Density functional study of the chemisorption of O2 on the armchair surface of graphite

The reaction between O₂ and the armchair surface of a model graphite molecule has been studied using density functional calculations at the B3LYP/6-31G(d) level of theory. Both equilibrium and transition state geometries were optimized to provide a fundamental understanding of the energetics and kinetics of the chemisorption, desorption, rearrangement, and migration reactions that contribute to carbon gasification. A small barrier of 18 kJ mol⁻¹ was found for the chemisorption reaction, which is 578 kJ mol⁻¹ exothermic overall, producing a stable quinone. A number of reaction pathways with barriers below 578 kJ mol⁻¹ were characterized. Gasification of carbon occurs as CO, with barriers of 296 and 435 kJ mol⁻¹ for the first and second CO loss, respectively. The stable quinone can also undergo a rearrangement reaction to form two ketene groups, with a barrier of 260 kJ mol⁻¹. If the armchair edge is extended to include an adjacent aromatic ring, the oxide can migrate along the surface. This initially forms a furan-like bridge structure, with a barrier of just 89 kJ mol⁻¹. A further barrier of 383 kJ mol⁻¹ leads to CO desorption from the furan. The furan can also rearrange further with a barrier of 212 kJ mol⁻¹ to form a five-membered lactone, the most stable structure identified on the potential energy surface. Rearrangement and migration reactions, which have not generally been incorporated into carbon gasification models, are shown to be potentially important pathways in carbon oxidation reactions.     

Electron-stimulated desorption of thin epitaxial films of KBr grown on (100)InSb

We have measured time-of-flight (TOF) distributions of Br atoms desorbed from thin (less than 1000 Å) epitaxial films of KBr on (100) InSb with a 2 keV electron beam. Although the general structure of the TOF spectra was similar to that obtained previously for the thick crystals, both the fast and the slow (thermal) components of the distribution were strongly dependent on the film thickness. We argue that this dependence is due to two different diffusion processes involved in the transport of the primary excitation products from the bulk to the surface. By measuring the velocity resolved ESD yield for films of various thicknesses, we determined that a diffusion length of the carriers responsible for the thermal ESD component varied from 30 to 700 Å with temperature in the range 20–300°C. In contrast, for the non-thermal desorption we found the carrier diffusion length of about 140 Å which did not depend significantly on the temperature.     

Hydrogen dissociation on high-temperature tungsten

H₂ dissociation on polycrystalline tungsten is measured from 1700 to 3000 K using the filament temperature (T) change and a normalized H-atom density at the chamber surface. The dissociation probability per H₂ filament collision (P_diss) saturates at 0.40 at high T and has a 2.25 ± 0.05 eV apparent activation energy when P_diss ? 1. This activation energy is consistent with prior data and models, but the H₂ pressure dependence is not. P_diss is independent of the H₂ pressure for this entire T range and the 1-85 mTorr pressure range studied, contradicting the primary model that has been used to explain H₂ dissociation on tungsten and other metals. We show that some apparently contradictory prior measurements are actually consistent with our observations and with each other, once this pressure dependence of P_diss is recognized.     

Origin and information content of the compensation effect

An attempt is made to assess: (i) The conditions under which a compensation effect should be observable, (ii) The associated physical properties affected by such compensation. (iii) The nature of the information which can be gleaned from studies of compensation. Specific attention is given to simple desorption processes and the main conclusion is that the compensation law in adsorption indicates a phenomenon involving many molecules. However the Meyer-Neldel rule in semiconductors is also embraced, as well as observations of the compensation effect in liquids.Dedicated to Professor J. Koutecký on the occasion of his 65th birthday     

湘鄂西地区五峰-龙马溪组泥页岩黄铁矿粒径特征

湘鄂西地区位于中扬子板块,该地区五峰-龙马溪组富有机质页岩有机质类型以Ⅱ1型为主,Ⅱ2型次之,具有高TOC含量(0.55%~4.28%)、高成熟度(2.4%~3.2%)的特征;且富有机质页岩中黄铁矿普遍发育。通过岩心样品及扫描电镜观察发现,龙马溪组黑色页岩常发育自形-半自形黄铁矿,扫描电镜下常见草莓状黄铁矿;五峰组黑色页岩岩心观察无明显晶形,扫描电镜下常现呈微晶黄铁矿颗粒,以细小颗粒状分布在有机质中。草莓状黄铁矿通常由微晶颗粒聚集而来,其草莓状直径大小由硫复铁矿的形成和沉积水动力控制。根据草莓状黄铁矿直径D与深度关系分析出湘鄂西地区黑色页岩的沉积环境表现为五峰组闭塞环境、龙马溪组闭塞环境、龙马溪组贫氧-缺氧环境三种。由草莓状黄铁矿直径D与微晶黄铁矿直径d建立D/d的关系表明:从沉积期到成岩期,五峰组闭塞环境的还原性比龙马溪组闭塞环境的还原性强;且五峰组闭塞环境的沉积水动力要比龙马溪组闭塞环境的沉积水动力要弱,水体更稳定。此外,D与d之间的关系能侧面反映该地区五峰-龙马溪组富有机质页岩孔隙度的变化趋势。D/d值与页岩解吸气量也有良好的对应关系,龙马溪组D/d值越大,解吸气量越少。五峰组D/d值较龙马溪组普遍偏小,解吸气量远大于龙马溪组。上述结果表明水体还原环境的强弱是湘鄂西烃源岩有机质形成和保存的重要因素,从而影响页岩气的富集。     

页岩基质中甲烷传质输运产能计算模型

页岩气藏基质中存在吸附气和游离气,通过扩散和渗流两种传输机制进行流动。为了研究页岩气藏基质产气规律,推导了一维页岩基质产气量计算公式,扩散体积流量与入口压力成线性正比关系,渗流体积流量与入口压力成二次函数关系,渗透率越高、扩散系数越大,则体积流量越大。在此基础上,设计了全直径页岩岩心甲烷解吸、扩散、渗流耦合实验,研究了产气量与压力的变化关系;并通过拟稳态阶段的实验数据验证了一维页岩基质产气量计算公式的正确性。利用模型计算结果预测了页岩气传质输运实验未来体积流量的变化趋势:当入口压力达到15 MPa时,渗流体积流量在耦合流量中所占比例接近50%;当入口压力低于15 MPa时,扩散体积流量在耦合流量中所占比例较高。     

An influence of deposition temperature on structural,optical and electrical properties of sprayed ZnO thin films of identical thickness

Nanocrystalline ZnO thin films were deposited at different temperatures (T_s = 325 °C–500 °C) by intermittent spray pyrolysis technique. The thickness (300 ± 10 nm) independent effect of T_s on physical properties was explored. X-Ray diffraction analysis revealed the growth of wurtzite type polycrystalline ZnO films with dominant c-axis orientation along [002] direction. The crystallite size increased (31 nm–60 nm) and optical band-gap energy decreased (3.272 eV–3.242 eV) due to rise in T_s. Scanning electron microscopic analysis of films deposited at 450 °C confirmed uniform growth of vertically aligned ZnO nanorods. The films deposited at higher T_s demonstrated increased hydrophobic behavior. These films exhibited high transmittance (>91%), low dark resistivity (～10^?2 Ω-cm), superior figure of merit (～10^?3 Ω^?1) and low sheet resistance (～10² Ω/□). The charge carrier concentration (η -/cm³) and mobility (μ – cm²V^?1s^?1) are primarily governed by crystallinity, grain boundary passivation and oxygen desorption effects.     

Highly efficient,economic, and recyclable glutathione decorated magnetically separable nanocomposite for uranium(VI) adsorption from aqueous solution

A green and environment-friendly magnetically separable nanocomposite, glutathione@magnetite was fabricated sonochemically through the functionalization of Fe₃O₄ by glutathione which was well characterized using Fourier-transform infrared spectroscopy, ultravoilet-visible spectroscopy, scanning electron microscope, energy-dispersive X-ray spectroscopy, X-ray photoelectron spectroscopy, X-ray diffraction, thermogravimetric analysis, vibrating sample magnetometer, Brunauer-Emmett-Teller, and high-resolution transmission electron microscope. The parameters affecting adsorption including pH, temperature, contact time, initial adsorbate concentration, and adsorbent amount were optimized by batch experiments. The magnetic glutathione@magnetite was applied for the removal of uranium(VI) in water with maximum adsorption capacity found to be 333.33 mg/g in 120 min at a neutral pH at 25 °C showing high efficiency for U(VI) ions. Furthermore, adsorption results obtained from UV-vis spectroscopy were validated by inductively coupled plasma optical emission spectroscopy. The thermodynamic parameters, viz Gibbs free energy (ΔGº), standard enthalpy change (ΔHº), and standard entropy change (ΔSº) of the process were calculated using the Langmuir constants. The pseudo-second-order kinetics model is seen to be applicable for describing the uptake process using a kinetics test. Moreover, desorption studies reveals that glutathione@magnetite can be used repeatedly, and removal efficiency shows only a small decrease after six cycles. Thus, glutathione@magnetite acts as a potential adsorbent for the removal of U(VI) from the water with great adsorption performance.     

Preparation of carbon coated Fe3O4 nanoparticles for magnetic separation of uranium

Uranium(VI) was removed from aqueous solutions using carbon coated Fe₃O₄ nanoparticles (Fe₃O₄@C). Batch experiments were conducted to study the effects of initial pH, shaking time and temperature on uranium sorption efficiency. It was found that the maximum adsorption capacity of the Fe₃O₄@C toward uranium(VI) was ∼120.20 mg g⁻¹ when the initial uranium(VI) concentration was 100 mg L⁻¹, displaying a high efficiency for the removal of uranium(VI) ions. Kinetics of the uranium(VI) removal is found to follow pseudo-second-order rate equation. In addition, the uranium(VI)-loaded Fe₃O₄@C nanoparticles can be recovered easily from aqueous solution by magnetic separation and regenerated by acid treatment. Present study suggested that magnetic Fe₃O₄@C composite particles can be used as an effective and recyclable adsorbent for the removal of uranium(VI) from aqueous solutions.     

Adsorption behavior of Pb(II) on montmorillonite

The present work investigated the adsorption and desorption behaviors of Pb(II) on montmorillonite. The adsorption experiments were carried out using batch process. The results show that the adsorption is dependent on the pH value of the medium, and the uptake of Pb(II) increases with the pH increasing in the pH range of 2.0–10.0. The adsorption kinetics is in better agreement with pseudo-second order kinetics, and the adsorption data is a good fit with Langmuir isotherm. The presence of EDTA may result in a decrease of the amount of Pb(II) adsorbed. The presence of electrolyte and EDTA may enhance the desorption of Pb(II) ions adsorbed. The adsorption mechanism of Pb(II) on montmorillonite may be explained in two aspects: the chemical binding between Pb(II) ions and surface hydroxyl groups; and the electrostatic binding between Pb(II) ions and the permanent negatively charged sites of montmorillonite.