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.     

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 O₂ to H₂O₂ and further reduction of H₂O₂ to H₂O. The first 2-electron reduction of O₂ 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 RDE studies show a potential dependent change in the number of electrons on gold electrode. The oxygen reduction reaction on boron-doped diamond (BDD) 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.     

Ethanol oxidation on novel, carbon supported Pt alloy catalysts—Model studies under defined diffusion conditions

The structure, surface composition and activity/selectivity for ethanol oxidation of carbon supported Pt alloy catalysts with different composition and catalyst loading, which were synthesized via the polyol-route, were investigated and characterized by microscopic/spectroscopic methods (TEM, EDX, XRD) and electrochemical (RDE, on-line DEMS) measurements under well-defined transport and diffusion conditions. The performance of the polyol-type Pt/C (20 wt.%), PtRu/C (20, 40 and 60 wt.%), and Pt₃Sn/C (20 wt.%) catalysts was compared with that of commercial Pt/C, PtRu/C and Pt₃Sn/C (E-Tek) catalysts. The metal particle sizes of the polyol-type catalysts are significantly smaller than those of the corresponding commercial catalysts, nevertheless both the mass specific activities and, more pronounced, the inherent, active surface area specific activities are lower than those of the commercial catalysts, which is related to the lower degree of alloy formation in the polyol-type catalysts. For all catalysts, incomplete ethanol oxidation to C2 products (acetaldehyde and acetic acid) prevails under conditions of this study, CO₂ formation contributes by ≤1% for potentiostatic reaction conditions. The lower activity of the polyol-type catalysts is mainly due to the lower activity for acetaldehyde formation. Implications and further strategies for fuel cell applications are discussed.     

The stability of an acidic tin methanesulfonate electrolyte in the presence of a hydroquinone antioxidant

The electrodeposition of tin at a (0.28 cm²) copper surface from 0.014 mol dm⁻³ SnSO₄ and 12.5 vol.% methanesulfonic acid (MSA 1.93 mol dm⁻³) at 296 K was studied. Hydroquinone concentrations of 0.005, 0.05 and 0.5 mol dm⁻³ (corresponding to a molar concentration ratio of hydroquinone to stannous ions of 0.36, 3.6 and 36, respectively) were used. Cyclic and linear sweep voltammetry served to characterise the electrochemical behaviour of tin deposition and stripping. The effects of potential sweep rate and electrode rotation speed on the voltammetry were studied. The stability of the electrolyte with storage time was quantified by changes in the limiting current density for tin deposition at a smooth rotating disc electrode and the peak current density at a static disc electrode. The influence of hydroquinone on mass transport controlled tin deposition and suppression of hydrogen evolution was evaluated.     

Uncovering the mind-sets of consumers towards food safety messages

Knowing the specific characteristics which trigger a strong sense of safe versus unsafe allows risk communicators to reach consumers effectively with targeted messages. Using experimental design of ideas and conjoint measurement, we assessed consumer interest in and perceived safety of food characteristics that consumers think to be important when they make a purchase decision. The study identified the specific characteristics and the associated phrasing. The data generate a database by which we understand the perceptions of risk. In turn the database shows how these risk perceptions vary by conventional subgroups (age, gender, ethnicity), and by different mind-sets that exist in the population. The results combine insights about acceptance with insights about safety, answering questions that could not have been previously addressed in this efficient, quantitative way. The study is the first in a series designed to create a large-scale database of safety for food, beverage, and eating situation, based on the perceptions of consumers. The study opens up a new area for consumer understanding dealing with the perception of intangible topics including safety, compliance, and ‘good-for-you’.     

Kinetics and electrocatalytic activity of nanostructured Ir-V/C for oxygen reduction reaction

Active, carbon-supported Ir-V nanoparticle catalysts have been synthesized by an ethylene glycol reduction method under controlled conditions at pH 10-13 and 120 °C, then further reduced at elevated temperature from 150 to 500 °C using IrCl₃ and NH₄VO₃ as the Ir and V precursors. The nanostructured catalysts have been characterized by X-ray diffraction (XRD) and high-resolution transmission electron microscopy (TEM). Ir nanoparticles, after modification with V, show a narrow particle size distribution in the range 0.5-4.5 nm, centered at 1.8 nm, and are uniformly dispersed on Vulcan XC-72. No particle agglomeration was observed, not even at high V loadings (V:Ir = 4:1 in atomic ratio). Investigation of the catalytic activity of the Ir-V/C by means of cyclic voltammetry (CV) and linear sweep voltammetry (LSV) employing a rotating disk electrode (RDE) has revealed that the presence of V may suppress the electrochemical oxidation of Ir and stabilize the Ir active centers. About six times higher kinetic current density was obtained for Ir-V/C compared to that of the pure Ir/C catalyst at 0.8 V versus RHE for the oxygen reduction reaction (ORR). The ORR in acid solution proceeds by an approximately four-electron pathway, through which molecular oxygen is directly reduced to water. The performance of a membrane electrode assembly (MEA) prepared with the most active 40% Ir-10% V/C as the cathode catalyst in a single proton-exchange membrane fuel cell (PEMFC) generated a maximum power density of 517 mW cm⁻² at 0.431 V and 70 °C, and 100 h of stable cell operation due to no loss of catalyst sites on the cathode.     

基于BP神经网络的车辆碳排放测算研究

研究轻型车辆碳排放测算方法,分析车辆碳排放与运行工况关系。基于车辆实际行驶污染物排放(Real Drive Emission, RDE)车载测试数据,以CO2当量CO2e代表碳排放,分析得出碳排放速率随车速、比功率(Vehicle Specific Power, VSP)增大而上升;运用BP (Back Propagation)神经网络算法建立车辆碳排放与车速、加速度、比功率多参数间非线性关系测算模型,计算得出世界轻型车测试循环(World Light Vehicle Test Cycle,WLTC)、新欧洲行驶循环(New European Driving Cycle, NEDC)和中国轻型商用车行驶工况(China Light-duty Vehicle Test Cycle-commercial Car,CLTC-C)3种台架测试循环工况下的碳排放因子。比较发现3种台架测试循环工况下的碳排放因子均高于实际道路行驶碳排放因子,其中WLTC下碳排放因子最高,其次是NEDC,再是CLTC-C,原因是加速度越大、车速越高的测试工况导致碳排放增加。     

Mesoporous carbon as Pt support for PEM fuel cell

A mesoporous carbon (MP) supported Pt nanocatalyst was evaluated as anode and cathode catalyst for PEM fuel cell. Kinetics study of the oxygen reduction reaction were characterized by using the rotating disk electrode (RDE) and rotating ring disk electrode (RRDE) techniques in acid media. Membrane electrode assemblies (MEAs) were prepared using Pt supported on MP as anodic and cathodic catalysts and the fuel cell performance evaluated. Polarization and power curves show a similar performance as cathode catalyst when compared to commercial catalyst while there is an 8% improvement when used as anode catalyst.     

A melamine formaldehyderesin route to in situ encapsulate Co2O3 into carbon black for enhanced oxygen reduction in alkaline media

Enhancing the activity and stability of the non-precious metal catalyst (NPMC) for oxygen reduction reaction (ORR) is vital for the commercialization of fuel cells. Herein, we put forward a method in which the melamine formaldehyderesin was used as a precursor to encapsulate in situ Co₂O₃ into carbon black to form Co₂O₃@MF-C catalysts. The prepared catalysts were characterized by TEM, XRD, XPS, BET, and Raman spectroscopy. The electrocatalytic activity was measured by using rotating disk electrode (RDE) voltammetry. The Co₂O₃@MF-Cs shows outstanding electrocatalytic activity in alkaline solution compared with the commercial Pt/C catalyst. The 20%Co₂O₃@MF-C-650 shows the highest activity for ORR and its initial reduction potential and half-wave potential reach 1.01 V and 0.94 V, respectively, in 0.1 M KOH solution. The prepared catalysts also follow the 4-electron pathway ORR process both in alkaline and in acid conditions.