Electro‑copolymerized film of ruthenium catalyst and redox mediator for electrocatalytic water oxidation

Electro-copolymerized film containing ruthenium complexes as electron-transfer(or redox)mediators and water-oxidation catalysts by an oxidative copolymerization method is presented.The addition of the redox mediator significantly improved the electrocatalytic water-oxidation activity and reduced the overpotential to 220 mV.The prepared electrode showed a water-oxidation catalytic rate constant kobs of 31.7 s^(-1)and an initial turnover frequency of 1.01 s^(-1)in 1000 s by potential electrolysis at 1.7 V applied bias vs NHE(normal hydrogen electrode).The kinetic isotope effect study suggests that the catalytic water oxidation reaction on the electrode surface occurs via a bimolecular coupling mechanism.

Advances in the studies of the supported ruthenium catalysts for CO_(2) methanation

CO_(2) methanation has a potential in the large-scale utilization of carbon dioxide.It has also been considered to be useful for the renewable energy storage.The commercial pipeline for natural gas transportation can be directly applied for the methane product of CO_(2) methanation.The supported ruthenium(Ru)catalyst has been confirmed to be active and stable for CO_(2) methanation with its high ability in the dissociation of hydrogen and the strong binding of carbon monoxide.CO_(2) methanation over the supported Ru catalyst is structure sensitive.The size of the Ru catalyst and the support have significant effects on the activity and the mechanism.A significant challenge re-mained is the structural controllable preparation of the supported Ru catalyst toward a sufficiently high low-temperature activity.In this review,the recent progresses in the investigations of the supported Ru catalysts for CO_(2) methanation are summarized.The challenges and the future devel-opments are also discussed.

Metastable face-centered cubic ruthenium-based binary alloy for efficient alkaline hydrogen oxidation electrocatalysis

Metastable nanostructured electrocatalyst with a completely different surface environment compared to conventional phase-based electrocatalyst often shows distinctive catalytic property.Although Ru-based electrocatalysts have been widely investigated toward hydrogen oxidation reaction(HOR)under alkaline electrolytes,these studies are mostly limited to conventional hexagonal-close-packed(hcp)phase,mainly arising from the lack of sufficient synthesis strategies.In this study,we report the precise synthesis of metastable binary RuW alloy with face-centered-cubic(fcc)phase.We find that the introduction of W can serve as fcc phase seeds and reduce the formation energy of metastable fcc-RuW alloy.Impressively,fcc-RuW exhibits remarkable alkaline HOR performance and stability with the activity of 0.67 mA cm_(Ru)^(-2)which is almost five and three times higher than that of hcp-Ru and commercial Pt/C,respectively,which is attributed to the optimized binding strength of adsorbed hydroxide intermediate derived from tailored electronic structure through W doping and phase engineering.Moreover,this strategy can also be applied to synthesize other metastable fcc-RuCr and fcc-RuMo alloys with enhanced HOR performances.

Ru团簇对Ni/Ni_(3)Al合金纳米线形变影响的原子模拟

镍基高温合金是制造先进航空发动机热端部件的关键材料之一,其高温力学性能直接关系到发动机运行安全和使用寿命.本文采用改进分析型嵌入原子模型(MAEAM)和分子动力学(MD)研究合金化元素钌(Ru)团簇对Ni/Ni_(3)Al纳米线形变机制的影响,结果表明:在单轴拉伸应变下,纳米线的弹性模量和屈服强度随温度升高而降低.温度较低时,纳米线形变由位错产生与发射而导致晶格滑移所引起.由于晶格热振动非谐效应不明显,Ru团簇阻碍效果显著,使得晶格滑移区域仅限于Ru团簇与Ni/Ni_(3)Al相界面之间且呈非对称分布.温度较高时,纳米线的形变由位错发射而引起晶格滑移所致,但因非谐效应显著,Ru团簇无法阻碍位错运动,滑移区域在Ru团簇周围对称分布于Ni_(3)Al相中.最后从Ru团簇微观结构及其稳定性的角度进一步分析其对纳米线形变影响.

Effect of ruthenium on γ' precipitation behavior and evolution in single crystal superalloys

The effect of Ru on γ＇ precipitation behavior and evolution in single crystal superalloys with different Ru contents were investigated by scanning electron microscopy with energy dispersive spectroscopy,3D atomic probing,differential scanning calorimetry.The results show that the solvus of the γ＇ phase decreases gradually with increasing Ru content in the alloys by casting or by the same solution and aging treatments,the alloy with a larger Ru content yields a smaller γ＇ phase.The addition of Ru increases the growth rate and coarsening rate of the γ＇ phase.Ru mainly distributes in the γ phase,which causes more Re and Mo partition into the γ＇ phase,increasing the absolute value of mismatch and the rafting rate of the γ＇ phase.

Gas-solid catalytic reactions over ruthenium-based catalysts

Ruthenium （Ru）‐based catalysts are widely employed in several types of gas‐solid reactions because of their high catalytic activities. This review provides theoretical research on Ru‐based catalysts and an analysis of their basic properties and oxidation behavior. There is particular emphasis on Ru‐catalyzed gas‐solid catalytic reactions, including the catalytic oxidation of VOCs, preferential oxidation of CO, synthesis of ammonia, oxidation of HCl and partial oxidation of CH4. Recent litera‐ture on catalysis is summarized and compared. Finally, we describe current challenges in the field and propose approaches for future development of Ru‐based catalysts.

Electronic Structures, DNA-binding, SAR, and Spectral Properties of Ruthenium Methylimidazole Complexes [Ru（MeIm）4L]^2＋（L=iip,tip,2ntz）

Theoretical studies on the electronic and geometric structures, the trend in DNA-binding affinities as well as the the structure-activity relationship （SAR） of a series of water-soluble Ru（II） methylimidazole complexes, i.e. [Ru（Mehn）4iip]^2＋ （1） （MeIm=l-methylimidazole, iip=2-（1H-imidazo-4-group）-lH-imidazo[n,5-f][1,10]phenanthroline）, [Ru（MeIm）4tip]^2＋ （2） （tip=2-（thiophene-2-group）-lH-imidazo[4,5-f] [i,10]phenanthroline）, and [Ru（Melm）42ntz]^2＋ （3） （2ntz=2-（2-nitro-l,3-thiazole-5-group）-lH-imidazo[4,5-f][1,10]phenanthroline）, were car- ried out using the density functional theory （DFT）. The electronic structures of these Ru（II） complexes were analyzed on the basis of their geometric structures optimized in aqueous solution, and the trend in the DNA-binding constants （Kb） was reasonably explained. The results show that the replacement of imidazole ligand by thiophene ligand can effectively improve the DNA-binding affinity of the complex. Meanwhile, it was found that introduc- ing the stronger electronegative N atom and NO2 group on terminal loop of intercalative ligand can obviously reduce the complex＇s LUMO and HOMO-LUMO gap energies. Based on these findings, the designed complex [Ru（MeIm）42ntz]^2＋ （3） can be expected to have the greatest Kb value in complexes 1-3. In addition, the structure-activity relationships and antitumor mechanism were also carefully discussed, and the antimetastatic activity of the designed complex 3 was predicted. Finally, the electronic absorption spectra of this series of complexes in aqueous solution were calculated, simulated and assigned using DFT/TDDFT methods as well as conductor-like polarizable continuum model （CPCM）, and were in good agreement with the experimental results.

Ru、Y对铸造高温合金与陶瓷界面反应的影响

在定向凝固炉中,采用相同的硅基陶瓷型芯,刚玉陶瓷型壳,熔炼工艺和定向凝固工艺制备了四种不同Ru、Y含量的单晶高温合金叶片,研究了组织稳定性提升元素Ru、抗氧化性增强元素Y对合金与陶瓷材料界面反应的影响。研究结果表明,合金中不含Ru、Y时,合金与型壳发生的界面反应主要为物理粘砂作用,未见合金元素与型壳发生明显的化学反应,合金与型芯发生轻微的界面反应,除了物理作用,还发生了Al与SiO2的化学反应。合金中添加Ru,对合金与型壳或型芯的界面反应无影响。合金中添加0.01%Y后,合金与陶瓷型壳或型芯的界面反应稍有增加,但由于其添加量较少,故影响较小。

Novel Ruthenium Catalyst (K-Ru/C_(60/70)) for Ammonia Synthesis

A novel ammonia-synthesis catalyst. potassium-promoted ruthenium supported on fullerene (K-Ru/C60/70 ). was prepared and evaluated, It was found that K-Ru/C60/70 was the most active catalyst for ammonia synthesis at atmospheric pressure and 623 K compared with other support materials such as silica, activated carbon. zeolite, λ-Al2O3 and rare earth metal oxide.

石墨烯负载的超微Ru纳米颗粒催化NaBH_(4)水解制氢

氢能被认为是绿色、清洁的新型能源形式,在未来的“碳中和碳达峰”战略中扮演重要的作用。相比于液化储氢方式,固态储氢具有运输和储存安全,使用条件温和等优势。其中NaBH_(4)是目前固态储放氢中研究最为广泛和深入的一种。采用改进的液相沉积-气相还原法可控制备了平均粒径为1.1 nm的超微Ru/rGO催化剂,采用透射电子显微镜对其形貌和物相进行了表征。考察了催化剂的量、NaOH浓度、NaBH_(4)浓度和反应温度对NaBH_(4)水解产氢活性的影响。同时研究了催化剂的循环稳定性以及循环后Ru/rGO的形貌和Ru尺寸分布,该工作将其超微Ru催化剂催化NaBH_(4)水解制氢提供一定的理论和实践参考。

Highly Efficient,Green Oxidation of Alcohols Using Novel Heterogeneous Ruthenium Catalyst

MnFe1.4Ru0.45Cu0.15O4 was an effective heterogeneous catalyst for the oxidation of various types of alcohols to the corresponding carbonyl compounds using atmospheric pressure of oxygen under mild conditions. Furthermore, this catalyst was also effective towards alcohol oxidation using water as solvent instead of toluene.

Ruthenium(Ⅲ) chloride as an efficient catalyst for the synthesis of perimidine derivatives under mild conditions

Various biologically important perimidine derivatives have been synthesized efficiently from various ketones and naphthalene- 1,8-diamine by using a catalytic amount of RuCl_3(1 mol%).This method is a very simple and high yielding reaction for the synthesis of perimidine derivatives.

Effect of Activated Carbon as a Support on Metal Dispersion and Activity ofRuthenium Catalyst for Ammonia Synthesis

Ten kinds of activated carbon from different raw materials were used as supports to prepare ruthenium catalysts. N_2 physisorption and CO chemisorption were carried out to investigate the pore size distribution and the ruthenium dispersion of the catalysts. It was found that the Ru dispersion of the catalyst was closely related to not only the texture of carbon support but also the purity of activated carbon. The activities of a series of the carbon-supported barium-promoted Ru catalysts for ammonia synthesis were measured at 425 ℃, 10 0 MPa and 10 000 h -1. The result shows that the same raw material activated carbon, with a high purity, high surface area, large pore volume and reasonable pore size distribution might disperse ruthenium and promoter sufficiently, which activated carbon as support, could be used to manufacture ruthenium catalyst with a high activity for ammonia synthesis. The different raw material activated carbon as the support would greatly influence the catalytic properties of the ruthenium catalyst for ammonia synthesis. For example, with coconut shell carbon(AC1) as the support, the ammonia concentration in the effluent was 13 17% over 4%Ru-BaO/AC1 catalyst, while with the desulfurized coal carbon(AC10) as the support, that in the effluent was only 1 37% over 4%Ru-BaO/AC10 catalyst.

Formation mechanism of highly dispersed semi-embedded ruthenium nanoparticles in porous carbon matrix determined by in situ temperature-programmed infrared spectroscopy

The carbonization process of a sucrose‐RuCl3/SBA‐15composite towards a Ru‐containing ordered mesoporous carbon(Ru‐OMC)catalyst was studied by in situ temperature‐programmed infrared spectroscopy to identify the stabilization role of organic carbon precursors during the formation of highly dispersed Ru nanoparticles.The results show that the formation of metal carbonyl species results in the formation of homogeneously distributed Ru nanoparticles,and the rigid silica support and carbon matrix around the Ru(CO)x complex can significantly avoid the sintering and agglomeration of Ru metal particles during elevated temperature thermal treatment.These results ultimately demonstrate that sucrose plays important roles in the formation of homogeneously distributed Ru nanoparticles in a porous carbon matrix.?2018,Dalian Institute of Chemical Physics,Chinese Academy of Sciences.Published by Elsevier B.V.All rights reserved.

Study on the Characteristics of the Ruthenium Oxide pH Electrode

Ruthenium oxide,which fabricated by radio frequency sputtering is used as the sensitive membrane,which shows that the pH sensitivity is very high and has a linear response in different buffer solutions.The pH electrode,which applies the structure of separative structure EGFET (Extended Gate Field Effect Transistor) insteads of the conventional gate ISFET (Ion Sensitive Field Effect Transistor) for reducing the cost of the fabrication and measurement.Unfortunately,the performance of the pH sensor was falsified by the drift and hysteresis.In addition,the total response is composed of the intrinsic response and drift,and the hysteresis effect combines the slow response with drift.Consequently,we would also investigate the drift in the buffer solutions and hysteresis effect in the different paths.In this way,the more accurate sensing properties are obtained by the RuO_x pH electrode.

Photocatalytic properties of thin films of ruthenium metallopolymers/gold nanoparticle: Polyoxometalate composites using visible excitation

Thin layers of an electrostatically associated adduct RuPVP-AuNP:POM formed between the polyoxomolybdate, [S2 Mo18 O62 ]4, the polycationic metallopolymer [Ru(bpy)2(PVP)10 ](ClO4)2 and DMAP-protected gold nanoparticle have been deposited onto electrodes using two separate methods, alternate immersion layer-by-layer assembly and pre-assembled drop-casting; PVP is poly(4-vinylpyridine), BPY is 2,2'-bipyridyl, and DMAP is 4-dimethylaminopyridine. Significantly, the efficiency of the photocatalysis depends markedly on the structure of the [RuPVP-AuNP:POM] even when photonic properties are very similar. Strikingly, despite their similar photonic properties, an additional optical transition is observed in UV-vis and the Raman spectra of pre-assembled drop cast [RuPVP-AuNP:POM], which was not seen in dip coated [RuPVP-AuNP:POM]. Importantly, this electronic communication enhances the photocatalytic oxidation of benzaldehyde by a factor of more than four. While there is clear evidence for photosensitisation in the drop cast not present for the dip coated systems, the magnitude of the photocurrent, i.e.,(82.2 6.6) nA·cm 2for pre-assembled drop cast [RuPVP-AuNP:POM] at a ruthenium to Au nanoparticle mole ratio of 48:1, is twice as large as that those found in [Ru-PVP:POM] film.

Kinetics and product distribution studies on ruthenium-promoted cobalt/alumina Fischer-Tropsch synthesis catalyst

Hydrocarbon production rates and distributions on ruthenium promoted alumina supported cobalt Fischer-Tropsch synthesis （FTS） catalyst were studied by the concept of two superimposed Anderson-Schulz-Flory （ASF） distributions.The results indicated that the characterizing growth probabilities α1 and α2 were strongly dependent on reaction conditions.By increasing the H2 /CO partial pressure ratios and reaction temperatures,deviation from normal ASF distribution decreases and the double-α-ASF distribution changes into a straight line.Based on the concept of double-α-ASF distribution,a useful rate equation for the production of hydrocarbons under industrial reaction conditions is obtained.

Role of surface defects of carbon nanotubes on catalytic performance of barium promoted ruthenium catalyst for ammonia synthesis

Carbon nanotubes(CNTs) with abundant surface defects are prepared by a liquid oxidation and thermal annealing method. The defective CNTs-D supported Ba–Ru/CNTs-D catalysts exhibit superior catalytic performance in ammonia synthesis with a TOF be increased up to 0.30 s-1, which is 2.5 times of oxidized CNTs-O supported Ba–Ru/CNTs-O catalysts and 5 times of the Ba–Ru/CNTs. The characterizations by CO chemisorption, transmission electron microscope, Raman, and X-ray photoelectron spectroscopy revealed that the uniformly well dispersed Ru NPs can be stabilized on the defective sites of CNTs-D. The great improvement of the catalytic performance and stability of the Ba–Ru/CNTs-D is contributed to the strong interaction between Ru NPs and surface defect of the CNTs.

Pseudo-capacitance of ruthenium oxide/carbon black composites for electrochemical capacitors

Hydrous ruthenium oxide was formed by a new process. The precursor was obtained by mixing the aqueous solutions of RuCl3xH2O and NaHCO3. The addition of NaHCO3 led to the formation of an oxide with extremely fine RuO2 particles forming a porous network structure in the oxide electrode. Polyethylene glycol was added as a controller to partly inhibit the sol-gel reaction. The rate capacitance of 530 F·g^-1 was measured for the powder formed at an optimal annealing temperature of 210℃. Several details concerning this new material, including crystal structure, particle size as a function of temperature, and electrochemical properties, were also reported. In addition, the rate capacitance of the composite electrode reached 800 F·g^-1 after carbon black was added. By using the modified electrode of a RuO2/carbon black composite electrode, the electrochemical capacitor exhibits high energy density and stable power characteristics. The values of specific energy and maximum specific power of 24 Wh·kg^-1 and 4 kW·kg^-1, respectively, are demonstrated for a cell voltage between 0 and 1 V.

Ruthenium Bisphosphine Catalyst on Functionalized Silica: Novel Efficient Catalyst for Carbon Dioxide Hydrogenation to Formic Acid

A novel efficient catalyst for the hydrogenation of carbon dioxide to formic acid ruthenium bisphosphine on functionalized silica was in situ synthesized, affording turnover frequency （TOF） of 1190 h^-1 at 100% selectivity under 80℃ with total pressure of 16.0 MPa. The catalyst can be separated from the reaction mixture easily and reused with moderate loss of activity.