脉冲红外法测定难熔金属钛中氧含量

采用脉冲红外定氧仪测定了难熔金属钛及其合金中氧含量,并对影响测定结果的诸多因素,例如助熔剂的选择和比例、分析功率的确定、坩埚的选择、试样量的选择和空白值的设定进行了实验和讨论,对分析的准确度和稳定性进行了考察,取得了满意的结果。     

Low-frequency ultrasound induces oxygen vacancies formation and visible light absorption in TiO2 P-25 nanoparticles

Low-frequency ultrasound (LFUS) irradiation induces morphological, optical and surface changes in the commercial nano-TiO₂-based photocatalyst, Evonik-Degussa P-25. Low-temperature electron spin resonance (ESR) measurements performed on this material provided the first experimental evidence for the formation of oxygen vacancies (V_o), which were also found responsible for the visible-light absorption. The V_o surface defects might result from high-speed inter-particle collisions and shock waves generated by LFUS sonication impacting the TiO₂ particles. This is in contrast to a number of well-established technologies, where the formation of oxygen vacancies on the TiO₂ surface often requires harsh technological conditions and complicated procedures, such as annealing at high temperatures, radio-frequency-induced plasma or ion sputtering.Thus, this study reports for the first time the preparation of visible-light responsive TiO₂-based photocatalysts by using a simple LFUS-based approach to induce oxygen vacancies at the nano-TiO₂ surface. These findings might open new avenues for synthesis of novel nano-TiO₂-based photocatalysts capable of destroying water or airborne pollutants and microorganisms under visible light illumination.     

直线型l-CnH(n=5,6)自由基与氧气反应机理的理论研究

为了探索更长的碳链自由基l-C_nH与O₂反应的机理, 在CCSD(T)/CC-PVTZ+ZPVE//B3LYP/6-311++G(d,p)的计算水平下, 讨论了当n=5,6时, l-C_nH+O₂的各个异构化反应通道. 当n=5时, 主要反应通道为碳迁移过程, 生成主要产物为P2(CO₂+C₄H); 当n=6时, 碳-氧交换[产物为P1(CO+HC₅O)]和氧迁移过程[产物为P3(³O+HC₆O)]均为主要通道, 并具有很高的竞争性. 将所得结构与l-C_nH(n≤4)+O₂的反应机理进行了对比.     

基于动态光谱法的多波长脉搏血氧饱和度测量

目前临床上血氧饱和度的无创检测主要基于双波长的脉搏血氧饱和度测量原理,但其检测精度仍然需要进一步的探究和完善。近年来,国内外的很多研究者采用三波长甚至八波长的方法测量血氧饱和度,从某种程度上减小了误差。动态光谱法作为一种新型血液成分无创检测方法,能消除受试者个体差异和测量环境等的影响,在血红蛋白浓度的无创检测研究中取得了很好的效果。基于动态光谱法对多波长下脉搏血氧饱和度检测进行了研究：对60名重症监护患者进行动态光谱采集以及动脉抽血分析血氧饱和度值;采用高灵敏度光纤光谱仪,采集受试者指端透射多波长下的光谱信息;以单拍提取法提取波长范围为606.44~987.55 nm的动态光谱;以动脉血气分析中血氧饱和度值为参考真值,建立血氧饱和度与多波长动态光谱数据的组合间隔偏最小二乘校正模型;得到预测集的相对误差为±0.017 6,而两波长测量装置监护仪上得到的数据相对误差为±0.116 4。结果表明：利用高灵敏度光纤光谱仪采集多波长光谱信息,用动态光谱法进行数据预处理,进行多波长血氧饱和度检测,有效降低了血氧饱和度的测量误差。     

HOD分子在(~C)1B1态的光解动力学:产物OH/OD的分支比以及OD键解离能

Photodissociation of jet-cooled HOD via the ? state around 124 nm has been studied using the H(D)-atom Rydberg tagging time-of-flight technique. Rotational state resolved action spectrum and the product translational energy distribution spectra have been recorded for both D+OH and H+OD dissociation channels. Product channel OH/OD branching ratios for the individual ?- X rotational transition have been determined. A comparison is also given with the B- X and ?- X transitions. In addition, the dissociation energy of the OD bond in HOD has been determined accurately to be 41751.3±5 cm^-1.     

VUV Photoionization and Dissociation of Tyramine and Dopamine: the Joint Experimental and Theoretical Studies

Photon induced dissociation investigations of neutral tyramine and dopamine are carried out with synchrotron vacuum ultraviolet photoionization mass spectrometry and theoretical calculations. At low photon energy, only molecular ions are measured by virtue of near-threshold photoionization. While increasing photon energy to 11.7 eV or more, four distinct fragment ions are obtained for tyramine and dopamine, respectively. Besides, the ioniza-tion energies of tyramine and dopamine are determined to be 7.98±0.05 and 7.67±0.05 eV by measuring the photoionization efficiency curves of corresponding molecular ions. With help of density function theory calculations, the detailed fragmentation pathways are es-tablished as well. These two molecular cations have similar aminoethyl group elimination pathways, C₇H₈O₂^+·(m/z=124) and C₇H₈O^+·(m/z=108) are supposed to be generated by the McLafferty rearrangement via γ-hydrogen (γ-H) shift inducing β-fission. And CH₂NH₂⁺ is proposed to derive from the direct fission of C7-C8 bond. Besides, the McLafferty rear-rangement and the C7-C8 bond fission are validated to be dominant dissociation pathways for tyramine and dopamine cations.     

Acrolein coupling on reduced TiO2(1 1 0): The effect of surface oxidation and the role of subsurface defects

Reactions of acrolein, water, and oxygen with the vacuum-reduced surface of TiO₂(1 1 0) are reported in a temperature programmed reaction study of the interaction of an aldehydic pollutant with a reducible metal oxide. A total of 25% of the acrolein that binds to the surface is converted to products. Notably, carbon-carbon coupling occurs with 86% selectivity for formation of C₆ products: C₆H₈, identified as 1,3-cyclohexadiene, in a peak at 500 K and benzene immediately thereafter at 530 K. Acrolein is evolved from the surface in three peaks: a peak independent of coverage at 495 K, attributed to decomposition of an intermediate that is partly converted to C₆H₈; a coverage-dependent peak that shifts from 370 K (low coverage) to 260 K (high coverage), which is attributed to adsorption at 5-fold coordinated Ti sites; and a multilayer state at 160 K. Water and acrolein compete for 5-fold coordinated titanium sites when dosed sequentially. The addition of water also opens a new reaction pathway, leading to the hydrogenation of acrolein to form propanal. Water has no effect on the yield of 1,3-cyclohexadiene. Exposure of the surface to oxygen prior to acrolein dosing quenches the evolution of acrolein at 495 K and concurrently eliminates the coupling. From these results, we propose that reduced subsurface defects such as titanium ion interstitials play a role in the reactions observed here. The notion that subsurface defects may contribute to the reactivity of organic molecules over reducible oxide substrates may prove to be general.     

Oxygen (O6+) ion beam irradiation effects on etching parameter in lexan polymeric track detector

The polymer Lexan was irradiated to 80MeV O⁶⁺ ion beam using the 15UD pelletron at Inter University Accelerator Centre, New Delhi. The ion fluence ranging from 10¹¹ to 3 × 10¹² ions/cm² has been used to study the dose effects of irradiation on Lexan. By using the etching technique, it is observed that the bulk etch rate of the sample increases with increasing the ion influence, while the activation energy associated with it show a decreasing trend which can be explained on the basis of polymer degradation.      

Energetics of oxygen embedment into unreconstructed and reconstructed Cu(1 0 0) surfaces: Density functional theory calculations

Atomic oxygen embedment into a Cu(1 0 0) surface is studied by density functional theory calculation and the nudged elastic band method. As the oxygen coverage increases on the unreconstructed surface from 0.25 monolayer (ML) to 0.75 ML, the energy barrier for oxygen embedment decreases and an energetically favorable sub-surface site is found at 0.75 ML coverage. At a fixed oxygen coverage of 0.5 ML, the oxygen embedment energetics vary with the surface morphology and the embedment is found to be more probable for reconstructed structures compared to the bare surface. On the missing-row reconstructed surface, we find that the energy barrier for atomic oxygen embedment is smaller through the missing-row compared to other paths, suggesting a mechanism for the formation of sub-surface oxygen structures that are consistent with a recent experiment. The energy barrier for sub-surface oxygen diffusion is predicted to be less than that for on-surface diffusion.     

Low energy oxygen implantation induced improved crystallinity and optical properties of surface modified ZnO single crystals

We report on the low energy oxygen implantation induced improvement in crystallinity and optical properties of surface modified ZnO single crystals. Undoped ZnO (0 0 0 1) single crystal wafers are implanted with 100 keV oxygen ions at a dose of 5 × 10¹³ and 5 × 10¹⁴ cm⁻² and subsequently annealed at 500 and 600 °C in oxygen ambient. The as-implanted and annealed ZnO wafers are studied by Rutherford back scattering spectrometry (RBS), channeling, Raman, photoluminescence (PL), and Fourier transform infrared spectroscopy (FTIR). Channeling studies show a relatively high χ_min (>20%) in the virgin ZnO wafer. After implantation and two-step annealing, RBS studies show improved crystallinity. Raman line width analysis for the mode indicates reduction in strain in the annealed samples as compared to the virgin ZnO wafer. As-implanted samples show drastic quenching of the near band-edge (NBE) PL band due to defects created by the implantation. However, after two-step annealing, the low-dose implanted sample show a five-fold increase in intensity ratio of NBE band (376 nm) to defect related broad band (∼530 nm) at room temperature. Implantation induced changes in the composition and improved crystallinity in the near surface region is accounted for the major improvement in the PL emission.