Phytic acid-assisted fabrication of superhydrophilic Ru 3D electrode for electrocatalytic hydrogenation of p-Nitrophenol

A superhydrophilic Ru-based 3D electrode, denoted as Ru-PA/NF, was fabricated under the assistance of phytic acid (PA) for electrocatalytic hydrogenation of p-Nitrophenol. PA serves as a multifunctional modulator to facilitate the dispersion of active Ru species in porous nickel foam (NF), meanwhile enhance the surface wettability as well as adjust the micromorphology. In alkaline media, the Ru-PA/NF electrode shows the PNP conversion of 94.68% and the PAP selectivity of 99% after 9 h, accompanied by the faraday efficiency (FE) of 73.15%. Over the superhydrophilic Ru-PA/NF the rate constant of PNP conversion into PAP is 2.62-times higher than that over the hydrophobic Ru/NF prepared without the aid of PA, and FE of Ru-PA/NF is 1.28-times higher than Ru/NF. This can be ascribed to intriguing features of Ru-PA/NF involving higher Ru loading, more exposed sites, superior electrolyte wetting along with faster charge transfer rate.     

Hydrotreatment of jatropha oil over noble metal catalysts

Jatropha oil is a promising nonedible feedstock for producing renewable diesel. In this work, the hydrotreatment processing of jatropha oil was investigated. Instead of using conventional alumina-supported Co–Mo, Ni–Mo, and Ni–W catalysts that need sulfidation pretreatment, noble metals such as Pd and Ru were chosen. Trials were performed in an isothermal trickle-bed reactor and the reaction conditions were as follows: temperature 603–663?K, weight hourly space velocity (WHSV) 1 to 4/h, pressure 1.5–3?MPa, and H₂/oil ratio 200–800 (v/v). Yield of n-C₁₅ to n-C₁₈ hydrocarbons was maximized (70.3 and 43.8% for Pd/Al₂O₃ and Ru/Al₂O₃, respectively) at the following conditions: T?=?663 K, WHSV?=?2/h, P?=?3?MPa, and H₂/oil ratio?=?600 (v/v). Since Ru favored cracking reactions to a larger extent than Pd, the yield of C₁₅ to C₁₈ hydrocarbons over Ru/Al₂O₃ was lowered. Using simple first-order plots for oil conversion, activation energies for the hydrotreating process over Pd/Al₂O₃ and Ru/Al₂O₃ were found and they were equal to 109 and 121?kJ/mol, correspondingly.     

Facile construction of composition-tuned ruthenium-nickel nanoparticles on g-C3N4 for enhanced hydrolysis of ammonia borane without base additives

Developing high-efficiency and low-cost catalysts for hydrogen evolution from hydrolysis of ammonia borane (AB) is significant and critical for the exploitation and utilization of hydrogen energy. Herein, the in-situ fabrication of well-dispersed and small bimetallic RuNi alloy nanoparticles (NPs) with tuned compositions and concomitant hydrolysis of AB are successfully achieved by using graphitic carbon nitride (g-C₃N₄) as a NP support without additional stabilizing ligands. The optimized Ru₁Ni_7.5/g-C₃N₄ catalyst exhibits an excellent catalytic activity with a high turnover frequency of 901 min^?1 and an activation energy of 28.46 kJ mol^?1 without any base additives, overtaking the activities of many previously reported catalysts for AB hydrolysis. The kinetic studies indicate that the AB hydrolysis over Ru₁Ni_7.5/g-C₃N₄ is first-order and zero-order reactions with respect to the catalyst and AB concentrations, respectively. Ru₁Ni_7.5/g-C₃N₄ has a good recyclability with 46% of the initial catalytic activity retained even after five runs. The high performance of Ru₁Ni_7.5/g-C₃N₄ should be assigned to the small-sized alloy NPs with abundant accessible active sites and the synergistic effect between the composition-tuned Ru–Ni bimetals. This work highlights a potentially powerful and simple strategy for preparing highly active bimetallic alloy catalysts for AB hydrolysis to generate hydrogen.     

Modification of platinum surfaces by spontaneous deposition: Methanol oxidation electrocatalysis

The presence of a second metal on platinum surfaces affects the performance of methanol oxidation. However, most of the electrocatalytic reactions are studied by using electrochemically deposited platinum alloys, but in the case of spontaneous deposition the situation is not so clear since the surface distribution, stability and morphology are usually not well documented. The formation of surface decorated samples on mono- and poly-crystalline platinum is followed by electrochemical and spectroscopic techniques and analysis of their performance towards methanol adsorption and oxidation compared with that on pure platinum. Pt/Sn and Pt/Ru are of special interest because of their well-known performance in methanol fuel cells. Methanol oxidation on Pt(111)/Ru, Pt(111)/Sn and Pt(111) shows that ruthenium is the only one able to promote the reaction since the simultaneous dissolution of tin occurs and competes with the process of interest. The in situ infrared spectroscopy is used to compare methanol oxidation on Pt(111)/Ru and Pt(111) in acid media using p-polarized light. The formation of bridge bound carbon monoxide is inhibited in the presence of ruthenium ad-species, whereas on Pt(111) the three adsorption configurations are observed. Linear sweep polarization curves and Tafel slopes (calculated from steady state potentiostatic plots) for methanol oxidation are compared on polycrystalline surfaces modified by tin or ruthenium at different coverages. There is almost no change in the Tafel slopes due to the presence of the foreign metal except for Pt/Ru, where a 0.09 V decade⁻¹ slope was calculated below 0.55 V due to hydroxyl adsorbates on ruthenium islands. The anodic stripping of methanol residues on the three surfaces indicates a lower amount of carbon monoxide-type adsorbates on Pt/Ru, and the simultaneous tin dissolution process leading to residues oxidation on Pt/Sn electrodes.     

Chemical vapor deposition of amorphous ruthenium-phosphorus alloy films

Chemical vapor deposition growth of amorphous ruthenium-phosphorus films on SiO₂ containing ∼ 15% phosphorus is reported. cis-Ruthenium(II)dihydridotetrakis-(trimethylphosphine), cis-RuH₂(PMe₃)₄ (Me = CH₃) was used at growth temperatures ranging from 525 to 575 K. Both Ru and P are zero-valent. The films are metastable, becoming increasingly more polycrystalline upon annealing to 775 and 975 K. Surface studies illustrate that demethylation is quite efficient near 560 K. Precursor adsorption at 135 K or 210 K and heating reveal the precursor undergoes a complex decomposition process in which the hydride and trimethylphosphine ligands are lost at temperatures as low at 280 K. Phosphorus and its manner of incorporation appear responsible for the amorphous-like character. Molecular dynamics simulations are presented to suggest the local structure in the films and the causes for phosphorus stabilizing the amorphous phase.     

Catalytic steam reforming of methane over La0.8Sr0.2CrO3 based Ru catalysts

La_0.8Sr_0.2CrO₃ based Ru catalysts were studied as potential new anodic materials for Solid Oxide Fuel Cells directly fed with methane and operating at intermediate temperature under water deficient conditions. Two kinds of materials very close in composition were obtained following two different preparation procedures. Catalyst samples were characterized by physicochemical methods (XRD, SEM, BET and Chemical Analysis) and studied in methane steam reforming under water deficient conditions. Carbon formation during catalytic testing was studied by temperature programmed oxidation (TPO). Both types of catalysts were found very active and resistant to carbon formation. The unusual oscillatory behavior of the catalytic activity observed for one type of catalyst was discussed.     

Effects of thermal oxidation conditions of silicon electrodes on cathodic electrochemiluminescence of Ru(bpy)3 chelate

Hot electrons emitted from thin oxide film-coated heavily doped silicon electrodes by cathodic pulse polarization can induce electrochemiluminescence from luminophores. The intensity of electrochemiluminescence produced at the electrode surface is dependent on the features of thin oxide films formed by thermal oxidation. As a preliminary study, we investigated the effect of thermal oxide growth conditions on the intensity of electrochemiluminescence produced at these electrodes, such as oxidation atmospheres, oxidation temperature, oxidation time and pre-treatment of wafers, using ruthenium(II) tris-(2,2′-bipyridine) chelate as a model luminophore. Optimal oxidation conditions of heavily doped silicon electrodes were obtained for the generation of intense electrochemiluminescence at this kind of silicon electrodes.     

Experimental assessment of the Ru–Al–Ni ternary phase diagram at 1000 and 1100 °C

Knowledge of phase equilibria in the Ru–Al–Ni ternary system is relevant to the development of new single crystal Ni-based superalloys as well as to new high temperature protective coating systems for these alloys. A series of diffusion couple investigations have been performed across the Ru–Al–Ni ternary system in order to establish phase fields and possible diffusion paths. A continuous B2 phase has been shown to exist across the Ru–Al–Ni ternary between the RuAl and NiAl phases at temperatures of 1000 and 1100 °C. Ternary isothermal sections for Ru–Al–Ni at 1000 and 1100 °C are presented.