几种醇类阳离子的密度泛函理论研究

用B3LYP方法及6—31G（d,P）、6—31＋G（d,p）、6—311G（d,P）和6—311＋G（d,P）基组,对若干醇类阳离子CH3OH＋、CH3CH2OH＋和CH3CH2CH2OH＋做了理论研究,优化了它们的电子基态的结构,计算了对应分子的垂直电离势（VIP）和绝热电离势（AIP）．结果表明,这些离子的对称性与对应分子相同;自然布居分析计算表明,这些离子的正电荷主要分布在各H原子上;B3LYP／6—3ll＋G（d,P）级别上计算的各分子的VIP值和实验值符合得很好．     

VUV threshold photoelectron spectroscopy of the C2H3Cl molecule

The threshold photoelectron spectrum of the C₂H₃Cl molecule is studied by using synchrotron radiation light source and supersonic molecular beam. The vertical ionization potentials of different orbital electrons and some vibrational structures are obtained. The observed Rydberg autoionization peaks are assigned by A²A¹ state of C₂H₃Cl₊.     

NaB_5H_n团簇的几何结构与电子性质的理论研究

使用密度泛函理论（DFT）的杂化密度泛函B3LYP方法在6-311＋g（d）基组水平上对NaB5Hn团簇各种可能的构型进行几何结构优化,预测了各团簇的最稳定结构：并对最稳定结构的平均结合能（Eb）,二阶能量差分（△2E）和能隙（Eg）等进行了理论研究：结果表明,随着氢原子数的增加,NaB5Hn团簇的结构由平面转变为复杂的三维立体结构,当氢原子数小于4时,簇的结构为平面构型,其他所有的团簇都是三维立体结构;NaB5Hn团簇的平均结合能、二阶差分能和能隙等均表现出明显的＂奇-偶＂振荡和＂幻数＂效应;NaB5H8,NaB5H12,NaB5H18和NaB5H20团簇稳定性大于NaB5Hn中的其他团簇,为NaB5Hn团簇中最稳定的几种团簇。     

Gas-Liquid Interfacial Plasma engineering under dilute nitric acid to improve hydrophilicity and OER performance of nickel foam

The world has been moving rapidly to find new eco-friendly energy sources. Water electrolysis consists of two reactions of Oxygen Evolution Reaction (OER) and Hydrogen Evolution Reaction (HER), whereas the OER is considered the rate-limiting step. The most commercialized electrode for OER in the alkaline electrolyte is Ni foam, but its original surface is hydrophobic. It is possible to accelerate the adsorption and desorption process of reactants and products during OER by adding hydrophilic functional groups such as –OH on the surface of Ni foam. In this study, a novel Gas-Liquid Interfacial Plasma (GLIP) engineering at room temperature was successfully applied to modify the Ni foam surface dilute (1 ?M) HNO₃ solution. At a current density of 400 ?mA ?cm^?2, GLIP-treated Ni foam electrodes at 1 ?M HNO₃ concentrations showed OER overpotentials of 458 ?mV. Among all, GLIP with 1 ?M HNO₃ treatment of 30 ?min showed 129 ?mV less overpotential than the nickel foam before treatment. In summary, GLIP can be justified as an environmentally friendly and efficient surface treatment to improve the wettability and OER performance of Ni-based electrodes in water electrolysis.     

Rate constants for the reaction of ozone with <Emphasis Type="Italic">n</Emphasis>-butyl, <Emphasis Type="Italic">s</Emphasis>-butyl and <Emphasis Type="Italic">t</Emphasis>-butyl methyl sulfides

The rate constants for the ozone reactions with n-butyl methyl sulfide （n-BMS, CHaCH2CH2CH2SCH3）, sec-butyl methyl sulfide （s-BMS, CH3CH2（CH3）CHSCHa） and tert-butyl methyl sulfide （t-BMS, （CH3）3CSCH3） were measured using our smog chamber under supposedly pseudo-first-order conditions at 30002 K and 760 Torr. The experimental determined rate constants for n-butyl, s-butyl and t-butyl methyl sulfide are （1.23 ± 0.06）×10-19, （5.08 ± 0.19）×10-20 and （2.26 ± 0.14）×10-20 cm3 molecule-1· s-1, respectively. The reactivity-structure relationship of the reactions was discussed and used to illustrate the mechanism of the ozone reaction with thioethers. The results enrich the kinetics data of atmospheric chemistry.     

UV/H2O2作用下冰中苯酚的光转化及其与羟基自由基的关系

在UV和H₂O₂作用下考察pH值、 光强、 H₂O₂初始浓度和无机离子等对冰中苯酚光解的影响, 并利用二甲基亚砜（DMSO）捕获体系中生成的
羟基自由基（·OH）研究·OH对冰中苯酚光解的影响. 实验结果表明: H₂O₂可显著促进冰中产生·OH及苯酚光解; 改变光强、 pH值和H₂O₂的初始浓度, 苯酚的光解率随体系中·OH浓度的增加而增大; 加入NO^-₂和NO^-₃可抑制体系中产生·OH及苯酚光解; 加入SO^2-₄不影响体系中·OH的产生及苯酚光解; 加入CO^2-₃和HCO^-₃可抑制体系中产生·OH, 但对苯酚光解影响较小, 这是由于体系中产生了其他自由基所致.     

A novel Fe/HNT visible light-driven heterogeneous photocatalyst: Development as a semiconductor and photocatalytic application

Fe/HNT (Iron/Halloysite-nanotube) heterogeneous semiconductor catalysts operating effectively under visible light were developed by using FeCl₃, FeSO₄ and Fe(OH)₃ sludge precipitated after electro-Fenton process and named as Fe/HNT-I, Fe/HNT-II and Fe/HNT-III, respectively. Chemical configuration and particle morphology of the catalysts were characterized with XRD, SEM-EDS and UV–vis DRS. Effect of the developed Fe/HNT photocatalysts was investigated for the degradation of Reactive Orange 16 (RO16) textile dye under visible light. The photocatalytic decolorization of RO16 was 95.6%, 99.3% and 96.6%, respectively. It was found that the photocatalytic performance of Fe/HNT-III catalyst under visible light was effective compared to Fe/HNT-I and Fe/HNT-II. The iron ratio in the catalyst's structure (Fe:HNT ratio 0.25, 0.5 and 0.75 (w/w)) and pH value (4, 7 and 9) in production phase were also changed to investigate the photocatalytic effect of Fe/HNT-III. An Fe:HNT ratio of 0.25 and a pH of 4 were determined as the optimum conditions for catalyst production. Optimum H₂O₂ dosage value was also investigated for photocatalytic oxidation process and determined to be 10 ?mM. Finally, the optimum conditions were further used for the degradation of Terbinafine hydrochloride (TerHCl) active drug and the treatment of wastewater from the textile and pharmaceutical industries.     

Theoretical investigation on mechanism of dissociation of furan

Conclusion  According to the calculated results for the dissociation mechanism of C₄H₄O⁺, we come to a conclusion as follows:

Effect of CH3OOH on the atmospheric concentration of OH radicals

Methyl hydroperoxide (CH₃OOH, MHP) is known to be a significant sink and reservoir of HO_x and RO_x radicals in the atmosphere. In order to investigate the impact of MHP on the concentration of atmospheric OH radicals, two key gas-phase reactions of MHP, i.e. the reactions with OH radicals and with UV photolysis, have been simulated at temperature of 293±2 K and total pressure of 1.01×10⁵ Pa, using the long path Fourier transform infrared (LP-FTIR) spectrometry. OH radicals are generated by the photolysis of O₃ in the presence of water vapor. Combined with the relative rate method, the reaction rate constant of MHP with OH radicals is determined to be (3.99±0.15)×10^-12 cm³?molecule^-1?s^-1, and thus the atmospheric lifetime of MHP is estimated at 2.9 days. Furthermore, from detailed analysis of the UV photolysis of MHP, the yield of OH radicals is obtained to be 0.91±0.04. Based on the MHP atmospheric lifetime and the yield of OH radicals, it is concluded that MHP plays an essential role in the redistribution of OH radicals in the troposphere.     

Effect of CH3OOH on the atmospheric concentration of OH radicals

Methyl hydroperoxide (CH₃OOH, MHP) is known to be a significant sink and reservoir of HO_x and RO_x radicals in the atmosphere. In order to investigate the impact of MHP on the concentration of atmospheric OH radicals, two key gas-phase reactions of MHP, i.e. the reactions with OH radicals and with UV photolysis, have been simulated at temperature of 293±2 K and total pressure of 1.01×10⁵ Pa, using the long path Fourier transform infrared (LP-FTIR) spectrometry. OH radicals are generated by the photolysis of O₃ in the presence of water vapor. Combined with the relative rate method, the reaction rate constant of MHP with OH radicals is determined to be (3.99±0.15)×10^-12 cm³?molecule^-1?s^-1, and thus the atmospheric lifetime of MHP is estimated at 2.9 days. Furthermore, from detailed analysis of the UV photolysis of MHP, the yield of OH radicals is obtained to be 0.91±0.04. Based on the MHP atmospheric lifetime and the yield of OH radicals, it is concluded that MHP plays an essential role in the redistribution of OH radicals in the troposphere.     

Cu2O-templated fabrication of Ni(OH)2·0.75H2O hollow tubes for electrocatalytic oxygen evolution reaction

Cu₂O is an ideal template material for the preparation of transition metal hydroxide/oxyhydroxides with oxygen evolution reaction (OER) enhanced catalytic performance. Here, inspired by Pearson's principle, Cu₂O wires were prepared and used as a sacrificial template to prepare Ni(OH)₂·0.75H₂O hollow tubes (Ni(OH)₂ HTs) with highly improved surface roughness. Benefiting from unique structural advantages, the Ni(OH)₂ HTs showed excellent catalytic activity, rapid kinetics and a long-term stability as the OER catalyst, where an overpotential of only 207 ?mV was required to drive a current density of 10 ?mA ?cm^?2, an ideal kinetics with a Tafel slope as 79.8 ?mV dec^?1 was calculated, and no obvious attenuation in chronoamperometry was discovered after operation for 24 ?h. This paper provides a novel template-assisted strategy to prepare high-performance transition metal-based OER catalysts possessing hollow and tubular structures.     

S2分子电离能的多参考方法计算

应用多组态准简并微扰理论, 计算了S₂分子基态和S⁺₂分子离子基态与激发态的绝热势能曲线, 并拟合光谱参数,  得到了S₂分子9~16 eV的3p电子电离的绝热电离能和垂直电离能. 计算结果表明, S₂分子的第一绝热电离能为9.34 eV, 与实验值(9.356±0.002)eV相符. 比较了其他电离谱带绝热和垂直电离能的理论计算值与实验值, 并分析了误差产生因素,  结合计算结果对S⁺₂(A²Π_u)和S⁺₂(B²Σ^-_g)电离谱带进行了确认.     

Physical chemistry mechanisms of CDR system in sulphide mineral flotation

The flotation tests, zeta potential measurements, and Fourier transform infrared spectroscopy (FTIR) analysis on galena, sphalerite, and pyrite were studied in a collecting-depressing-reactivating (CDR) system. In this system, sulphide minerals were first collected and activated by the collector, and then depressed strongly by Ca(OH)₂ in a strong alkaline solution. Finally, they were reactivated by H₂SO₄. The flotation tests of pure minerals showed that in the Ca(OH)₂ depressing process sulphide minerals had similar flotation characteristics because they had already been influenced by the collector. Hence, the flotability differences between them were reduced. However, in the H₂SO₄ reactivating process considerable differences in the flotability between galena and sphalerite/pyrite were produced. That is to say, galena was relatively easy to be reactivated by H₂SO₄, but sphalerite and pyrite were not reactivated at pH > 11. The zeta potentials of sulfide minerals measured by the Zeta Plus presented irreversible characteristics on the change of pH values. The results of the FTIR spectra analysis indicated that the collectors already adsorbed on the mineral surface were removed partially by Ca(OH)₂.     

Shock tube study on auto-ignition characteristics of kerosene/air mixtures

Ignition delay times are obtained for kerosene/air mixtures behind the reflected shock waves at temperatures between 1445 and 1650 K,at a pressure of 0.11 MPa and an equivalence ratio of 1.0.A nebulization device with Laval nozzle is used to nebulize kerosene and form an aerosol phase,which evaporates and diffuses rapidly behind the incident shock waves.Mixtures auto-ignite behind the reflected shock waves.An ICCD is used to visualize the kerosene/air mixture’s ignition characteristics.The mixture’s ignition intensity increases with increase in initial temperature.Continuous and irregular flames exist below 1515 K while plane and discontinuous flames exist over 1560 K.Ignition delay times decrease with increase in initial temperature.Experimental data shows good agreement with results reported previously in the literature.A new surrogate (consisting of 10% toluene,10% ethylbenzene and 80% n-decane) is proposed for kerosene.Honnet et al.’s mechanism is used to simulate the ignition of kerosene with calculations agreeing well with the experimental data.The sensitivity of reaction H+O2 <=>OH+O,which shows the highest sensitivity to the ignition delay time,increases with an increase in temperature.The chain breaching reaction of CH3 with O2 accelerates the total reaction rate and the H-atom abstraction of n-decane controls the total reaction rate.The rate of production and instantaneous heat production indicate that two reactions,H+O2 <=>OH+O and O+H2 <=>OH+H,are the key reactions to the formation of OH radicals,as well as the main endothermic reaction.However,the reaction of R3 is the main heat release reaction during ignition.Flame structure analysis shows that initial pressure is increased slightly as CO and H2O will appear before main ignition.     

高级氧化技术研究现状及其发展趋势

 中国面临环境保护的重大压力,高级氧化技术(AOT)是解决环境污染的理想绿色技术,而高级氧化技术是指·OH制备以及诱发一系列的攻击污染物及微生物反应,从源头上解决了治理污染过程中再污染的问题。高级氧化技术规模制备·OH是其标志性核心关键问题。基于此,学术界进行了一系列羟基自由基制备研究工作。本文介绍了在水中制备·OH的方法,主要介绍O₃/H₂O₂、O₃/UV、H₂O₂/UV、Fenton、光催化氧化、电子辐射和水激励等方法;也介绍了在气体中制备·OH的方法,主要有脉冲电晕放电法、电子束和强电离放电法等。强电离放电法有望同时解决在水、气中规模制备·OH过程中存在的问题。     

KF4-和KF4系列超卤化物稳定性及热裂解的理论研究

目的对KFn-和KFn(n=1～4)系列超卤化物进行理论研究。方法采用密度泛函理论B3LYP/6-311+G(3df)方法。结果得到了KF n-和KFn系列卤化物的稳定构型、垂直电离能VDE、垂直电子亲合能EAvert、绝热电子亲合能EAad、同位素效应及裂解反应热力学信息。结论同位素效应不影响VDE,EAvert,EAad及裂解反应热力学能变的值。中性物质每一步的裂解均易于其负离子的对应裂解。相对电离而言,热裂解更容易破坏该类负离子。     

K,Cu,Rb,Ag和Cs原子第一离化势的相对论HFS计算

本文在相对论的Hartree-Fock-Slater(RHFS)近似中,考虑了原子中价电子和核实电子之间的极化效应,使用类似于“冻结核实”和“弛豫核实”近似的方法,对K,Cu,Rb,Ag和Cs原子的第一离化势分别进行了计算。计算结果与实验数据比较,偏差较小。     

Resonance-enhanced multiphoton ionization spectroscopy on the B′2Σ+ and B2Π states of NS

Resonance-enhanced multiphoton ionization （REMPI） spectra of N^32S and N^34S have been recorded in the range of 35700-40200 cm^-1. The radical was generated by a pulsed dc discharge of a mixture of SF6 and N2 under a supersonic free jet condition. All the 16 observed bands of N^32S radicals have been assigned, among which 12 bands belong to three transition progressions （v′=0-4, 0）, （v′=1-4, 1） and （v′=2-4, 2） from the X^2П ground state to the B′^2∑^＋ upper state and the rest correspond to （9, 0）, （10, 0）, （11, 0） and （12, 0） bands of B^2П-X^2П transition, respectively. Analysis of the rotationally resolved spectra yields exhaustive spectroscopic constants of both the X^2П ground state and the B′^2∑^＋ excited state. The electronic transition bands of the isotopic molecule N^34S have been rotationally analyzed for the first time and the rotational constants of the ground and upper states have been determined simultaneously.     

Kinetics of C2(a3Πu) radical reactions with NO, N2O, O2, H2 and NH3

Pulsed laser photolysis/laser-induced fluorescence (LP-LIF) is utilized to measure rate constants for C₂(a³Π_u) reactions with NO, N₂O, O₂, H₂ and NH₃. Multiphoton dissociation of C₂Cl₄ at 266 nm is employed for the generation of C₂(a³Π_u) radicals. The C₂(a³Π_u) concentration is monitored by the fluorescence of the (0, 0) band of the (d³Π_g&#8596;a³Π_u) transition at 516.5 nm. C₂(a³Π_u) removal rate constants for the reactions are determined as k_NO = (5.46 ± 0.10) × 10^-11 cm³ molecule^-1 s^-1 , k_N2O = (1.63 ± 0.20) × 10^-13 cm³ molecule^-1 s^-1 , k_N2O = (1.58 ± 0.16) × 10^-11 cm³ molecule^-1 s^-1, k_O2 = (5.92 ± 1.00) × 10^-14 cm³ molecule^-1 s^-1, k_H2< 1.0× 10^-14 cm³ molecule^-1 s^-1. Based on the data analysis and theoretical calculation, we suggest that the C₂(a³Π_u) reactions with H₂ and NH₃ proceed via the hydrogen abstraction mechanism, barriers exist at the entrance channel of the reactions of C₂(a³Π_u) with H₂ and NH₃.     

The impact of HS radicals on the measured rate constant of H<Subscript>2</Subscript>S with OH radicals

The rate constant for the reaction of OH radicals and hydrogen sulfide (H₂S) was studied in different bath gases (including N₂, air, O₂ and He) by using relative technique at 298 K. The small difference of the measured rate constants between N₂ and those with the presence of O₂ suggested possible influence of HS self reaction. Further experiments with NO_x presence for scavenging HS demonstrated this assumption. The rate constant of (5.48±0.12) ×10^–12 cm³ molecule^–1 s^–1 obtained with 4.09 ×10^–4 mol m₃ NO presence may be accurate for estimating the atmospheric lifetime of H2S. The results provided circumstantial evidence that the rapid reaction of HS with N₂O is suspected.