hydroxide.     

Development of platinum-free catalyst and catalyst with low platinum content for cathodic oxygen reduction in acidic electrolytes

Studies are presented of the kinetics and mechanism of oxygen electroreduction on CoPd catalysts synthesized on XC 72 carbon black. As shown both in model conditions and in tests with the cathodes of hydrogen–oxygen fuel cells with proton conducting electrolyte, the CoPd/C system features higher activity as compared to Co/C. It is found by means of structural analysis that CoPd alloy is formed in the course of the catalyst synthesis. This provides the higher catalytic activity of the binary systems. CoPd/C catalyst is also more stable in respect to corrosion than Pd on carbon black. Measurements on a rotating ring–disc electrode show that the CoPd/C system provides preferential oxygen reduction to water in the practically important range of potentials (E > 0.7 V). The similarity of the kinetic parameters of the oxygen reduction reaction on CoPd/C and Pt/C catalysts points to a similar reaction mechanism. The slow step of the reaction is the addition of the first electron to the adsorbed and previously protonated O₂ molecule. Studies of the most active catalyst in the fuel cell cathodes are performed. Binary PtCo catalysts (metal atomic ratio of 1 : 1) with low platinum content (7.3 wt.%) modified by phosphorus or sulfur are developed and studied. It is demonstrated that the specific activity of the PtCoS/C (Pt : S = 1 : 1) catalytic system for the O₂ reduction reaction exceeds that of a commercial Pt/C catalyst (E-TEK). The tolerance of the catalyst modified with sulfur is at least six times higher than that of Pt/C (E-TEK).     

Formation of sorbitol by cathodic reduction of glucose

The steady-state formation of sorbitol by cathodic reduction of glucose was studied in a parallel-plate reactor of 200 cm² electrode area. Earlier work was extended to explore the effect of flow rate, pH and current density. The effect of temperature between 20° and 47° C and the use of amalgamated lead as compared with chemical lead and other metals is discussed. It is shown that addition of Zn²⁺ ions accelerates the reaction and the reasons for this are discussed. The implications for industrial application are considered.     

The effect of phosphorus in nitrogen-containing carbon nanostructures on oxygen reduction in PEM fuel cells

Phosphorus added to the growth media of nitrogen-containing carbon nanostructures was found to dramatically improve the electrocatalytic activity for oxygen reduction. Phosphorus doping was achieved by growing carbon-nitrogen-phosphorus catalyst (CN_xP_y) over triphenylphospine- and iron acetate-impregnated magnesia support in N₂ saturated with CH₃CN, at 900 °C. Catalysts grown in phosphorus-containing media showed improved onset of activity, increased current density and higher selectivity for water formation. The incorporation of both phosphorus and nitrogen into graphite materials allows for the tailoring of the physical and electrochemical properties.     

The effect of boron doping into Co-C-N and Fe-C-N electrocatalysts on the oxygen reduction reaction

Co-C-N and Fe-C-N thin film catalysts have been modified by controlled doping with boron. Corresponding novel thin film catalysts Co-C-N-B and Fe-C-N-B were synthesized by combinatorial magnetron sputter deposition in an Ar/N₂ gas mixture followed by subsequent heat-treatment between 700 and 1000 °C in an argon atmosphere. The nitrogen content of the as-prepared thin film catalysts could be increased by the addition of boron. Furthermore, the amount of remaining nitrogen in heat-treated catalyst samples was significantly higher in case of boron containing samples. The thin film catalysts were characterized by means of X-ray diffraction (XRD) analysis, electron microprobe and electrochemical measurements. For electrochemical studies the activity as oxygen reduction reaction (ORR) catalyst was investigated using the rotating ring-disk electrode (RRDE) technique in 0.1 M HClO₄ solution at room temperature. The catalytic activity was found to decrease with the boron content in the thin film catalysts even though the N-content increased.     

Preparation of nitrogen-doped carbon nanotube arrays and their catalysis towards cathodic oxygen reduction in acidic and alkaline media

Nitrogen-doped carbon nanotube (N-CNT) arrays were prepared by chemical vapor deposition, using ferrocene as the catalyst precursor and imidazole as the carbon and nitrogen precursor. For the reduction of oxygen, the N-CNTs showed excellent electrocatalytic activity in both acidic and alkaline media. The N-CNTs were characterized by scanning and transmission electron microscopy, X-ray diffraction, X-ray photoelectron spectroscopy, and elemental analysis. The samples had a high nitrogen content (8.54 at.%) and a bamboo-like structure, and their activity varied according to the amount of pyridinic nitrogen they contained.     

The cathodic reduction of o-halonitrobenzenes in acidic propanol/water

The electrochemical reduction of three o-halonitrobenzenes at mercury in acidic 50% n-propanol/water has been studied and compared with that of nitrobenzene. The objective of this study was to seek conditions for the complete 6e reduction to the corresponding anilines; with the fluoro- and chloro-compounds this could be achieved in yields exceeding 75% and at current densities above 100 mA cm⁻² using 0.1 M H₂SO₄ as the electrolyte. With o-bromonitrobenezene the yield was lower because of competing cleavage of the C---Br bond.     

The electrochemical reduction of oxygen in sulpholane

The electrochemical reduction of oxygen on mercury has been studied in sulpholane, a dipolar aprotic solvent, by polarography and cyclic voltammetry. The influences of the nature of the supporting electrolyte, the water concentration and the addition of phenol, a more powerful proton donor than water, have been studied. A reaction scheme is proposed. A simple electrochemical method for determining the oxygen content of sulpholane has been developed.     

Inhibiting effect of oxidized zirconium on parasitic cathodic reactions in the sodium chlorate process Part I: Hypochlorite reduction

To clarify the effect of oxidized zirconium on parasitic cathodic reactions in the chlorate process, electrochemical studies were carried out at laboratory scale. The techniques used were cyclic voltammetry and recording of polarization curves. In this paper the reduction of hypochlorite ions to chloride ions was studied. It is shown that oxidized zirconium cathodes reduces the rate of hypochlorite reduction, although not entirely inhibiting it, which is mainly related to a lowered active area due to the porous layer of zirconium dioxide. Further, it has also been shown that the oxidized samples are partly passivated, giving high overvoltages for the hydrogen evolution reaction. These overvoltages gradually decrease during cathodic polarization due to the simultaneous reduction of the zirconium oxide. Studies of the selectivity indicate that hypochlorite reduction occurs on the oxidised zirconium cathodes to a high extent, the thermal oxide being somewhat better. This further proves that zirconium oxide is not a suitable cathode material for the sodium chlorate process.     

A cyclic voltammetric study of some quinoxaline di-n-oxides and quinoxalines in acetonitrile: substituent effect on the cathodic reduction

The cathodic reductions of two series of substituted quinoxaline di-N-oxides and quinoxalines in acetonitrile were measured in the potential range of 0 to −2.0 V and 0 to −2.3 V vs sce, respectively. Two irreversible reductions were observed in the first series, and one reversible reduction for the second. The effect of substituent on these reduction is reported.     

The effect of cathodic water on performance of a polymer electrolyte fuel cell

A simple analytical model of water transport in the polymer electrolyte fuel cell is developed. Nonlinear membrane resistance and voltage loss due to incomplete membrane humidification are calculated. Both values depend on parameter r, the ratio of mass transport coefficients of water in the membrane and in the backing layer. Simple equation for cell performance curve, which incorporates the effect of cathodic water is constructed. Depending of the value of r, the cell may operate in one of the two regimes. When r ≥ 1, incomplete membrane humidification simply reduces cell voltage; the limiting current density is determined by oxygen transport in the backing layer (oxygen-limiting regime). If r < 1, limiting current density is determined by membrane drying (water-limiting regime). In that case there exists optimal current density, which provides minimal membrane resistance. It is shown that membrane drying may lead to parasitic “in-plane” proton current.