Heavy metal phosphate nanophases in silica: influence of radiolysis probed via f-electron state properties

We have assessed the feasibility of carrying out time- and wavelength-resolved laser-induced fluorescence measurements of radiation damage in glassy silica. The consequences of alpha decay of Es-253 in LaPO₄ nanophases embedded in silica were probed based on excitation of 5f states of Cm³⁺, Bk³⁺, and Es³⁺ ions. The recorded emission spectra and luminescence decays showed that alpha decay of Es-253 ejected Bk-249 decay daughter ions into the surrounding silica and created radiation damage within the LaPO₄ nanophases. This conclusion is consistent with predictions of an ion transport code commonly used to model ion implantation. Luminescence from the ⁶D_7/2 state of Cm³⁺was used as an internal standard. Ion-ion energy transfer dominated the dynamics of the observed emitting 5f states and strongly influenced the intensity of observed spectra. In appropriate sample materials, laser-induced fluorescence provides a powerful method for fundamental investigation of alpha-induced radiation damage in silica.     

聚氯乙烯结构缺陷和热不稳定性之间关系的研究 2.各种结构缺陷含量和热脱氯化氢速率之间的关系

本工作采用溴加成法、酚解法、FTIR法及臭氧裂解法分别测定了五种不饱和蒸气压下聚合的PVC样品(u-PVC)和五种商品PVC样品(s-PVC)的总双键、总不稳定氯、孤立双键和内部双键的含量.通过研究结构缺陷和PVC的平均分子量及脱HCl速率的相互关系,揭示了不饱和总双键值,总不稳定氯和孤立双键含量彼此的相关性是建立在它们分别与1/M_n的相关性基础之上,从而得出了这三种定量值测得的主要都是端基烯丙基氯结构.根据三者对脱HCl速率的良好线性相关性,首次提出了端基烯丙基氯结构在HCl催化作用下异构化成内部烯丙基氯从而成为脱HCl速率主要原因的机理.     

High-Resolution Infrared Synchrotron Investigation of (HCN)2 and a Semi-Experimental Determination of the Dissociation Energy D0

The high-resolution infrared absorption spectrum of the donor bending fundamental band ν of the homodimer (HCN)₂ has been collected by long-path static gas-phase Fourier transform spectroscopy at 207 K employing the highly brilliant 2.75 GeV electron storage ring source at Synchrotron SOLEIL. The rovibrational structure of the ν transition has the typical appearance of a perpendicular type band associated with a Σ–Π transition for a linear polyatomic molecule. The total number of 100 assigned transitions are fitted employing a standard semi-rigid linear molecule Hamiltonian, providing the band origin ν₀ of 779.05182(50) cm⁻¹ together with spectroscopic parameters for the degenerate excited state. This band origin, blue-shifted by 67.15 cm⁻¹ relative to the HCN monomer, provides the final significant contribution to the change of intra-molecular vibrational zero-point energy upon HCN dimerization. The combination with the vibrational zero-point energy contribution determined recently for the class of large-amplitude inter-molecular fundamental transitions then enables a complete determination of the total change of vibrational zero-point energy of 3.35±0.30 kJ mol⁻¹. The new spectroscopic findings together with previously reported benchmark CCSDT(Q)/CBS electronic energies [Hoobler et al. ChemPhysChem. 19 , 3257–3265 (2018)] provide the best semi-experimental estimate of 16.48±0.30 kJ mol⁻¹ for the dissociation energy D₀ of this prototypical homodimer.     

Carbon-Supported Silver Catalysts for CO Selective Oxidation in Excess Hydrogen

Carbon materials were used as supports for Ag catalysts that are prepared using the conventional wet impregnation method, and their catalytic properties for CO selective oxidation in excess hydrogen at temperatures below 483 K were tested. A variety of techniques, e.g. N2 adsorption, XPS, TPD, UV-Vis DRS, TEM and SEM, were used to determine the influence of physical and chemical properties of the carbon on the properties of Ag catalyst. It was found that defects on the carbon surface served as nucleation sites for silver ions, while functional groups on carbon surface induced their reduction to the metallic form. The formation of silver particles on carbon was governed by homogeneous and/or heterogeneous nucleation during the impregnation and subsequent activation processes. The best catalytic performance was obtained with a Ag/carbon black catalyst with a uniform size distribution of silver nanoparticles (about 12 nm), moderate BET surface area (with a mesoporous structure), and a limited amount of carbon-oxygen groups. The research indicates that carbon materials are potentially good supports for silver catalysts for preferential oxidation of CO in excess hydrogen.     

氯磺化聚乙烯的γ—辐射交联

氯磺化聚乙烯(简称CSM)由于存在SO_2Cl基团很容易通过金属氧化物进行化学交联,但至今未见其辐射交联的详细报道.本文探讨氯含量对CSM辐射交联的影响. 所用CSM系吉林化工公司产品:20型(含氯量29～33％,下同),40型(33～37％)和30型(40～45％).将CSM和防老D按一定比例混炼均匀,再在140℃左右热压成形.试样用3.33×10~(15)Bg ~(60)Co于室温限量空气下进行辐照.辐照过的试样于80℃处理2小时以消除俘陷自由基.在氮气保护下先后用二甲苯和无水乙醇,加热回流48小时和8小时,测定凝胶含量.     

Investigations of the local distortions and EPR parameters for Cu2+ in xNa2O‐(30–x)K2O‐70B2O3 (5 ≤ x ≤ 25 mol%) glasses

The local distortions and electron paramagnetic resonance parameters for Cu²⁺ in the mixed alkali borate glasses xNa₂O‐(30–x)K₂O‐70B₂O₃ (5 ≤ x ≤ 25 mol%) are theoretically studied with distinct modifier Na₂O compositions x. Owing to the Jahn–Teller effect, the octahedral [CuO₆]¹⁰⁻ clusters show significant tetragonal elongation ratios p ~19% along the C₄ axis. With the increase of composition x, the cubic field parameter Dq and the orbital reduction factor k exhibit linearly and quasi‐linearly decreasing tendencies, respectively, whereas the relative tetragonal elongation ratio p has quasi‐linearly increasing rule with some fluctuations, leading to the minima of g factors at x = 10 mol%. The composition dependences of the optical spectra and the electron paramagnetic resonance parameters are suitably reproduced by the linear or quasi‐linear relationships of the relevant quantities (i.e., Dq, k, and p) with x. The above composition dependences are analyzed from mixed alkali effect, which brings forward the modifications of the local crystal‐fields and the electronic cloud distribution around Cu²⁺ with the variation of the composition of Na₂O.     

Radiation chemistry of tris(acetylacetonato) cobalt(iii) in aqueous solutions

Abstract

On radiolysis tris(acetylacetonato) cobalt(III) in aqueous solutions is found to get reduced by reaction with (1) hydrated electrons, (2) H atoms, (3) OH radicals and (4) C₂H₂OH radicals. The bimolecular rate constants for the first three reactions, determined by competition kinetics are: 4 × 10¹⁰, 2.3 × 10⁹ and 4.7 × 10⁹ M^?1sec^?1 respectively. Absorption spectra of the irradiated solutions indicate the formation of bis(acetylacetonato) cobalt(II) from reaction (1), but not from (3). The total cobaltous yield in air-free solutions is given byG(Co⁺⁺) = 5.6 and 6.5 at pH 6.5 and 1 respectively. It appears that G_eaq- ∽ _H ⁺ G_oH ∽ 2.8 in neutral solutions. Considerations of material balance for the primary yields of radiolysis of water suggest the possibility that the so-called independent H-atoms in neutral solutions are probably excited water molecules or ion-pairs.     

Defect-effects on the photoluminescence of ZrO2 bulk,film and nanocrystals

The photoluminescence (PL) properties of ZrO₂ have been measured at different temperatures between 7 and 300 K, using various kinds of ZrO₂ specimens: bulk crystal melt-grown by a large solar furnace, thermally oxidized zirconium plate (ZrO₂ film crystal on Zr ) and nanocrystals (surface area: 35–45m²/g, diameter: 20–30 nm). The results clarify the deep and shallow energy level structures in the energy gap. Reversible UV-laser-light-induced spectral changes are observed for all of the specimens in different specimen-atmospheres (vacuum and O₂ gas). The results elucidate the defect-effects of the PL properties and the PL enhancement mechanism in ZrO₂ nanocrystals.     

Production of palladium nanoparticles supported on multiwalled carbon nanotubes by gamma irradiation

Palladium nanoparticles were produced and supported on multiwalled carbon nanotubes (MWCNT) by gamma irradiation. A solution with a specific ratio of 2:1 of water-isopropanol was prepared and mixed with palladium chloride and the surfactant sodium dodecyl sulfate (SDS). The gamma radiolysis of water ultimately produces Pd metallic particles that serve as nucleation seeds. Isopropanol is used as an ion scavenger to balance the reaction, and the coalescence of the metal nanoparticles was controlled by the addition of SDS as a stabilizer. The size and distribution of nanoparticles on the carbon nanotubes (CNT) were studied at different surfactant concentrations and radiation doses. SEM, STEM and XPS were used for morphological, chemical and structural characterization of the nanostructure. Nanoparticles obtained for doses between 10 and 40 kGy, ranged in size 5-30 nm. The smaller nanoparticles were obtained at the higher doses and vice versa. Histograms of particle size distributions at different doses are presented.