Behavior of Ruthenium in Fluoride-Volatility Processes, (VI)

Hydrogen gas evolution from water dispersing nanoparticles induced by ⁶⁰Co γ-ray irradiation was studied. Nanoparticles of TiO₂ and Al_2O3 with average sizes of 7–33 nm supplied from several suppliers were examined. It was indicated that reactions enhancing the hydrogen evolution proceed on particle's surface. It was implied that the yield depends on size of agglomerated particle regardless of their primary particle size and chemical species. Reactions that enhance the hydrogen yields were discussed, and radiolysis process was concluded dominant in the total enhancement mechanism.     

Combined generation and separation of hydrogen in an electrochemical water gas shift reactor (EWGSR)

Hydrogen rich gas, originating from fossil fuel reforming processes or biomass gasification, contains a significant amount of CO. Typically, the yield of H₂ is increased with subsequent water gas shift units, converting CO to CO₂ and additional H₂. This study describes a new reactor concept enabling the water gas shift reaction and the separation of the generated hydrogen in one process step by using electrical energy. This electrochemical water gas shift reactor applies a H₃PO₄-doped Poly(2,5-benzimidazole) membrane as electrolyte and carbon supported Pt or PtRu as anode catalyst. The reactor operation was investigated at 130 °C and 150 °C with a H₂ free anode feed stream of humidified CO and N₂. The experimental results show the feasibility of the reactor concept, as H₂ was generated at the cathode according to Faradays Law. Anodic PtRu led to lower power demands than Pt. The operation at the two temperatures showed that 130 °C results in a lower electrical power demand while generating an equal amount of H₂. The feasibility of the reactor was assessed using exergy efficiency analysis.     

Hydrogenation of CO2 to formic acid on supported ruthenium catalysts

We report on the preparation and application of novel heterogeneous supported ruthenium catalysts. The catalysts are active in the synthesis of formic acid from the hydrogenation of carbon dioxide and are characterized by Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy, X-ray powder diffraction analysis and transmission electron microscopy. Abundant hydroxyl groups, which interact with the ruthenium components, play an important role in the catalytic reactions. Highly dispersed ruthenium hydroxide species enhance the hydrogenation of CO₂, while crystalline RuO₂ species, which are formed from the relatively high ruthenium content or the pH of the solution during preparation of the catalyst, restrict the production of formic acid. Optimal activity of ruthenium hydroxide as a catalyst for the hydrogenation of CO₂ to formic acid is achieved over a γ-Al₂O₃ supported 2.0 wt% ruthenium catalyst, which is prepared in a solution of pH 12.8 with NH₃·H₂O as a titration solvent. A possible hydrogenation mechanism for the hydroxide ruthenium catalyst is proposed.     

Ru/C催化剂在苯选择加氢反应中的催化性能

采用沉积沉淀法制备了以活性炭(C)为载体的Ru催化剂,研究了Ru/C催化剂在苯选择加氢反应中的催化性能,并对Ru/C催化剂进行了表征.结果表明:Ru在催化剂中的分散性好,Ru/C催化剂具有较高的催化活性;适宜的反应条件为温度140℃,压力5.0 MPa,催化剂中Ru质量分数为4.0％,苯的转化率达40％以上,产物环己烯...     

染料敏化太阳能电池用钌系光敏化剂研究进展

钌系光敏化剂作为染料敏化太阳能电池(DSSC)敏化剂组件中最重要光敏化剂之一,近年来受到国内外研究人员的重视及研究。其中,以羧酸联吡啶钌配合物为光敏化剂的DSSC器件表现出最好的综合性能。简要介绍了钌系光敏剂的结构,以及其性能的主要影响因素。按照各个光敏化剂的结构,分别阐述了固定配体(含羧基、磺酸基等)和辅助配体(二联吡啶衍生物等)对钌系光敏化剂综合性能的影响,同时给出了对应的各类光敏化剂最新研究进展。     

从失效催化剂中回收钌的研究进展

总结了从失效催化剂中回收钌的多种方法和工艺,重点介绍了常用的熔融氧化蒸馏法。熔融氧化蒸馏法由于工艺繁杂、步骤冗长、对设备要求高等缺点,近年来不同学者和行业专家先后提出了还原沉淀法、直接氧化法和活泼金属置换法等方法,但尚未有工业化应用的报道。简化工艺流程、提高钌的回收率是目前钌回收研究工作并实现其工业化生产的重点和难点。     

Promotion of the electrocatalytic activity of a bimetallic platinum-ruthenium catalyst by repetitive redox treatments for direct methanol fuel cell

Pt-Ru/C catalyst (12 wt%) was prepared by the incipient wetness impregnation method followed by a redox heat-treatment. Transmission electron microscopy (TEM) results revealed uniformly distributed metallic crystallites of Pt-Ru alloy nanoparticles (d_PtRu = 2.1 ± 1.0 nm). The effect of redox treatments of the impregnated catalysts on methanol oxidation reaction (MOR) was examined by cyclic voltammetry (CV). The MOR activity of the PtRu/C was significantly improved after each oxidation step of the redox treatment cycles. The enhanced catalytic activity was found to be quite stable in chronoamperometry (CA) measurements. CV, X-ray photoelectron spectroscopy (XPS), and X-ray diffraction (XRD) results strongly suggested that the improved catalytic activity was due to the formation of a stable c-RuO_x (x = 2-3) domain during the oxidation treatments. A bifunctional based mechanism was proposed for the MOR on the oxidized PtRu/C catalysts. Formation of Ru-OH species on the surface of c-RuO_x domains was suggested as stale sites for the oxidation of carbon monoxide adsorbed on the Pt catalytic sites.     

Facile synthesis of a Bi-modified PtRu catalyst for methanol and ethanol electro-oxidation in alkaline medium

In this work a facile synthesis for a high-performance PtRuBi/C catalyst was presented through a simple mixture of commercial PtRu/C and Bi(NO₃)₃. Most of the Bimodified the PtRu particle surface via irreversible adsorption and deposition processes. X-ray photoelectron spectroscopy analysis indicated that Bi₂O₃ was the main form in the catalyst and that there exists an interaction between Bi₂O₃ and Pt. The current density of PtRuBi/C (1:1:0.2 for Pt:Ru:Bi) in the cyclic voltammograms for methanol or ethanol oxidation is over 2.6 times higher than that of PtRu/C. The anti-poisoning ability of this catalyst was also greatly improved. The Bi-containing catalyst had abundant oxygenated species and facilitated removal of poisonous intermediate species.     

Characterization of multi-walled carbon nanotube electrodes functionalized by electropolymerized tris(pyrrole-ether bipyridine) ruthenium (II)

We synthesized new electropolymerizable [Ru(bpy)_nL_m](PF₆)₂ (L = 4,4 bis(3-pyrrol-1-ylpropyloxy)bipyridyl) derivatives. The introduction of electron donating ether groups in the bipyridine ligand induced a negative shift of the Ru(III)/(II) redox couple. The electrochemical behavior of complex Ru1 (n = 2, m = 1) and complex Ru2 (n = 0, m = 3) were compared using platinum and Multi-Walled Carbon Nanotube (MWCNT) electrode. Higher polymerization yields and surface concentrations were obtained at MWCNT electrodes. Furthermore, MWCNT electrodes increase polymer permeability and decrease the charge trapping phenomenon involved in the oxidation and reduction of the polypyrrolic skeleton of the Ru(II) functionalized polymers.