Ultrahigh Loading Copper Single Atom Catalyst for Palladium-free Wacker Oxidation

Wacker oxidation is an industry-adopted process to transform olefins into value-added epoxides and carbonyls. However, traditional Wacker oxidation involves the use of homogeneous palladium and copper catalysts for the olefin addition and reductive elimination. Here, we demonstrated an ultrahigh loading Cu single atom catalyst(14% Cu, mass fraction) for the palladium-free Wacker oxidation of 4-vinylanisole into the corresponding ketone with N-methylhydroxylamine hydrochloride as an additive under mild conditions. Mechanistic studies by ¹⁸O and deuterium isotope labelling revealed a hydrogen shift mechanism in this palladium-free process using N-methylhydroxylamine hydrochloride as the oxygen source. The reaction scope can be further extended to Kucherov oxidation. Our study paves the way to replace noble metal catalysts in the traditional homogeneous processes with single atom catalysts.     

The visible and ultraviolet organic light-emitting diodes with germanium dioxide as facile solution-processed anode buffer layer

Germanium dioxide (GeO₂) aqueous solutions are facilely prepared and the corresponding anode buffer layers (ABLs) with solution process are demonstrated. Atomic force microscopy, X-ray photoelectron spectroscopy and ultraviolet photoelectron spectroscopy measurements show that solution-processed GeO₂ behaves superior film morphology and enhanced work function. Using GeO₂ as ABL of organic light-emitting diodes (OLEDs), the visible device with tris(8-hydroxy-quinolinato)aluminium as emitter gives maximum luminous efficiency of 6.5 cd/A and power efficiency of 3.5 lm/W, the ultraviolet device with 3-(4-biphenyl)-4-phenyl-5-tert-butylphenyl-1,2,4-triazole as emitter exhibits short-wavelength emission with peak of 376 nm, full-width at half-maximum of 42 nm, maximum radiance of 3.36 mW/cm² and external quantum efficiency of 1.5%. The performances are almost comparable to the counterparts with poly (3,4-ethylenedioxythiophene):poly (styrenesulfonate) as ABL. The current, impedance, phase and capacitance as a function of voltage characteristics elucidate that the GeO₂ ABL formed from appropriate concentration of GeO₂ aqueous solution favors hole injection enhancement and accordingly promoting device performance.     

The electronic structure of the interface between thin conjugated oligomer films and inorganic substrates with different work function

In this work, a comparison of the interfacial electronic properties between a semiconducting oligomer and a variety of substrates with different properties—metal, semiconductor and oxide layers—is reported. The interface formation was studied by X-ray and Ultraviolet photoelectron spectroscopies (XPS, UPS). High purity oligomer films with thickness up to 10 nm were prepared by stepwise evaporation on the clean substrates under ultrahigh vacuum (UHV) conditions. Analysis of the oligomer and substrate related XPS spectra clarified the interfacial chemistry and band bending in the semiconducting materials. The valence band structure and the interfacial dipoles were determined by UPS. The barriers for hole injection were measured at the interfaces of the organic film with all substrates. The interfacial energy band diagrams were deduced in all cases from the combination of XPS and UPS results. Emphasis was given on the influence of the substrate work function (eΦ) on the electronic properties of these interfaces.     

The epitaxial sexiphenyl (0 0 1) monolayer on TiO2(1 1 0): A grazing incidence X-ray diffraction study

A para-sexiphenyl monolayer of near up-right standing molecules (nominal thickness of 30 Å) is investigated in-situ by X-ray diffraction using synchrotron radiation and ex-situ by atomic force microscopy. A terrace like morphology is observed, the step height between the terraces is approximately one molecular length. The monolayer terraces, larger than 20 μm in size, are extended along the [0 0 1] direction of the TiO₂(1 1 0) substrate i.e. along the Ti-O rows of the reconstructed substrate surface. The structure of the monolayer and its epitaxial relationship to the substrate is determined by grazing incidence X-ray diffraction. Extremely sharp diffraction peaks reveal high crystalline order within the monolayer, which was found to have the bulk structure of sexiphenyl. The monolayer terraces are epitaxially oriented with the (0 0 1) plane parallel to the substrate surface (out-of-plane order). Four epitaxial relationships are observed. This in-plane alignment is determined by the arrangement of the terminal phenyl rings of the sexiphenyl molecules parallel to the oxygen rows of the substrate.     

Correlated and non-correlated growth kinetics of pentacene in the sub-monolayer regime

We present a study of the growth kinetics of pentacene monolayer islands on SiO₂ in the submonolayer regime by using Atomic Force Microscopy (AFM). Two distinct growth modes, namely correlated growth (CG) and non-correlated growth (NCG), have been identified by Voronoi tesselation. These two modes are characterized by different island growth kinetics. In the case of correlated growth, the average island size 〈A〉 scales with deposition time t i.e. 〈A〉 ∝ t whereas for non-correlated growth, 〈A〉 ∝ t². The CG and NCG regimes are defined by the level of re-evaporation which determines the capture zones around the islands: Wigner-Seitz cells for CG and coronas of width λ_D (λ_D is the mean diffusion distance on SiO₂ before re-evaporation) for NCG. A simple model is proposed to reproduce the experimental growth kinetics in both modes.     

Nitrated polynuclear aromatic hydrocarbons in ambient air in Italy. A brief overview

When nitrated polynuclear aromatic hydrocarbons (NPAH) were recognised as long‐term toxic compounds and were also identified in several anthropogenic emissions and among the by‐products of photochemical smog they became objects of investigation in ambient air in both polluted and clean environments. In Italy the first investigations focussing on atmospheric NPAH were performed in the early eighties and encompassed both the canyon streets and dwelling areas of Rome. Because NPAH were indicated as markers of vehicle emission, new investigations were performed in other cities and also in rural and (nominally) unpolluted locations. In general, the first measurements of NPAH were episodic and could not be assumed to be strictly representative of the sites investigated. In contrast, nowadays consistent data bases on NPAH have been built up and are discussed in the technical literature, so that both neat concentrations and the yearly timed variation of the most important NPAH congeners have been measured in Italian air. Although concentrations of NPAH in air are usually much lower than those of PAH, owing to their very high potency in inducing mutations and tumours NPAH are regarded as having an important health impact on populations living in Italian urban areas. In this regard the genotoxicity of atmospheric aerosols is partly associated with nitrofluoranthenes and nitropyrenes whereas nitronaphthalenes and methylnitronaphthalenes seem to contribute to that of the gaseous organic fraction. Several civic and regional administrations are introducing control of atmospheric NPAH among ways of improving air quality in cities.     

若干具有[(PO4)2Mo5O15]簇骼的化合物的光谱研究

本文对所合成的具有 [(PO4 ) 2 Mo5O1 5]簇骼的 3种新颖的有机 磷钼酸盐簇合物(NH3CH2 CH2 NH3) 2 5[(PO4 ) (HPO4 )Mo5O1 5]·7 5H2 O (Ⅰ ) ,(H3NCH2 CH2 NH3) 3·[(PO4 ) 2 Mo5O1 5]·3H2 O (Ⅱ )和(H3NCH2 CH2 NH3) 2 ·[Cu(en) ][(PO4 ) 2 Mo5O1 5]·5H2 O (Ⅲ )用FTIR ,NIR Raman ,紫外 可见漫反射光谱 (UV VisDRS)和荧光光谱等研究手段 ,对其进行光谱研究 ,探讨其结构和性能的关系。在这些化合物中 ,化合物Ⅰ和Ⅱ具有孤立的 [(PO4 ) 2 Mo5O1 5]簇骼基元 ,而化合物Ⅲ的 [(PO4 ) 2 Mo5O1 5]簇骼基元是由 [Cuen]基团桥联成链 ;磷钼酸盐的特征振动频率和这些化合物的结构相关 ;UV VisDRS显示 ,在 2 0 0和 2 6 0nm左右有两个杂多化合物的特征吸收谱带 ;化合物的稳态荧光光谱中 ,观察到以 2 4 0nm激发 ,在大约 4 0 0nm附近出现的由金属氧簇Oμ→Mo跃迁激发所引起的较强的发射峰 ,在化合物 (Ⅲ )中 ,还观察到通过 [Cuen]的荷移跃迁的以 5 70nm激发所产生的 6 0 4nm的发射峰。     

Magneto-Optical Measurement of Organic Conductor Using Rotational Cavity System

We have developed a new magneto-optical measurement system using a rotational cavity system equipped with a millimeter vector network analyzer and a 14 T solenoid type super conducting magnet. The measurement can be performed in the transmission configuration down to 1.6 K. The results of the precise angular dependence measurement of quasi-one-dimensional organic conductor (DMET)₂I₃ using the new system are shown, and its Fermi surface will be discussed in connection with the previous reports.     

用光学差分吸收光谱监测大气中污染气体浓度

在实验室内模拟测量了实际大气中污染气体的差分吸收光谱 (DOAS) .本文在介绍差分吸收光谱技术同时 ,分析计算了污染气体的浓度 .实验设计中被测气体为大气中的 2种主要污染气体 :工业锅炉的主要排放物SO2 和机动车尾气的主要成分NO .用氘灯作为光源测量其在紫外波段的特征吸收 ,并通过光纤束连接光栅光谱仪 ,由计算机自动采集和处理数据 .