Few-Layer Borocarbonitride Nanosheets: Platinum-Free Catalyst for the Oxygen Reduction Reaction

The present study demonstrates the use of few-layer borocarbonitride nanosheets synthesized by a simple method as non-platinum cathode catalysts for the oxygen reduction reaction (ORR) in alkaline medium. Composition-dependent ORR activity is observed and the best performance was found when the composition was carbon-rich. Mechanistic aspects reveal that ORR follows the 4e(-) pathway with kinetic parameters comparable to those of the commercial Pt/C catalyst. Excellent methanol tolerance is observed with the BCN nanosheets unlike with Pt/C.

Hetero-atom Doped Carbon Nanotubes for Dye Degradation and Oxygen Reduction Reaction

We report the synthesis of nitrogen doped vertically aligned multi-walled (MWNCNTs) carbon nanotubes by pyrolysis and its catalytic performance for degradation of methylene blue (MB) dye & oxygen reduction reaction (ORR). The degradation of MB was monitored spectrophotometrically with time. Kinetic studies show the degradation of MB follows a first order kinetic with rate constant k=0.0178 min(-1). The present rate constant is better than that reported for various supported/non-supported semiconducting nanomaterials. Further ORR performance in alkaline media makes MWNCNTs a promising cost-effective, fuel crossover tolerance, metal-free, eco-friendly cathode catalyst for direct alcohol fuel cell.

Primary and rechargeable zinc-air batteries using ceramic and highly stable TiCN as an oxygen reduction reaction electrocatalyst

Primary and secondary zinc-air batteries based on ceramic, stable, one dimensional titanium carbonitride (TiCN) nanostructures are reported. The optimized titanium carbonitride composition by density functional theory reveals their good activity towards the oxygen reduction reaction (ORR). Electrochemical measurements show their superior performance for the ORR in alkaline media coupled with favourable kinetics. The nanostructured TiCN lends itself amenable to be used as an air cathode material in primary and rechargeable zinc-air batteries. The battery performance and cyclability are found to be good. Further, we have demonstrated a gel-based electrolyte for rechargeable zinc-air batteries based on a TiCN cathode under ambient, atmospheric conditions without any oxygen supply from a cylinder. The present cell can work at current densities of 10-20 mA cm(2) (app. 10 000 mA g(-1) of TiCN) for several hours (63 h in the case of 10 mA cm(-2)) with a charge retention of 98%. The low cost, noble metal-free, mechanically stable and corrosion resistant TiCN is a very good alternative to Pt for metal-air battery chemistry.

Carbon-Supported Pt-TiO2 as a Methanol-Tolerant Oxygen-Reduction Catalyst for DMFCs

Carbon-supported Pt-TiO2 (Pt-TiO2/C) catalysts with varying at. wt ratios of Pt to Ti, namely, 1:1, 2:1, and 3:1, are prepared by the sol-gel method. The electrocatalytic activity of the catalysts toward oxygen reduction reaction (ORR), both in the presence and absence of methanol, is evaluated for application in direct methanol fuel cells (DMFCs). The optimum at. wt ratio of Pt to Ti in Pt-TiO2/C is established by fuel cell polarization, linear sweep voltammetry, and cyclic voltammetry studies. Pt-TiO2/C heattreated at 750 degrees C with Pt and Ti in an at. wt ratio of 2:1 shows enhanced methanol tolerance, while maintaining high catalytic activity toward ORR. The DMFC with a Pt-TiO2/C cathode catalyst exhibits an enhanced peak power density of 180 mW/cm(2) in contrast to the 80 mW/cm(2) achieved from the DMFC with carbon-supported Pt catalyst while operating under identical conditions. Complementary data on the influence of TiO2 on the crystallinity of Pt, surface morphology, and particle size, surface oxidation states of individual constituents, and bulk and surface compositions are also obtained by powder X-ray diffraction, scanning and transmission electron microscopy, X-ray photoelectron spectroscopy, energy dispersive analysis by X-ray, and inductively coupled plasm optical emission spectrometry.

Electrochemical reduction of oxygen on gold and boron-doped diamond electrodes in ambient temperature, molten acetamide-urea-ammonium nitrate eutectic melt

The electrochemical reduction of oxygen has been studied on gold, boron-doped diamond (BDD) and glassy carbon (GC) electrodes in a ternary eutectic mixture of acetamide (CH3CONH2), urea (NH2CONH2) and ammonium nitrate (NH4NO3). Cyclic voltammetry (CV), differential pulse voltammetry (DPV), chronoamperometry and rotating disk electrode (RDE) voltammetry techniques have been employed to follow oxygen reduction reaction (ORR). The mechanism for the electrochemical reduction of oxygen on polycrystalline gold involves 2-step. 2-electron pathways of O-2 to H2O2 and further reduction of H2O2 to H2O. The first 2-electron reduction of O-2 to H2O2 passes through superoxide intermediate by 1-electron reduction of oxygen. Kinetic results suggest that the initial 1-electron reduction of oxygen to HO2 is the rate-determining step of ORR on gold surfaces. The chronoamperometric and ROE studies show a potential dependent change in the number of electrons on gold electrode. The oxygen reduction reaction on boron-doped diamond (BOO) seems to proceed via a direct 4-electron process. The reduction of oxygen on the glassy carbon (GC) electrode is a single step, irreversible, diffusion limited 2-electron reduction process to peroxide. (C) 2010 Elsevier Ltd. All rights reserved.

Vapor-Pressure Of Calcium Corresponding To The Reduction Of Calcia By Aluminum

The equilibrium pressure of calcium corresponding to the reduction reaction 6CaO (s) + 2Al (l) half-arrow-right-over-half-arrow-left 3CaO.Al2O3 (s) + 3Ca (g) has been measured by Knudsen effusion - mass loss analysis in the temperature range 1190 - 1500 K. The measured vapour pressure can be expressed as a function of temperature by the relation: log p(Ca) (Pa) = -10,670/T + 9.267 The calcium generated is partially absorbed by aluminium to form an alloy. The equilibrium composition of the alloy at 1373 K was found to be 22 mol% Ca - 78 mol% Al. The measured vapour pressure is in good agreement with that computed from thermodynamic data.

A PEFC With Pt-TiO2/C as Oxygen-Reduction Catalyst

Carbon-supported Pt-TiO2 (Pt-TiO2/C) catalyst with varying atomic ratio of Pt to Ti, namely, 1: 1, 2: 1, and 3: 1, is prepared by sol-gel method and its electrocatalytic activity toward oxygen-reduction reaction (ORR) is evaluated for the application in polymer electrolyte fuel cells (PEFCs). The optimum atomic ratio of Pt to Ti in Pt-TiO2/C and annealing temperature are established by cyclic voltammetry and fuel-cell-polarization studies. Pt-TiO2/C annealed at 750 degrees C with Pt and Ti in atomic ratio of 2: 1, namely, 750 Pt-TiO2/C (2: 1), shows enhanced electrocatalytic activity toward ORR. It is found that the incorporation of TiO2 with Pt ameliorates both electrocatalytic activity and stability of cathode in relation to pristine Pt cathode, currently being used in PEFCs. A power density of 0.75 W/cm(2) is achieved at 0.6 V for the PEFC with 750 Pt-TiO2/C (2: 1) as compared with 0.62 W/cm(2) at 0.6 V achieved with the PEFC comprising Pt/C as cathode catalyst while operating under identical conditions. Interestingly, carbon-supported Pt-TiO2 cathode exhibits only 6% loss in electrochemical surface area after 5000 potential cycles while it is as high as 25% for Pt/C. DOI: 10.1115/1.4002466]

Pt-Au/C cathode with enhanced oxygen-reduction activity in PEFCs

Carbon-supported Pt-Au (Pt-Au/C) catalyst is prepared separately by impregnation, colloidal and micro-emulsion methods, and characterized by physical and electrochemical methods. Highest catalytic activity towards oxygen-reduction reaction (ORR) is exhibited by Pt-Au/C catalyst prepared by colloidal method. The optimum atomic ratio of Pt to Au in Pt-Au/C catalyst prepared by colloidal method is determined using linear-sweep and cyclic voltammetry in conjunction with cell-polarization studies. Among 3:1, 2:1 and 1:1 Pt-Au/C catalysts, (3:1) Pt-Au/C exhibits maximum electrochemical activity towards ORR. Powder X-ray diffraction pattern and transmission electron micrograph suggest Pt-Au alloy nanoparticles to be well dispersed onto the carbon-support. Energy dispersive X-ray analysis and inductively coupled plasma-optical emission spectroscopy data suggest that the atomic ratios of the alloying elements match well with the expected values. A polymer electrolyte fuel cell (PEFC) operating at 0 center dot 6 V with (3:1) Pt-Au/C cathode delivers a maximum power-density of 0 center dot 65 W/cm (2) in relation to 0 center dot 53 W/cm (2) delivered by the PEFC with pristine carbon-supported Pt cathode.

Dilithium phthalocyanine as a catalyst for oxygen reduction in non-aqueous Li-O-2 cells

The electrochemical performance of Li-O-2 cells depends mainly on the kinetics of the cathode reaction, namely, oxygen reduction reaction in non-aqueous electrolytes. The catalyst plays an important role on the kinetics of the reaction. In the present work, dilithium phthalocyanine is used as the catalyst in the cathode of Li-O-2 cells. Dual-layer O-2 electrodes are fabricated employing a high surface area microporous carbon with Ni gauge current collector present between the two layers. Discharge capacity of Li-O-2 cell measured at 0.2 mA.cm(-2) is about 30 mAh.cm(-2). Phthalocyanine ring is considered to interact with O-2 producing Li2Pc+delta - O-2(-delta) as a reaction intermediate, which facilitates the electron-transfer reaction.

Morphology dependent oxygen reduction activity of titanium carbide: bulk vs. nanowires

Titanium carbide (TiC) possesses fascinating properties like high electrical conductivity and high mechanical strength coupled with high corrosion resistance and stability in acidic and alkaline environments. The present study demonstrates the tunability of mechanistic aspects of oxygen reduction reaction (ORR) using TiC nanostructures. One dimensional TiC nanostructures (TiC-NW) have been synthesized using a simple, hydrothermal method and used as a catalyst for ORR. Shape dependent electroactivity is demonstrated by comparing the activity of TiC-NW with its bulk counterparts. Comparative studies reveal higher ORR activities in the case of 1D TiC-NW involving similar to 4 electrons showing efficient reduction of molecular oxygen. Excellent stability and high methanol tolerance with good selectivity for ORR is reported.

The morphology dependent electrocatalytic activity of Ir nanostructures towards oxygen reduction

Iridium nanostructures with different morphologies are synthesized by a simple, environmentally friendly approach in aqueous media under mild conditions. The morphology dependent electrocatalytic activity of Ir nanochains and nanoparticles towards oxygen reduction reaction (ORR) has been demonstrated in both acidic and alkaline media. Comparative electrochemical studies reveal that nanochains exhibit significantly enhanced ORR activities in both acidic and alkaline media as compared with nanoparticles, as a result of the continuous structure of interconnected particles. The mechanism of oxygen reduction on Ir nanostructures predominantly follows a four-electron pathway in alkaline and acidic solutions. Excellent stability and good selectivity towards methanol tolerance are reported.

Ag nanoparticles-anchored reduced graphene oxide catalyst for oxygen electrode reaction in aqueous electrolytes and also a non-aqueous electrolyte for Li-O-2 cells

Silver nanoparticles-anchored reduced graphene oxide (Ag-RGO) is prepared by simultaneous reduction of graphene oxide and Ag+ ions in an aqueous medium by ethylene glycol as the reducing agent. Ag particles of average size of 4.7 nm were uniformly distributed on the RGO sheets. Oxygen reduction reaction (ORR) is studied on Ag-RGO catalyst in both aqueous and non-aqueous electrolytes by using cyclic voltammetry and rotating disk electrode techniques. As the interest in non-aqueous electrolyte is to study the catalytic performance of Ag-RGO for rechargeable Li-O-2 cells, these cells are assembled and characterized. Li-O-2 cells with Ag-RGO as the oxygen electrode catalyst are subjected to charge-discharge cycling at several current densities. A discharge capacity of 11 950 mA h g(-1) (11.29 mA h cm(-2)) is obtained initially at low current density. Although there is a decrease in the capacity on repeated discharge-charge cycling initially, a stable capacity is observed for about 30 cycles. The results indicate that Ag-RGO is a suitable catalyst for rechargeable Li-O-2 cells.

Electronic structure origin of conductivity and oxygen reduction activity changes in low-level Cr-substituted (La, Sr)MnO3

The electronic structure of the (La0.8Sr0.2)(0.98)Mn1-xCrxO3 model series (x = 0, 0.05, or 0.1) was measured using soft X-ray synchrotron radiation at room and elevated temperature. O K-edge near-edge X-ray absorption fine structure (NEXAFS) spectra showed that low-level chromium substitution of (La, Sr)MnO3 resulted in lowered hybridisation between O 2p orbitals and M 3d and M 4sp valance orbitals. Mn L-3-edge resonant photoemission spectroscopy measurements indicated lowered Mn 3d-O 2p hybridisation with chromium substitution. Deconvolution of O K-edge NEXAFS spectra took into account the effects of exchange and crystal field splitting and included a novel approach whereby the pre-peak region was described using the nominally filled t(2g) up arrow state. 10% chromium substitution resulted in a 0.17 eV lowering in the energy of the t(2g) up arrow state, which appears to provide an explanation for the 0.15 eV rise in activation energy for the oxygen reduction reaction, while decreased overlap between hybrid O 2p-Mn 3d states was in qualitative agreement with lowered electronic conductivity. An orbital-level understanding of the thermodynamically predicted solid oxide fuel cell cathode poisoning mechanism involving low-level chromium substitution on the B-site of (La, Sr)MnO3 is presented. (C) 2015 AIP Publishing LLC.

Organic-inorganic hybrid PtCo nanoparticle with high electrocatalytic activity and durability for oxygen reduction

In Pt-transition metal (TM) alloy catalysts, the electron transfer from the TM to Pt is retarded owing to the inevitable oxidation of the TM surface by oxygen. In addition, acidic electrolytes such as those employed in fuel cells accelerate the dissolution of the surface TM oxide, which leads to catalyst degradation. Herein, we propose a novel synthesis strategy that selectively modifies the electronic structure of surface Co atoms with N-containing polymers, resulting in highly active and durable PtCo nanoparticle catalysts useful for the oxygen reduction reaction (ORR). The polymer, which is functionalized on carbon black, selectively interacts with the Co precursor, resulting in Co-N bond formation on the PtCo nanoparticle surface. Electron transfer from Co to Pt in the PtCo nanoparticles modified by the polymer is enhanced by the increase in the difference in electronegativity between Pt and Co compared with that in bare PtCo nanoparticles with the TM surface oxides. In addition, the dissolution of Co and Pt is prevented by the selective passivation of surface Co atoms and the decrease in the O-binding energy of surface Pt atoms. As a result, the catalytic activity and durability of PtCo nanoparticles for the ORR are significantly improved by the electronic ensemble effects. The proposed organic/inorganic hybrid concept will provide new insights into the tuning of nanomaterials consisting of heterogeneous metallic elements for various electrochemical and chemical applications.

A Methanol-Tolerant Carbon-Supported Pt-Au Alloy Cathode Catalyst for Direct Methanol Fuel Cells and Its Evaluation by DFT

A Pt-Au alloy catalyst of varying compositions is prepared by codeposition of Pt and Au nanoparticles onto a carbon support to evaluate its electrocatalytic activity toward an oxygen reduction reaction (ORR) with methanol tolerance in direct methanol fuel cells. The optimum atomic weight ratio of Pt to Au in the carbon-supported Pt-Au alloy (Pt-Au/C) as established by cell polarization, linear-sweep voltammetry (LSV), and cyclic voltammetry (CV) studies is determined to be 2:1. A direct methanol fuel cell (DMFC) comprising a carbon-supported Pt-Au (2:1) alloy as the cathode catalyst delivers a peak power density of 120 mW/cm2 at 70 °C in contrast to the peak power density value of 80 mW/cm2 delivered by the DMFC with carbon-supported Pt catalyst operating under identical conditions. Density functional theory (DFT) calculations on a small model cluster reflect electron transfer from Pt to Au within the alloy to be responsible for the synergistic promotion of the oxygen-reduction reaction on a Pt-Au electrode.