Inorganic—Organic Hybrid 18—Molybdodiphosphate Nanoparticles Bullk—modified Carbon Paste Electrode and Its Electrocatalysis

A kind of inorganic‐organic hybrid 18‐molybdodiphosphate nanoparticles ([(C₄H₉)₄N]₆P₂Mo₁₈Q₆₂·4H₂O) was firstly used as a bulk‐modifier to fabricate a three‐dimensional chemically modified carbon paste electrode (CPE) by direct mixing. The electrochemical behavior of the solid nanoparticles dispersed in the CPE in acidic aqueous solution was characterized by cyclic and square‐wave voltammetry. The hybrid 18‐molybdodiphosphate nanoparticles bulk‐modified CPE (MNP‐CPE) displayed a high electrocatalytic activity towards the reduction of nitrite, bromate and hydrogen peroxide. The remarkable advantages of the MNP‐CPE over the traditional polyoxometalates‐modified electrodes are their excellent reproducibility of surface‐renewal and high stability owing to the insolubility of the hybrid 18‐molybdodiphosphate nanoparticles.     

Metal Nanoparticles on Stainless Steel Surfaces as Novel Heterogeneous Catalysts

The goal of this work was the development of a novel type of heterogeneous catalyst, consisting of bare metal nanoparticles on stainless steel foils, which can be shaped to any kind of architecture and, if necessary, heated electrically. Solutions of pre-prepared, ligand protected and monodispersed gold, palladium, platinum and rhodium nanoparticles were sprayed onto stainless steel foils, followed by the careful removal of the ligand molecules by an oxygen plasma treatment. Due to this, bare particles become irreversibly fixed on the steel support. It could be shown that the original particle sizes do not change during the plasma treatment. Foils, densely coated with the nanoparticles, were used for gas phase catalyses in a self-made reactor at room temperature or at 60 °C. Hydrogenation of 1,3-butadiene at 15 nm Pd and 2 nm Pt, CO oxidation at 16 nm, 8 nm and 1.4 nm gold and NO reduction with NH₃ at 2 nm Rh particles were performed, indicating that the novel catalysts might in principle be applicable in technical processes if the experimental conditions like form and temperature would be optimized. Dedicated to Professor Dieter Fenske on the occassion of his 65th birthday.     

Pd-H from Pd/C and triethylamine: Implications in palladium catalysed reactions involving amines

The palladium hydride-iminium complex generated from Pd/C and triethylamine catalyses the isomerisation of allylic alcohols into carbonyl compounds, and Pd/C catalyses the conjugate reduction of activated double bonds using triethylamine as the source of the two newly incorporated hydrogen atoms via the same complex.     

Electrocatalytic Proton Reduction by a Cobalt Complex Containing a Proton-Responsive Bis(alkylimdazole)methane Ligand: Involvement of a C−H Bond in H2 Formation

Homogeneous electrocatalytic proton reduction is reported using cobalt complex [ 1 ](BF₄)₂. This complex comprises two bis(1-methyl-4,5-diphenyl-1H-imidazol-2-yl)methane (HBMIM ) ligands that contain an acidic methylene moiety in their backbone. Upon reduction of [ 1 ](BF₄)₂ by either electrochemical or chemical means, one of its HBMIM ligands undergoes deprotonation under the formation of dihydrogen. Addition of a mild proton source (acetic acid) to deprotonated complex [ 2 ](BF₄) regenerates protonated complex [ 1 ](BF₄)₂. In presence of acetic acid in acetonitrile solvent [ 1 ](BF₄)₂ shows electrocatalytic proton reduction with a k_obs of ≈200 s⁻¹ at an overpotential of 590 mV. Mechanistic investigations supported by DFT (BP86) suggest that dihydrogen formation takes place in an intramolecular fashion through the participation of a methylene C−H bond of the HBMIM ligand and a Co^II−H bond through formal heterolytic splitting of the latter. These findings are of interest to the development of responsive ligands for molecular (base)metal (electro)catalysis.     

直接甲醇燃料电池阴极电催化剂的研究进展

直接甲醇燃料电池(DMFC)功率密度高，燃料甲醇价格低廉、储存和携带方便，特别适合作为电动车和小型电子设备的电源，是目前燃料电池研究领域的一个热点。本文介绍了40年来DMFC阴极电催化剂的发展历史及现状，并针对目前严重影响DMFC性能的“甲醇透过”问题，阐述了研制耐甲醇阴极电催化剂的重要性，讨论了今后DMFC阴极电催化剂的发展趋势。     

Active nickel-based reduction of organic compounds

The reducing system NiCl₂·2H₂O—Li—arene_cat (cat is catalyst) was proposed for use to reduce a wide range of organic compounds, including alkenes, alkynes, carbonyl compounds, imines, halogenated derivatives, sulfonates, aromatic compounds, hydrazines, azo and azoxy compounds, N-oxides, and nitrones. The degree of reduction can be controlled for some substrates. Deuterium can be incorporated in the reaction products using nickel chloride deuteriohydrate. Nitrones, N-alkoxyamides, and acyl azides are also reduced with the Li—arene_cat system containing no nickel salt.     

Synthesis of nitro and amino derivatives of benzothiacrown ethers

The condensation reaction of 1,2-bis(2-haloethoxy)-4-nitrobenzenes with acyclic α,ω-(oxa)alkanedithiols in the presence of alkali metal carbonates produced a series of nitrobenzodithiacrown ethers with macrocycles of different size. The structures of three ethers were established by X-ray diffraction. A new method was developed for the synthesis of nitrobenzomonothia-15-crown-5 ether. Nitro derivatives of benzodithiacrown ethers were tested as reagents for extraction of palladium(II), platinum(IV), and rhodium(III) from hydrochloric acid solutions. Extraction of Pd^II salts was found to be highly selective compared to that of Pt^IV and Rh^III salts. Benzodithia-15-crown-5 ether is the most efficient extractant for palladium(II). Reduction of nitrobenzothiacrown ethers with hydrazine hydrate in the presence of a platinum catalyst afforded their amino derivatives. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 5, pp. 958–966, May, 2007.     

Determination and fractionation of sulphur in a contaminated dredged sediment

Conversion of sulphur compounds in reduced, contaminated sediments that are brought in upland conditions may largely affect the potential mobility of heavy metal contaminants. We applied selected methods for the determination of total sulphur and sulphur fractions in a contaminated sediment in the reduced state and after gradual drying and oxidation during 1 month. Dry ashing, followed by ion chromatographic detection, was reliable for the determination of total sulphur. Good recoveries were obtained in both reference samples and spiked samples. Total sulphur was 14.5±0.6 g kg⁻¹ relative to dry sediment. Wet chemical methods that involve the determination of acid-volatile, Zn–HCl-reducible, chromium-reducible, acetone-soluble and HI-reducible sulphur were used to estimate specific sulphur forms. Results for acetone-soluble sulphur were to high and not consistent with results for other fractions. Major part of sulphur in the sediment (90%) was inorganic. Sulphides were converted partially to sulphate and to intermediary oxidised sulphur compounds upon oxidation of the sediment. The results suggested that the intermediary oxidised sulphur pool in the reduced sediment (2.5 g kg⁻¹) mainly consisted of pyrite, that was not converted during drying and oxidation. No significant changes in organic sulphur were detected.     

分散法制备的CuCl/MCM-41上C3H6选择催化还原NO反应的研究

研究了由分散法制备的两种CuCl/MCM-41催化剂上丙烯在过量氧存在下选择催化还原NO反应, 发现所制备的CuCl/AlMCM-41催化剂的反应活性明显高于CuCl/SiMCM-41. XRD, IR, TPR及ESR的研究结果表明, CuCl/AlMCM-41催化剂上的主要活性中心是与骨架铝配位的铜离子(Cu2+/Cu+).     

以钛氧有机物为前驱物制备具有高光催化活性的纳米二氧化钛晶体

 纳米二氧化钛的制备方法及前驱物的差别影响其光催化活性．将20ml钛酸丁酯及30ml乙酐在密闭容器中与50ml环己烷混合，在70～85℃反应30min，生成微细的非晶钛氧有机物；经FT－IR和TGA分析，该物质被确认为计量式是TiOOOCCH3）2和TiO（OC4H9）（OOCCH3）的混合体．该钛氧有机物前驱物经焙烧后得到具有高光催化活性的纳米二氧化钛晶体．表征结果表明，钛氧有机物在焙烧过程中，其表面的吸附物及键合有机基团在400℃以前发生脱附和氧化分解；在389～405℃间形成锐钛矿型晶体，在600℃出现金红石晶型；600℃焙烧3h所得样品的比表面积为86m2／g，其二次粒子呈200～300nm条形体，孔隙大于20nm；单分散粒子为球形单晶，粒径为22nm；表面物理吸附水量为1．21％，加热至800℃时失重1．48％，粉体稳定纯净．光催化实验结果表明，以钛氧有机物为前驱物制备的纳米二氧化钛晶体具有高的光催化活性，光降解丁基罗丹明溶液的反应速率常数约为溶胶－凝胶法制备的催化剂样品的4倍．表面氧空缺和一定量的表面羟基可能是粉体具有高光催化活性的重要因素．