NEXAFS光谱分析聚合物修饰的单壁碳纳米管

利用C1s、O1s、N1s近边X射线吸收精细结构(Near Edge X-Ray Absorption Fine Structure,NEXAFS)光谱对聚合物修饰的碳纳米管进行了分析,研究了氧化及偶联聚合物对碳纳米管结构的影响。氧化碳纳米管及十八胺修饰的、聚合物/十八胺双修饰的碳纳米管的NEXAFS光谱均出现了碳/氧K边π*(C=O)和σ*(C-O)共振峰;而十八胺修饰的、聚合物/十八胺双修饰的碳纳米管则出现了氮K边π*(N-C=O)和σ*(N1s)共振峰。分析表明,NEXAFS光谱可有效表征聚合物修饰的碳纳米管。     

STXM-NEXAFS研究铁(III)离子诱发柠檬酸在高岭石表面的固定机制

热带地区土壤有机碳的稳定性受有机碳与高岭石、三价铁离子[Fe（Ⅲ）]交互作用的强烈影响.低分子量有机酸（LMWOAs）是土壤有机碳中最易被微生物降解的组分,研究LMWOAs在高岭石-Fe（Ⅲ）-LMWOAs三相系统中的固定机制对于理解热带地区土壤有机碳循环具有重要意义;然而LMWOAs在该三相系统中固定机制仍不清楚,并缺乏分子水平上的直接证据.本研究以柠檬酸（CA）为LMWOAs的典型代表,通过采集Fe/CA初始物质的量比2.0条件下获取的吸附样品,利用同步辐射X射线扫描透射显微术（STXM）在亚微米尺度上表征C,Fe和Si的分布特征,发现C-Fe分布的相关性与C-Si分布相当;并在高C,Fe微区中利用C的K边和Fe的L₃边X射线近边吸收精细结构谱（NEXAFS）在分子水平上揭示了Fe在不同富集微区分别以水铁矿和高岭石-Fe（Ⅲ）-CA三元配合体形式存在,从而表明水铁矿诱发的吸附/共沉淀以及以Fe（Ⅲ）为架桥形成高岭石-Fe（Ⅲ）-CA三元配合作用是CA固定的重要机制.本研究成果对于理解热带地区土壤中CA稳定性和低分子量有机酸的碳固定和循环机制提供了重要科学依据.     

Near-edge X-ray absorption fine structure spectroscopy and structural properties of Ni-doped CeO2 nanoparticles

Ni-doped CeO₂ nanoparticles were prepared by using the co-precipitation method. The prepared nanoparticles were characterized using X-ray diffraction (XRD), Fourier transform infrared (FTIR) spectroscopy, Raman spectroscopy, field emission scanning electron microscopy (FE-SEM) and near-edge X-ray absorption fine structure (NEXAFS) spectroscopy. The XRD results infer that Ni-doped CeO₂ nanoparticles have single phase nature similar to that of pure CeO₂ nanoparticles. We have calculated lattice parameters using Powder-X software, particle size using Scherer’s formula and strain using the Williamson-Hall method for all the synthesized samples. We have observed a systematic decrease in the lattice parameters, particle size and strain with an increase in Ni doping in CeO₂. The FE-SEM micrographs also confirm that Ni-doped CeO₂ have nanocrystalline behavior and particles are spherical shaped. From the Raman spectra, it is observed that the intensity of classical CeO₂ vibration modes first increases then decreases with Ni doping. The NEXAFS spectra measured at Ce M_4,5 and Ni L_3,2 edges clearly indicate that Ce ions are in the +4 valence state and Ni ions are in the +2 valence state.     

Density functional theory study of the near edge X-ray absorption fine structure and infrared spectroscopy of acetylene and benzene on group IV semiconductor surfaces

The near edge X-ray absorption fine structure and infrared spectroscopy of acetylene and benzene adsorbed on C(1 0 0)-2 × 1, Si(1 0 0)-2 × 1 and Ge(1 0 0)-2 × 1 surfaces is studied with density functional theory calculations. Time dependent density functional theory calculations of the near edge X-ray absorption fine structure with a modified exchange-correlation functional agree well with experiment, and show that the spectral features arise from excitation to π^∗, and orbitals, where X represents C, Si or Ge. The excitation energies are dependent on the surface, and for acetylene, the location of the π^∗ band also varies with the surface. Calculations of the vibrational modes show the CH stretching frequencies for carbon atoms bonded directly to the surface vary significantly between the three surfaces, while those for carbon atoms not bonded to the surface do not change significantly.     

Species formed at cuprite fracture surfaces; observation of O 1s surface core level shift

Surfaces of mineral cuprite prepared by fracture under UHV have been characterised by synchrotron XPS and near-edge X-ray absorption spectroscopy before and after exposure to ambient air. Before exposure of the cuprite, the Cu 2p photoelectron and Cu L_2,3-edge absorption spectra were consistent with Cu^I with very little d⁹ character. Surface-enhanced O 1s spectra from the unexposed mineral revealed a surface species, with binding energy 0.95 ± 0.05 eV below the principal cuprous oxide peak, assigned to under-coordinated oxygen. A second surface species, with binding energy about 1 eV higher than the principal peak, was assigned to either hydroxyl derived from chemisorbed water vapour or surface oxygen dimers produced by restructuring of the cuprite fracture surface. The width of the principal O 1s peak was 0.66 ± 0.02 eV. The observed Cu L₃- and O K-edge absorption spectra were in good agreement with those simulated for the cuprite structure. After exposure of the fracture surface to ambient air, the low binding energy O 1s surface species was barely discernible, the original high binding energy O 1s surface species remained of comparable intensity, new intensity appeared at an even higher (∼1.9 eV) binding energy, and the Cu L_2,3-edge spectrum indicated the presence of Cu^II, consistent with the formation of a thin surface layer of Cu(OH)₂.     

H2O induced structural modification of pentacene crystal

Water is one of the obstacles for prolonged life-time of organic based field-effect-transistors (OFETs). Here, we show how H₂O molecules adsorb and affect pentacene crystal by using photoelectron spectroscopic methods. Diffusion into the crystal is accompanied with accumulation of H₂O onto the crystal. Valence band, core level, and X-ray absorption spectra show that H₂O molecules physisorb on the pentacene surface via oxygen, resulting in the increase of the hole-injection barrier. The diffused molecules results in the deteriorated crystallinity, and they reflect the weakening inter-molecular interactions of pentacene crystal.     

Enhancement effect in photon-stimulated ion desorption for benzene adsorbed on silicon surfaces observed using angle-dependent technique

We have investigated photon-stimulated ion desorption from deuterated benzene (C₆D₆) adsorbed on Si(1 0 0) and Si(1 1 1) surfaces following C 1s core excitation. Using time-of-flight mass spectrometry combined with angle-dependent technique, we measured the dependences of mass-spectra of desorption ions on photon energies and on incident angle (θ) of synchrotron beam. We have found the ion yields for adsorbate-derived fragments of CD⁺ and CD₂⁺ are enhanced in very small angles of incident X-rays. Moreover, molecular orientation effect appeared in excitation energy dependences of D⁺ ions from the Si(1 0 0) and Si(1 1 1) surfaces; that is, ion yield spectra measured at θ = 10° are different from that at θ = 65°. Furthermore, it was found that desorption ion yields increase greatly with decreasing incident angles. The angular dependences are consistently similar for all ion species, excitation energies, and indexes of substrates. Possible desorption processes are described on the basis of the observations.     

Er -Li ion exchange in lithium niobate crystals: an EXAFS study

Lithium niobate crystals doped with erbium by the ion exchange process were studied by means of extended X-ray absorption fine structure spectroscopy and secondary ion mass spectrometry. The study of the local atomic order allowed the determination of the erbium environment in the crystal matrix and the investigation on the role of preparation conditions. Received 21 November 2002 Published online 1st April 2003 RID="a" ID="a"e-mail: sada@padova.infm.it     

Formation of argentic clusters and small Ag nanoparticles in soda-lime silicate glass

The formation of argentic clusters and very small Ag nanoparticles of 0.5 to 2 nm size in commercial soda-lime glass silver-doped by Ag/Na ion exchange in a mixed nitrate melt has been studied by electron microscopy and EXAFS. Particles formation was induced already during the ion exchange procedure, or by subsequent ion irradiation with 1.5 MeV He⁺ or 3 MeV Au⁺. The presence of nanoparticles was also macroscopically revealed by their surface plasmon resonance. The structural characterization indicates that specific configurations of silver oxide-like structures, so-called argentic clusters, are involved in the initial stage of nanoparticles formation.