Electropolymerization of polypyrrole, modified with germanium, on a passivated titanium electrode in aqueous nitrate solution: new results on catalytic reduction of protons and dissolved oxygen

Conductive polypyrrole (PPy) films and PPy films containing Ge microparticles were synthesized by anodic oxidation of pyrrole in acidic nitrate solutions using a bare passivated titanium electrode. Well-adhering black PPy films were obtained both under galvanostatic and potentiodynamic polarization. After the formation of the PPy film, during the first anodic cycle, an increase of the anodic deposition current with the number of cycles was observed, revealing the increase of conductivity of the growing film. The variations of the electrode surface area were estimated by impedance spectroscopy measurements. The kinetics of the PPy film formation is controlled by diffusion of the Py monomer in the solution. The diffusion coefficient, estimated by two different methods, was ca. 2×10^–6 cm² s^–1. The reduction rate of oxygen and protons at the Ti/PPy/Ge electrodes depends on how the Ge microparticles are incorporated in the PPy film. Optimum conditions for this incorporation are realized with thin PPy films and high Ge loading. Thermogravimetric analysis shows that the PPy film containing Ge microparticles is more thermally stable than the blank PPy film. Electronic Publication     

沸石表面有机金属化学ZSM-5外表面上——Ge(n-C4H9)x基团的接枝及其性质研究

用气体分析及IR,NMR和元素分析等方法研究了真空系统中230℃和280℃下四丁基锗在ZSM-5沸石表面上的接枝反应,并对所得沸石的热稳定性和吸附性质进行了表征,与作者曾报道的硅胶及丝光沸石上的反应类似,四丁基锗也能与ZSM-5沸石表面上的硅羟基发生缩合反应,在其外表面或孔口生成组成为(=Si-O)xGe(n-C4H9)4-x(x=2~3)的表面有机锗化合物,在２３０℃接枝丁基锗基团不影响沸石的结构和表面积,仅改变它的孔口大小,在改性后的沸石上,Ｎ２的吸附性质没有改变,而不同分子尺寸的烃,加正已烷,２-甲基戊烷,２,３-二甲基丁烷却呈现出完全不同于起始ＺＳＭ-５沸石的择形吸附效应.     

Promising solid electrolyte material for an IT‐SOFC: crystal structure of the cerium gadolinium holmium oxide Ce0.8Gd0.1Ho0.1O1.9 between 295 and 1023 K

The crystal structure of Ce_0.8Gd_0.1Ho_0.1O_1.9 (cerium gadolinium holmium oxide) has been determined from powder X‐ray diffraction data. This is a promising material for application as a solid electrolyte for intermediate‐temperature solid oxide fuel cells (IT‐SOFCs). Nanoparticles were prepared using a novel sodium alginate sol‐gel method, where the sodium ion was exchanged with ions of interest and, after washing, the gel was calcined at 723 K in air. The crystallographic features of Gd and Ho co‐doped cerium oxide were investigated around the desired operating temperatures of IT‐SOFCs, i.e. 573 ≤ T ≤ 1023 K. We find that the crystal structure is a stable fluorite structure with the space group Fmm in the entire temperature range. In addition, the trend in lattice parameters shows that there is a monotonic increase with increasing temperature.     

Tuning physical surface properties of tin dioxide nanopowders using zinc oxide as template

With a view to energetic and (opto)electronic applications, tin (IV) oxide (SnO₂) nanoparticles have been successfully prepared at the nanoscale by a templating approach based on the use of zinc (II) oxide (ZnO) as template. The procedure consisted in preparing a mixture of tin precursor and template, subsequently calcined at 650 °C under air to lead to the formation of a SnO₂/ZnO composite material. Finally, the material was washed with an alkali solution to remove the template. The template/tin precursor mass ratio was varied in order to tailor the tin (IV) oxide material, especially with a view to main particle size. The resulting SnO₂ nanomaterials were characterized by X-ray diffraction, Fourier transform infrared spectroscopy, nitrogen adsorption and electron microscopy. The tin (IV) oxide nanomaterial exhibited enhanced textural and physical surface properties (particle size, surface area, pore size) correlated to an increasing template/tin precursor mass ratio. For instance, from optimized experimental conditions, the specific surface area and pore volume were heightened twofold, reaching values of 49 m²/g and 0.32 cm³/g, respectively.     

Mechanism of Evolution of Koneramine Complexes from One‐Pot Reactions: Snapshots of Intermediates Offer Facile Routes to New Dipicolylamines

Koneramines (L^ROR′, R=Ph or Ts; R′=Me, iPr) and their complexes were found to emerge from the system of pyridine‐2‐carboxaldehyde and N‐phenyl/tosylethylenediamine when a primary or secondary alcohol was used as solvent. Imidazolidinylpyridines (L^R, R=Ph or Ts) became major emergents whereas hemi‐aminals (L^ROH, R=Ph or Ts) are minor emergents of the system when tertiary butanol was used as the solvent; the bulky tertiary butyl group prevented the addition of alcohol to the iminium ion that diverted the equilibrium towards imidazolidinylpyridines. By playing with the components of the reaction mixture, crystals of the metastable intermediates bound to copper(II) and/or zinc(II) were obtained and the structures were determined by X‐ray diffraction analysis. The reported results shed light on how to control the emergents of the multicomponent reaction mixture that forms koneramines. Reactivity studies of the intermediates pave the way for a new type of koneramine complexes that are new dipicolylamines where the two pyridine moieties of the resulting koneramine are not the same.     

Intermediate detection in real time using reactive surface desorption dielectric‐barrier discharge ionization mass spectrometry

Reactive intermediates play key roles for reaction mechanism elucidation. A suitable tool for identifying the key intermediates is crucial and highly desirable. In this study, surface desorption dielectric‐barrier discharge ionization (reactive SDDBDI) was developed for characterization of the reactive intermediates. In reactive SDDBDI, the plasma is doped with a reagent before the plasma ions are directed at a cover slip surface bearing another analyte. Different from SDDBDI, reactive SDDBDI can be used both as an ambient ionization source and as a means to produce reagent ions for ambient ion/molecule reactions. The online derivation of 4‐aminophenol with trifluoroacetic anhydride demonstrated that reactive SDDBDI can be used for chemical analysis where improved specificity or sensitivity is required. The utility of this approach for real‐time detection of reactive intermediate was demonstrated by the Schiff‐base and Eberlin reactions. The formed intermediates and products could be readily detected and identified by tandem mass spectrometry. These results indicate that reactive SDDBDI can be used to generate reagent ions that undergo ion/molecule reactions in the open air with an analyte at condensed phase on a surface. Reactive SDDBDI has high‐efficiency ion transmission and high MS sensitivity. It is thus a potential tool to perform ambient ion/molecule reactions and detect reactive intermediates.     

Surface Tension Effect on Harmonics of Rayleigh-Taylor Instability

Using the method of the parameter expansion up to the third order, explicitly investigates surface tension effect on harmonics at weakly nonlinear stage in Rayleigh-Taylor instability (RTI) for arbitrary Atwood numbers and compares the results with those of classical RTI within the framework of the third-order weakly nonlinear theory. It is found that surface tension strongly reduces the linear growth rate of time, resulting in mild growth of the amplitude of the fundamental mode, and changes amplitudes of the second and third harmonics, as is expressed as a tension factor coupling in amplitudes of the harmonics. On the one hand, surface tension can either decrease or increase the space amplitude; on the other hand, surface tension can also change their phases for some conditions which are explicitly determined.     

Theories and Applications of Mixed Quantum-Classical Non-adiabatic Dynamics

Electronically non-adiabatic processes are essential parts of photochemical process, collisions of excited species, electron transfer processes, and quantum information processing. Various non-adiabatic dynamics methods and their numerical implementation have been developed in the last decades. This review summarizes the most significant development of mixed quantum-classical methods and their applications which mainly include the Liouville equation, Ehrenfest mean-field, trajectory surface hopping, and multiple spawning methods. The recently developed quantum trajectory mean-field method that accounts for the decoherence corrections in a parameter-free fashion is discussed in more detail.     

Theoretical Study of Adsorption and Dehydrogenation of C2H4 on Cu(410)?

Adsorption and dehydrogenation of ethylene on Cu(410) surface are investigated with firstprinciples calculations and micro-kinetics analysis. Ethylene dehydrogenation is found to start from the most stable π-bonded state instead of the previously proposed di-σ-bonded state. Our vibrational frequencies calculations verify the π-bonded adsorption at step sites at low coverage and low surface temperature and di-σ-bonded ethylene on C-C dimer (C₂H₄-CC) is proposed to be the species contributing to the vibrational peaks experimentally observed at high coverage at 193 K. The presence of C₂H₄-CC indicates that the dehydrogenation of ethylene on Cu(410) can proceed at temperature as low as 193 K.     

高三尖杉酯碱和三尖杉酯碱的合成研究

天然药物高三尖杉酯碱和三尖杉酯碱是从三尖杉植物的叶和茎中分离得到的微量生物碱,是手性化合物。结构上,二者不仅含有一个共同的母核三尖杉碱,酯基侧链的α位也均为手性叔醇。因母核三尖杉碱和酯基侧链较大的空间位阻,两个结构片段的酯化偶联具有较大的挑战性。设计合成位阻较小的侧链中间体是酯化反应发生的关键。因此,化学家们相继合成了结构多样的α-羰基羧酸侧链以及含有杂环的侧链中间体,如四元内酯杂环侧链、四氢呋喃杂环侧链、六氢吡喃杂环侧链、七元内酯杂环侧链,并成功地完成了高三尖杉酯碱、三尖杉酯碱和同属其他活性生物碱的合成。本文基于本课题组的相关研究,根据侧链片段的构建策略和方法,综述了天然药物高三尖杉酯碱、三尖杉酯碱以及其他天然产物的合成研究。不仅总结了近几年来的新进展,还对我国老一辈的科学家们在此方面作出的贡献进行了回顾。