Ir(III) and Ru(II) Complexes in Photoredox Catalysis and Photodynamic Therapy: A New Paradigm towards Anticancer Applications

Individually, photoredox catalysis (PC) and photodynamic therapy (PDT) are well-established concepts that have experienced a remarkable resurgence in recent years, leading to significant progress in organic synthesis for PC and clinical approval of anticancer drugs for PDT. But, very recently, new photoredox catalyst systems based on Ir(III) and Ru(II) complexes have garnered significant interest because they can simultaneously be used as PDT agents apart from their demonstrated PC activity. This highlight discusses the unique PC behavior of emerging Ir(III)- and Ru(II)-based systems while also examining their potential PDT activity in cancer treatment.     

Pt–Ru nanoparticles anchored on poly(brilliant cresyl blue) as a new polymeric support: Application as an efficient electrocatalyst in methanol oxidation reaction

The glassy carbon electrode is modified by poly(brilliant cresyl blue) (PBCB) to be applied as a new green and efficient platform for Pt and Pt–Ru alloy nanoparticles deposition. Surface composition, morphology and catalytic activity of these modified electrodes towards methanol oxidation are assessed by applying X-ray diffraction, field emission scanning electron microscopy, cyclic voltammetry and electrochemical impedance spectroscopy techniques. The X-ray diffraction patterns reveal that the highly crystalline Pt and Pt–Ru alloy and RuO₂ nanoparticles with low crystallinity are deposited on the PBCB modified glassy carbon electrodes. The microscopic images indicate smaller size and better distribution of deposited nanoparticles on the surface of PBCB modified electrodes. Cyclic voltammetry and electrochemical impedance spectroscopy results reveal that PBCB supported Pt and Pt–Ru nanoparticles have better electrocatalytic performance and durability towards methanol oxidation rather than the unsupported nanoparticles. From the obtained results it can be concluded that the presence of PBCB not only improves the stability of nanoparticles on the surface, but also leads to the formation of smaller size and more uniform distribution of nanoparticles on the surface, which, in turn, cause the nanoparticles to provide a higher accessible surface area and more active centers for the oxidation of methanol. The results will be valuable in extending the applications of this polymer in surface modification steps and in developing promising catalyst supports to be applied in direct methanol fuel cells.     

CO2 abatement and CH4 recovery at vehicle exhausts: Comparison and characterization of Ru powder and pellet catalysts

The catalytic conversion of CO₂ to CH₄ (Sabatier reaction) has been studied to develop an after-treatment process at vehicles exhausts. Three different formulations of Ru commercial catalysts, two in powder and one in pellets shape, were tested and characterized by means of X-ray powder diffraction, scanning electron microscopy (SEM-EDX), N₂ adsorption at −196 °C and temperature-programmed reduction (TPR).Experimental results show a high CO₂ conversion (X_CO2 = 0.96 @ T = 280 °C) for one powder catalyst formulation whereas the other one has maximum CO₂ conversion = 0.69. In both cases a high CH₄ selectivity is measured. High CO₂ conversion (X_CO2 = 0.92 @ T = 300 °C) is obtained also with pellet catalysts but only at lower GHSV values. The different behavior of the catalysts was ascribed to the different physicochemical properties and the key parameters for the application development of the process were identified. In particular, the possibility to use pellets or monolithic reactors, thus minimizing the pressure drops in the reactor, makes possible a commercial application in the treatment of vehicles exhausts.     

Ru的添加量对FeMn尖晶石的结构 及其氧化性能的影响

 考察了随着FeMn尖晶石催化剂中Ru的添加量的变化以及助剂Cu的加入，催化剂物理结构及化学性质的变化。结果表明，Cu的添加不仅对催化剂的比表面和孔径分布有较大的影响，还对各元素的化学环境有较大的影响。当n(Ru)/n(Mn)为0.05时，由于尚未破坏尖晶石的结构，Ru的存在对于催化剂中其它元素如Mn、Fe和O的化学环境具有较大的影响，当n(Ru)/n(Mn)大于0.15时，尖晶石结构被破坏，Ru含量的增加对于其它元素如Mn、Fe和O的化学环境影响不大，对于比表面积和孔径分布等物理性质也影响很小。所研究的催化剂均可催化氧化醇至醛或酮，Ru的含量越大，催化醇液相氧化性能越好。     

Kelogg合成氨工艺进展

综述了以先进合成氨工艺和转化换热系统技术为代表的Ｋｅｌｏｇｇ第二代合成氨工艺。较详细介绍了钌基催化剂和转化换热器     

Ru-catalyzed anode materials for direct hydrocarbon SOFCs

A solid oxide fuel cell using a thin ceria-based electrolyte film with a Ru-catalyzed anode was directly operated on hydrocarbons, including methane, ethane, and propane, at 600 °C. The role of the Ru catalyst in the anode reaction was to promote the reforming reaction of the unreacted hydrocarbons by the produced steam and CO₂, which avoided interference from steam and CO₂ in the gas-phase diffusion of the fuels. The resulting peak power density reached 750 mW cm⁻² with dry methane, which was comparable to the peak power density of 769 mW cm⁻² with wet (2.9 vol.% H₂O) hydrogen. More important was the fact that the cell performance was maintained at a high level regardless of the change in the methane utilization from 12 to 46% but was significantly reduced by increasing the hydrogen utilization from 13 to 42%. While the anodic reaction of hydrogen was controlled by the slow gas diffusion, the anodic reaction of methane was not subject to the onset of such a gas-diffusion process.     

Thermochemical behaviour of Ru(II) complex-SiO2 microcomposites

The results from DSC and thermogravimetric analysis of gels produced from a mixture of tetraethoxysilane (TEOS) and octyltriethoxysilane (OtEOS) both with and without immobilized Ru(II) tris(4,7-diphenyl-1,10-phenanthroline) dichloride as well as DSC and TG data for films deposited by deep-or spin-coating from the same gels, are reported. The initial products are characterized by elemental analysis, IR, solid state NMR and mass spectroscopy. Elemental analysis and IR spectroscopy are applied for identification of some of the intermediates obtained after heating at different temperatures. The final products are characterized by X-ray diffractometry. A hypothesis for the thermodecomposition processes taking place is proposed. The results reported contribute to elucidation of the properties as well as the temperature intervals in which the studied microcomposites could be used as sensing components of oxygen sensors.     

混合溶剂对Ru(Ⅳ)萃取的研究

一、前言 在一定浓度盐酸介质中,Ru(Ⅳ)以RuCl_6~(2-)络阴离子状态存在,可被C类溶剂TOA(三辛胺)以离子缔合机制定量地萃入有机相。由实验得到在相同条件下,TOA对Ru(Ⅳ)的萃取率随稀释剂介电常数的增加而下降。     

Ru/CN催化对苯二甲酸二甲酯加氢制备1,4-环己烷二甲酸二甲酯

通过超声辅助NaBH4还原法制备了3%Ru/CN催化剂（Ru的质量分数）,该催化剂用于对苯二甲酸二甲酯（DMT）加氢制备1,4-环己烷二甲酸二甲酯（DMCD）。采用Raman、SEM、TEM、N2吸脱附、XRD、XPS等对载体和催化剂的组成、表面性质进行表征,结果表明,氮元素成功掺入碳骨架中且氮掺杂碳材料为介孔结构。研究了催化剂的用量、反应温度、H2 压力、反应时间等对催化剂加氢性能的影响。结果表明,当反应物用量为1.00 g,催化剂（含载体）用量为0.05 g,反应温度140 ℃,反应压力5.0 MPa,反应时间1 h时,DMT转化率为100%,DMCD选择性为99.3%。3%Ru/CN-1000催化剂循环使用5次后,催化剂催化性能未见明显下降,DMT转化率为98.8%,DMCD选择性为99.7%。     

氮在钌单晶表面Ru(0001)上的吸附

钌系氨合成催化剂作为第二代氨合成催化剂,近年来日益受到重视。研究氮分子在钌表面上的离解吸附对提高钌催化剂的催化性能有着十分重要的意义。综述了氮分子在Ru(0001)单晶表面吸附的研究进展，并指出钌催化剂的发展方向。