Co-electrodeposition of Pt–Ru electrocatalysts in electrolytes with varying compositions by a double-potential pulse method for the oxidation of MeOH and CO

The co-eletrodeposition of Pt–Ru on carbon electrodes was carried out using a double-potential pulse method in electrolytes containing varying concentrations of RuCl₃ + H₂PtCl₆ in an attempt to deposit highly dispersed Pt–Ru electrocatalyst with a controlled composition. The amounts of the Pt and Ru deposited on the electrodes were analyzed using an inductively coupled plasma atomic emission spectrometer (ICP-AES). The results revealed that the Pt loading on the substrates increases linearly with H₂PtCl₆ concentrations in the bath while the Ru loading is not related to the concentration of RuCl₃, indicating that the reduction of Pt ions is the dominant reaction in the cathodic deposition of Pt–Ru clusters on the substrate. The Pt–Ru/C electrodes were characterized by X-ray diffraction (XRD) and scanning electron microscopy (SEM). The optimum Ru content in the deposited Pt–Ru electrode for promoting the electro-oxidation of MeOH and adsorbed CO was found to be 25 atm%, by CO-stripping measurements in 0.5 M H₂SO₄ and by cyclic voltammography in a solution comprising CH₃OH (2.0 M) +0.5 M H₂SO₄ (0.5 M). SEM results showed that the generation of nucleation sites and growth of the deposits progresses continuously on carbon substrate and already deposited Pt–Ru particles. The particle size and loading amount of the deposits was found to increase with an increase in the number of cycles of the repeating double-potential pulse.     

An asymmetric anthraquinone-modified carbon/ruthenium oxide supercapacitor

An asymmetric supercapacitor with improved energy and power density, relative to a symmetric Ru oxide device, has been constructed with anthraquinone-modified carbon fabric (Spectracarb 2225) as the negative electrode and Ru oxide as the positive electrode. The performance of the supercapacitor was characterized by cyclic voltammetry and constant current discharging. Use of the anthraquinone-modified electrode extends the negative potential limit that can be used, relative to Ru oxide, and allows higher cell voltages to be used. The maximum energy density obtained was 26.7 Wh kg⁻¹ and an energy density of 12.7 Wh kg⁻¹ was obtained at a 0.8 A cm⁻² discharge rate and average power density of 17.3 kW kg⁻¹. The C-AQ/Ru oxide supercapacitor requires 64% less Ru relative to a symmetric Ru oxide supercapacitor.     

Highly active and durable FexCuyNi1-x-y/FeOOH/NiOOH/CuO complex oxides for oxygen evolution reaction in alkaline media

Oxygen evolution reaction (OER) catalyzed by Ru/Ir-free electrocatalysts is pivotal for preparing oxygen in efficient way, yet our understanding of the relationship between microphysical properties and OER performance is still insufficient. Here we report on 41 kinds of Fe_xCu_yNi_1-x-y/FeOOH/NiOOH/CuO complexes (FCN-x) to investigate the Cu and Fe induced electronic perturbation and what it brings to OER performance. As result, the activity mapping of FCN-x shows an optimal composition of 1:2:7 (FCN-7) showing a comparable overpotential potential of 170.3 mV, Tafel slop of 75.9 mV dec^?1 and durability of 24 h (～29% activity loss) to that of mainstream Ru/Ir-free catalysts. Such enhancement could be attributed to the role of alloying contribution of Fe/Cu, electronic perturbation and surface modification of surface oxides. Additionally, the incompletely oxidized Fe_xCu_yNi_1-x-y not only provide a platform for electron conduction, but also work as a sacrificial material to forming fresh oxides to maintain the content of surface oxides, which is a key driver of the excellent durability of FCN-7. This synthetic strategy may give an effective way to design and screen Ru/Ir-free OER catalysts.     

钌系厚膜电阻器电阻温度系数及变化规律

研究以RuO2,Bi2Ru2O7,Pb2Ru2O6.5等导电相制备的电阻浆料的电阻温度系数及其变化规律.试验结果表明当导电相低于一定含量时,TCR为负值,反之,TCR为正值.电阻温度系数为正值的电阻器以金属型传导为主,TCR为负值的电阻器以隧道势垒传导为主.还考查了MnO2对RuO2和钌酸盐正温度系数的改进.     

Methanol electrooxidation on synthesized PtRu nanocatalyst supported on acetylene black in half cell and in direct methanol fuel cell

We reported the direct reduction of H₂PtCl₆ and RuCl₃ solution containing acetylene black powder by Na₂S₂O₄ to make Pt–Ru (20–10 wt%) supported on acetylene black (Pt–Ru/AB) as a nanocatalyst for methanol electrooxidation in acidic media. The electrochemical activity of catalyst was studied by electrochemical impedance spectroscopy, linear sweep voltammetry, cyclic voltammetry and chronoamperometry. Structural aspects of the Pt–Ru (20–10 wt%)/AB were studied by transmission electron microscopy (TEM) and X-ray diffraction (XRD) techniques. The analysis of electrochemical results indicated lower charge transfer resistance, higher peak current for Pt–Ru (20–10 wt%)/AB compared to the commercial catalyst, Pt–Ru (20–10 wt%)/carbon Vulcan. XRD spectra verified a face centered cubic structure for the synthesized Pt–Ru/AB and its particle size was mostly 10 nm according to TEM and XRD images. In DMFC, Pt–Ru/AB had superior performance compared to the commercial catalyst in all current densities, which could be attributed to enhancement of the methanol oxidation kinetics, higher conductivity, and more uniform distribution of the ionomer in anode catalyst layer.     

Impacts of air bleeding on membrane degradation in polymer electrolyte fuel cells

A long-term accelerated test (4600 h) of a 25 cm² single cell with excess air bleeding (5%) was carried out to investigate the effects of air bleeding on membrane degradation in polymer electrolyte fuel cells. The rate of membrane degradation was negligibly low (fluoride-ion release rate = 1.3 × 10⁻¹⁰ mol cm⁻² h⁻¹ in average) up to 2000 h. However, membrane degradation rate was gradually increased after 2000 h. The CO tolerance of the anode gradually dropped, which indicated that the anode catalyst was deteriorated during the test. The results of the rotating ring–disk electrode measurements revealed that deterioration of Pt–Ru/C catalyst by potential cycling greatly enhances H₂O₂ formation in oxygen reduction reaction in the anode potential range (∼0 V). Furthermore, membrane degradation rate of the MEA increased after the anode catalyst was forced to be deteriorated by potential cycling. It was concluded that excess air bleeding deteriorated the anode catalyst, which greatly enhanced H₂O₂ formation upon air bleeding and resulted in the increased membrane degradation rate after 2000 h.     

Development of highly efficient and reusable Ruthenium complex catalyst for hydrogen evolution

Herein, we report an efficient, environmentally friendly and stable catalyst development to hydrogen evolution from sodium borohydride hydrolysis. For this purpose, Ruthenium complex catalyst successfully fabricated via 5-Amino-2,4-dichlorophenol-3,5-ditertbutylsalisylaldimine ligand and RuCl₃·H₂O salt. Ru complex catalyst was identified with X-Ray Diffraction Analysis, Infrared Spectroscopy, Elemental Analysis, Transmission electron microscopy, Scanning Electron Microscope and Brunauer-Emmett-Teller Surface Area Analysis. According to the analysis results, it was confirmed that Ru complex catalyst was successfully synthesized. Ru complex was used as a catalyst in NaBH₄ hydrolysis. The kinetic performance of Ru complex catalyst was evaluated at various reaction temperatures, various sodium borohydride concentration, catalyst concentration and sodium hydroxide concentration in hydrogen evolution. The apparent activation energy for the hydrolysis of sodium borohydride was determined as 25.8 kJ mol^?1. With fully conversion, the promised well durability of Ru complex was achieved by the five consecutive cycles for hydrogen evolution in sodium borohydride hydrolysis The hydrogen evolution rates were 299,220 and 160,832 mL H₂ g_cat^?1 min^?1 in order of at 50 °C and 30 °C. Furthermore, the proposed mechanism of Ru complex catalyzed sodium borohydride hydrolysis was defined step by step. This study provides different insight into the rational design and utilization and catalytic effects of ruthenium complex in hydrogen evolution performance.     

Preparation and characterization of Co-Ru/TiO2/MWCNTs electrocatalysts in PEM hydrogen electrolyzer

The subject of this study is preparation and characterization of hypo-hyper d-electrocatalysts with reduced amount of precious metals aimed for water electrolysis. The studied electrocatalysts contain 10% mixed metallic phase (Co:Ru = 1:1 wt., Co:Ru = 4:1 wt. and Co:Ru:Pt = 4:0.5:0.5 wt.), 18% TiO₂ as a crystalline anatase deposited on multiwalled carbon nanotubes (MWCNTs). Previously, MWCNTs were activated in 28% nitric acid. As a reference electrocatalyst for hydrogen evolution reaction, corresponding electrocatalysts with pure Pt metallic phase and mixed CoPt (Co:Pt = 1:1 wt.) metallic phase were prepared. Also, as a reference electrocatalyst for oxygen evolution reaction, electrocatalyst with pure Ru metallic phase was prepared.The prepared electrocatalysts were structurally characterized by means of XPS, XRD, TEM, SEM and FTIR analysis.Electrochemical characterization was performed by means of cyclic voltammetry and potentiodynamic method in the PEM hydrogen electrolyzer. The range of the catalytic activity for hydrogen evolution of studied electrocatalysts was the following: CoRuPt (4:0.5:0.5) > CoPt (1:1) > Pt > CoRu (1:1) > CoRu (4:1). The order of the catalytic activity for oxygen evolution was the following: CoRu (1:1) > Ru > CoRu (4:1) > Pt > CoRuPt (4:0.5:0.5) > CoPt (1:1).     

Kinetics of NaBH4 hydrolysis on carbon-supported ruthenium catalysts

In this work, different shapes (powder and spherical) of ruthenium-active carbon catalysts (Ru/C) were prepared by impregnation reduction method for hydrogen generation (HG) from the hydrolysis reaction of the alkaline NaBH₄ solution. The effects of temperature, amount of catalysts, and concentration of NaOH and NaBH₄ on the hydrolysis of NaBH₄ solution were investigated with different shapes of Ru/C catalysts. The results show that the HG kinetics of NaBH₄ solution with the powder Ru/C catalysts is completely different from that with the spherical Ru/C catalysts. The main reason is that both mass and heat transfer play important roles during the reaction with Ru/C catalysts. The HG overall kinetic rate equations for NaBH₄ hydrolysis using the powder Ru/C catalysts and the spherical catalysts are described as r = A exp (−50740/RT) [catalyst]^1.05 [NaOH]^−0.13 [NaBH₄]^−0.25 and r = A exp (−52,120/RT) [catalyst]^1.00 [NaOH]^−0.21 [NaBH₄]^0.27 respectively.