Comparison of Pt and Pd anode catalysts supported on nanocrystalline Ru–SnO2 for ethanol oxidation in fuel cell applications

The article presents promising catalysts, applicable for direct alcohol fuel cells (DAFC) for portable and mobile applications. The goal of this work is development of Pt and Pd catalysts deposited on interactive nanocrystalline Ru doped SnO₂ support with improved performance. The structure and the morphology of the prepared metal-oxide catalyst support and Pt and Pd based catalysts were examined using XRPD, SEM/EDX and TEM techniques. Electrocatalytic activities of the prepared Pt or Pd based catalysts were evaluated in both alkaline and acidic conditions. The ethanol oxidation reaction (EOR) was studied using conventional electrochemical techniques. The interactive nature of the novel Ru doped SnO₂ catalyst support was confirmed, resulting in the enhancement of the EOR kinetics, in comparison to commercially available catalysts. New and simplified synthetic route applied for preparation of interactive catalyst support was presented with the aim to enable easy scale-up of the catalyst production process. Obtained results on the novel catalysts promise great potential in improving the performance and durability of the DAFC.     

Methanol oxidation on carbon supported Pt–Ru catalysts prepared by electrodeposition – Evaluation of Nafion 117 film effect

Diverse electrochemical techniques were performed in order to obtain meaningful information about the methanol oxidation reaction on nanostructured planar carbon supported Pt–Ru electrodes prepared by electrodeposition, on which a layer of Nafion ionomer was incorporated. A metallic deposit consisting of dendritic agglomerates (between 50 and 200 nm) constituted by smaller particles (6 nm) was obtained. The average bulk Ru content obtained by EDX analysis was between 23 and 25 at. %. A decrease of the activity in the electrodes for methanol oxidation was determined when the thickness of the Nafion 117 film was increased. These results may be associated with the partial blocking of the surface active sites by hydrophobic domains of the polymer, and the presence of CO₂ molecules retained within the Nafion hydrophilic microchannels. EIS results indicated that methanol electro-oxidation mechanism does not change with Nafion presence.     

Pt–Ru catalysts supported on carbon xerogels for PEM fuel cells

Pt–Ru electrocatalysts supported on carbon xerogels were synthesized by reduction of metal precursors with formate ions (SFM method). The carbon xerogel was chemically and heat treated in order to evaluate the different procedures to generate oxygenated groups on the surface. Temperature-programmed desorption (TPD) of xerogels showed that heat treatment of previously chemically modified support gradually removes the oxygenated groups from the carbon surface. Physical characterization of the catalyst was performed using X-ray dispersive energy (EDX) and X-ray diffraction (XRD) techniques. Results confirmed that Pt–Ru catalysts with similar metal content (20%) and atomic ratios (Pt:Ru 1:1) were obtained.     

Large–scale DMFC stack model: The effect of a condensation front on stack performance

The cathode flooding has a significant impact on DMFC performance. Liquid water reduces diffusion of oxygen through the cathode GDL. Oxygen transport problems on the cathode side redistribute the rate of methanol consumption and eventually lead to transport limitations on the anode side. Our model shows that there is a critical level of flooding of the cathode backing layer below which the cell performance suffers greatly, eventually running the risk of cell reversal. This critical point is reached when the oxygen diffusivity in the flooded domain drops by a factor of five with respect to the normal non-flooded level.     

Sputtered Ir–Ru based catalysts for oxygen evolution reaction: Study of iridium effect on stability

Magnetron sputtered low-loading iridium-ruthenium thin films are investigated as catalysts for the Oxygen Evolution Reaction at the anode of the Proton Exchange Membrane Water Electrolyzer. Electrochemical performance of 50 nm thin catalysts (Ir pure, Ir–Ru 1:1, Ir–Ru 1:3, Ru pure) is tested in a Rotating Disk Electrode. Corresponding Tafel slopes are measured before and after the CV-based procedure to compare the activity and stability of prepared compounds. Calculated activities prior to the procedure confirm higher activity of ruthenium-containing catalysts (Ru pure > Ir–Ru 1:3 > Ir–Ru 1:1 > Ir pure). However, after the procedure a higher activity and less degradation of Ir–Ru 1:3 is observed, compared to Ir–Ru 1:1, i.e. the sample with a higher amount of unstable ruthenium performs better. This contradicts the expected behavior of the catalyst. The comprehensive chemical and structural analysis unravels that the stability of Ir–Ru 1:3 sample is connected to RuO₂ chemical state and hcp structure. Obtained results are confirmed by measuring current densities in a single cell.     

Numerical study of the effect of hydrogen addition on methane–air mixtures combustion

The stoichiometric methane–hydrogen–air freely propagated laminar premixed flames at normal temperature and pressure were calculated by using PREMIX code of CHEMKIN II program with GRI-Mech 3.0 mechanism. The mole fraction profiles and the rate of production of the dominant reactions contributing to the major species and some selected intermediate species in the flames of methane–hydrogen–air were obtained. The rate of production analysis was conducted and the effect of hydrogen addition on the reactions of methane–air mixtures combustion was analyzed by the dominant elementary reactions for specific species. The results showed that the mole fractions of major species CH₄, CO and CO₂ were decreased while their normalized values were increased as hydrogen is added. The rate of production of the dominant reactions contributing to CH₄, CO and CO₂ shows a remarkable increase as hydrogen is added. The role of H₂ in the flame will change from an intermediate species to a reactant when hydrogen fraction in the blends exceeds 20%. The enhancement of combustion with hydrogen addition can be ascribed to the significant increase of H, O and OH in the flame as hydrogen is presented. The decrease of the mole fractions of CH₂O and CH₃CHO with hydrogen addition suggests a potential in the reduction of aldehydes emissions of methane combustion as hydrogen is added. The methane oxidation reaction pathways will move toward the lower carbon reaction pathways when hydrogen is available and this has the potential in reducing the soot formation. Chemical kinetics effect of hydrogen addition has a little influence on NO formation for methane combustion with hydrogen addition.     

Polyoxometallate-stabilized Pt–Ru catalysts on multiwalled carbon nanotubes: Influence of preparation conditions on the performance of direct methanol fuel cells

A novel catalyst, polyoxometallate-stabilized platinum–ruthenium alloy nanoparticles supported on multiwalled carbon nanotubes (Pt–Ru–PMo₁₂-MWNTs), was synthesized by a microwave-assisted polyol process. The effects of microwave reaction time, microwave reaction power, and pH value of the reaction solution on the electrocatalytic properties of Pt–Ru–PMo₁₂-MWNTs catalysts were also investigated. The polyoxometallate (PMo₁₂) formed a self-assembled monolayer on the surface of the Pt/Ru nanoparticles and MWNTs, which effectively prevented the agglomeration of Pt, Ru nanoparticles and MWNTs, due to the electrostatic repulsive interactions between the negatively charged PMo₁₂ monolayers. Energy dispersive spectroscopy examination and electrochemical measurements showed that the loading content of Pt/Ru and their electrochemical activity vary with the synthesis conditions, such as pH, reaction time, and microwave power. It was found that the a Pt–Ru–PMo₁₂-MWNTs electrocatalyst with high Pt loading content, small crystallite size, and good electrocatalytic activity could be synthesized using a long reaction time, intermediate microwave power, and a pH value of 7. The electrocatalysts obtained were characterized using X-ray diffraction, and scanning and transmission electron microscopy. Their electrocatalytic properties were also investigated by using the cyclic voltammetry technique.     

A comparative study for synthesis methods of nano-structured (9Ni–2Mg–Y) alloy catalysts and effect of the produced alloy on hydrogen desorption properties of MgH2

9Ni–2Mg–Y alloy powders were prepared by arc melting, induction melting, mechanical alloying, solid state reaction and subsequent ball milling processes. The results showed that melting processes are not suitable for preparation of 9Ni–2Mg–Y alloy due to high losses of Mg and Y. Therefore, 9Ni–2Mg–Y alloy powder was prepared by three methods including: 1) mechanical alloying, 2) mechanical alloying + solid state reaction + ball milling, and 3) mixing + solid state reaction + ball milling. The prepared 9Ni–2Mg–Y alloy powders were compared for their catalytic effects on hydrogen desorption of MgH₂. It is found that 9Ni–2Mg–Y alloy powder prepared by mechanical alloying + solid state reaction + ball milling method has a smaller particle size (1–5 μm) and higher surface area (1.7 m² g⁻¹) than that of other methods. H₂ desorption tests revealed that addition of 9Ni–2Mg–Y alloy prepared by mechanical alloying + solid state reaction + ball milling to MgH₂ decreases the hydrogen desorption temperature of MgH₂ from 425 to 210 °C and improves the hydrogen desorption capacity from 0 to 3.5 wt.% at 350 °C during 8 min.     

The effect of ceria content in nickel–ceria composite anode catalysts on the discharge performance for solid oxide fuel cells

Optimum ceria content in nickel–ceria composite anode catalyst from the point of discharge performance is discussed. The ohmic loss increased when the ceria content was higher than 30 mol%. Even though the electrical conductivity of the anode decreased with increasing ceria content in the anode catalyst in association with decreasing nickel content, the ohmic loss was kept low until the ceria content was ≤30 mol% because the semiconducting ceria compensated for the decreased current path owing to the decreasing nickel content. The lowest activation loss was observed when the ceria content in the nickel anode catalyst was 30 mol% and the maximum activation loss was obtained for ceria content of 2 mol%. Ceria content in nickel anode influenced microstructure of the anode matrix. When the CeO₂ content was 2 mol%, sintering of anode catalyst was evident and the porosity of anode matrix was almost 57% - highest in this study. Whereas sintering of anode catalyst was not evident and the porosity of anode matrix was 46% when the ceria content in the nickel anode catalyst was 30 mol%. Activation loss was strongly influenced by microstructure of anode matrix, and highest activation loss when the CeO₂ content was 2 mol% was owing to the inappropriate microstructure for electrochemical reaction: sintering of the anode catalyst and excessive porosity of the anode.     

Evaluation of Pt–Ru–Ni and Pt–Sn–Ni catalysts as anodes in direct ethanol fuel cells

In this study, the electrooxidation of ethanol on carbon supported Pt–Ru–Ni and Pt–Sn–Ni catalysts is electrochemically studied through cyclic voltammetry at 50 °C in direct ethanol fuel cells. All electrocatalysts are prepared using the ethylene glycol-reduction process and are chemically characterized by energy-dispersive X-ray analysis (EDX). For fuel cell evaluation, electrodes are prepared by the transfer-decal method. Nickel addition to the anode improves DEFC performance. When Pt₇₅Ru₁₅Ni₁₀/C is used as an anode catalyst, the current density obtained in the fuel cell is greater than that of all other investigated catalysts. Tri-metallic catalytic mixtures have a higher performance relative to bi-metallic catalysts. These results are in agreement with CV results that display greater activity for PtRuNi at higher potentials.     

Electrodeposition of Pt–Ru and Pt–Ru–Ni nanoclusters on multi-walled carbon nanotubes for direct methanol fuel cell

A full-electrochemical method is developed to deposit three dimension structure (3D) flowerlike platinum-ruthenium (PtRu) and platinum-ruthenium-nickel (PtRuNi) alloy nanoparticle clusters on multi-walled carbon nanotubes (MWCNTs) through a three-step process. The structure and elemental composition of the PtRu/MWCNTs and PtRuNi/MWCNTs catalysts are characterized by transmission electron microscopy (TEM), energy dispersive X-ray spectroscopy (EDX), X-ray polycrystalline diffraction (XRD), IRIS advantage inductively coupled plasma atomic emission spectroscopy (ICP-AES), and X-ray photoelectron spectroscopy (XPS). The presence of Pt(0), Ru(0), Ni(0), Ni(OH)₂, NiOOH, RuO₂ and NiO is deduced from XPS data. Electrocatalytic properties of the resulting PtRu/MWCNTs and PtRuNi/MWCNTs nanocomposites for oxygen reduction reaction (ORR) and methanol oxidation reaction (MOR) are investigated. Compared with the Pt/MWCNTs, PtNi/MWCNTs and PtRu/MWCNTs electrodes, an enhanced electrocatalytic activity and an appreciably improved resistance to CO poisoning are observed for the PtRuNi/MWCNTs electrode, which are attributed to the synergetic effect of bifunctional catalysis, three dimension structure, and oxygen functional groups which generated after electrochemical activation treatment on MWCNTs surface. The effect of electrodeposition conditions for the metal complexes on the composition and performance of the alloy nanoparticle clusters is also investigated. The optimized ratios for PtRu and PtRuNi alloy nanoparticle clusters are 8:2 and 8:1:1, respectively, in this experiment condition. The PtRuNi catalyst thus prepared exhibits excellent performance in the direct methanol fuel cells (DMFCs). The enhanced activity of the catalyst is surely throwing some light on the research and development of effective DMFCs catalysts.     

Nanostructured Pt–Fe/C cathode catalysts for direct methanol fuel cell: The effect of catalyst composition

A series of carbon supported Pt–Fe bimetallic nanocatalysts (Pt–Fe/C) with varying Pt:Fe ratio were prepared by a modified ethylene glycol (EG) method, and then heat-treated under H₂–Ar (10 vol%-H₂) atmosphere at 900 °C. The Pt–Fe/C catalysts were characterized by X-ray diffraction (XRD), transmission electron spectroscopy (TEM), energy dispersive analysis by X-rays (EDX) and induced coupled plasma-atomic emission spectroscopy (ICP-AES). XRD analysis shows that Pt–Fe/C catalysts have small crystalline particles and form better Pt–Fe alloy structure with Fe amount increasing. TEM images evidence that small Pt–Fe nanoparticles homogeneously deposited on carbon support and addition of Fe can effectively prevent Pt particles agglomeration. EDX and ICP-AES show that Fe precursor cannot be fully reduced and deposited on carbon support through the adopted EG reduction approach. The electrochemical surface area of Pt–Fe/C catalyst obtained through hydrogen desorption areas in the CV curve increases with Fe atomic percentage increasing from 0 to ca. 50%, and then decreases with more Fe in the Pt–Fe/C catalyst. RDE tests show that the Pt–Fe/C with a Pt:Fe ratio of 1.2:1 and an optimized lattice parameter of around 3.894 Å has the highest mass activity and specific activity to oxygen reduction reaction (ORR). As cathode catalyst, this Pt–Fe/C (Pt:Fe ratio of 1.2:1) exhibits higher direct methanol fuel cell performance at 90 °C than Pt/C and other Pt–Fe/C catalysts, this could be attributed to its smaller particle size and better Pt–Fe alloy structure.     

Non-stoichiometric tungsten-carbide-oxide-supported Pt–Ru anode catalysts for PEM fuel cells – From basic electrochemistry to fuel cell performance

Durability and cost of Proton Exchange Membrane fuel cells (PEMFCs) are two major factors delaying their commercialization. Cost is associated with the price of the catalysts, while durability is associated with degradation and poisoning of the catalysts, primarily by CO. This motivated us to develop tungsten-carbide-oxide (W_xC_yO_z) as a new non-carbon based catalyst support for Pt–Ru–based anode PEMFC catalyst. The aim was to improve performance and obtain higher CO tolerance compared to commercial catalysts. The performance of obtained PtRu/W_xC_yO_z catalysts was investigated using cyclic voltammetry, linear scan voltammetry and rotating disk electrode voltammetry. Particular attention was given to the analysis of CO poisoning, to better understand how W_xC_yO_z species can contribute to the CO tolerance of PtRu/W_xC_yO_z. Improved oxidation of CO_ads at low potentials (E < 0.5 V vs. RHE) was ascribed to OH provided by the oxide phase at the interfacial region between the support and the PtRu particles. On the other hand, at high potentials (E > 0.5 V vs. RHE) CO removal proceeds dominantly via OH provided from the oxidized metal sites. The obtained catalyst with the best performance (30% PtRu/W_xC_yO_z) was tested as an anode catalyst in PEM fuel cell. When using synthetic reformate as a fuel in PEMFC, there is a significant power drop of 35.3 % for the commercial 30% PtRu/C catalyst, while for the PtRu/W_xC_yO_z anode catalyst this drop is around 16 %.     

Flame aerosol synthesis of carbon-supported Pt–Ru catalysts for a fuel cell electrode

This study describes how a flame spray pyrolysis method was successfully used to synthesize PtRu catalysts supported by carbon agglomerates. Nearly spherical catalysts composed of metallic Pt and Ru with molar ratio of 1:1 were produced in the flame and their size was about 1.9 nm. X-ray diffraction measurements revealed that amorphous-like Ru was well mixed into the Pt crystalline lattices. Through cyclic voltammetry for methanol oxidation reaction and CO stripping, it was found that the electrochemical activities of the catalysts produced from this process are comparable to or slightly better than those of an equivalent commercial sample with the same composition.     

The effect of the discharge rate on the electrochemical properties of AB3-type hydrogen storage alloy as anode in nickel–metal hydride batteries

In this work, the ternary CeY₂Ni₉ alloy was prepared and served as anode materials in the Ni–MH battery system. The effect of the discharge rate on the electrochemical proprieties of CeY₂Ni₉, such as activation capability, polarization, discharge capacities, hydrogen atomic diffusion capability and redox parameters, were also investigated systematically during activation and long cycling. Charge–discharge measurement showed that this alloy is characterized by fast activation and requires only three cycles to be activated regardless of the discharge rate, the maximum discharge capacity was obtained for the medium discharge rate (C/10). An important correlation was observed between the evolution of the electrochemical parameters and that of the kinetic parameters, such as the hydrogen atomic diffusion capability and the exchange current density.The total substitution of La by Ce in LaY₂Ni₉ parent alloy enhanced its activation, polarization and stability despite the decrease of its discharge capacities, especially at high rates.     

Combinatorial investigation of Pt–Ru–Sn alloys as an anode electrocatalysts for direct alcohol fuel cells

Low-temperature direct alcohol fuel cells fed with different kinds of alcohol (methanol, ethanol and 2-propanol) have been investigated by employing ternary electrocatalysts (Pt–Ru–Sn) as anode catalysts. Combinatorial chemistry has been applied to screen the 66-PtRuSn-anode arrays at the same time to reduce cost, time, and effort when we select the optimum composition of electrocatalysts for DAFCs (Direct Alcohol Fuel Cells). PtRuSn (80:20:0) showed the lowest onset potential for methanol electro-oxidation, PtRuSn (50:0:50) for ethanol, and PtRuSn (20:70:10) for 2-propanol in CV results respectively, and single cell performance test indicated that Ru is more suitable for direct methanol fuel cell system, Sn for direct ethanol fuel cell system, and 2-propanol could be applied as fuel with low platinum composition anode electrocatalyst. The single cell performance results and electrochemical results (CV) were well matched with the combinatorial electrochemical results. As a result, we could verify the availability of combinatorial chemistry by comparing the results of each extreme electrocatalysts compositions as follows: PtRuSn (80:20:0) for methanol, PtRuSn (50:0:50) for ethanol and PtRuSn (20:70:10) for 2-propanol.     

The effect of hydrogen addition on premixed laminar acetylene–hydrogen–air and ethanol–hydrogen–air flames

In the present work, the laminar premixed acetylene–hydrogen–air and ethanol–hydrogen–air flames were investigated numerically. Laminar flame speeds, the adiabatic flame temperatures were obtained utilizing CHEMKIN PREMIX and EQUI codes, respectively. Sensitivity analysis was performed and flame structure was analyzed. The results show that for acetylene–hydrogen–air flames, combustion is promoted by H and O radicals. The highest flame speed (247 cm/s) was obtained in mixture with 95% H₂–5% C₂H₂ at λ = 1.0. The region between 0.95 < X_H2 < 1.0 was referred to as the acetylene-accelerating hydrogen combustion since the flame speed increases with increase the acetylene fraction in the mixture. Further increase in the acetylene fraction decreases the H radicals in the flame front. In ethanol–hydrogen–air mixtures, the mixture reactivity is determined by H, OH and O radicals. For X_H2 < 0.6, the flame speed in this regime increases linearly with increasing the hydrogen fraction. For X_H2 > 0.8, the hydrogen chemistry control the combustion and ethanol addition inhibits the reactivity and reduces linearly the laminar flame speed. For 0.6 < X_H2 < 0.8, the laminar flame speed increases exponentially with the increase of hydrogen fraction.     

The hydriding kinetics of Mg–Ni based hydrogen storage alloys: A comparative study on Chou model and Jander model

Two kinds of kinetic models, which are Jander model and Chou model, were applied to investigate the hydriding kinetic behavior of Mg–Ni based alloys. By comparing the calculated values with experimental data, it can be seen that both models were successfully used in the diffusion-controlled hydrogen absorption process of Mg–Ni system. However, Chou model was not only convenient for use but also gave a set of physical meaningful explicit analytic expressions. Chou model should be preferentially recommended to deal with the calculation at multi-temperatures and multi-pressures without multistep calculation. The application of Chou model to Mg₂₀Ni₈Cu₂ and Mg₂₀Ni₈Co₂ alloys shows that the calculated results agreed well with the experimental data and it is reasonable to expect that this model will also suitable for other Mg–Ni based alloys if the mechanism is similar.     

The effect of residential solar photovoltaic systems on home value: A case study of Hawai‘i

An investment in solar photovoltaic (PV) is considered a home improvement, and should be reflected in home sales prices. However, uncertainty about PV policies and information asymmetries may result in an imperfect pass-through. Hawai‘i serves as an illustrative case study to assess the impact of PV on home prices because Hawai‘i has the highest number of PV installations per capita nationwide. Applying a hedonic pricing model using home resale and PV building permit data from 2000 to 2013 for Oʻahu, I find that the presence of PV adds on average 5.4% to the value of a home. The value of PV exceeds total average installed costs because many of Hawai‘i's electricity circuits have reached legal limits for PV installations and thus many neighborhoods could technically no longer install additional PV capacity. Therefore, the value of the system goes beyond its capital investment—on average, by $5000—to incorporate expected electricity savings.     

Endurance study of a solid polymer electrolyte direct ethanol fuel cell based on a Pt–Sn anode catalyst

The performance decay of a solid polymer electrolyte direct ethanol fuel cell (DEFC) based on a Pt₃Sn₁/C anode catalyst during an endurance test has been investigated. The effect of different cell shut-down procedures on the cycled behaviour of the DEFC has been studied. To get specific insights into the degradation mechanism, polarization and ac-impedance spectroscopy studies have been carried out. These analyses have been complemented by post-operation transmission electron microscopy and X-ray diffraction studies. The combination of these techniques has allowed to get information on recoverable and unrecoverable losses. This provides a basis for further improvement of DEFC components.