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.     

Kinetic study of the reaction of chlorine atoms with 3-methyl-3-buten-1-ol

The reaction of a typical unsaturated alcohol, 3-methyl-3-buten-1-ol （MBO331）, with Cl atoms, was investigated for the first time. The reaction was investigated using discharged flow-tube coupled with electron impact mass spectrometer. The experiments were performed over the temperature range of 248 K-298 K and at pressure of 1 torr in He as the bath gas. The obtained kinetic data were used to derive the Arrhenius expression： k1 = （3.47 ± 1.21） × 10^-11 exp[（ 599 ±69）/7] cm^3 molecule^-1 s^-1. Finally, atmospheric lifetimes of the MBO331 with respect to OH radicals, NO3 radicals and CI atoms have been calculated and the atmospheric implications are considered briefly.     

Synthesis of well-defined functional crystals by high temperature gas-phase reactions

Over the past decades, there have been many synthesis methods on producing well-defined crystals, due to their enormous application potentials in industrial field. Among them, high temperature gas-phase reactions （HTGR） approach may be one of the most promising processes for fabrication of well-defined crystals with controllable structure, size, shape, and composition. This review is focused on the recent progresses in synthesizing well-defined crystalline TiO2 dominated with, respectively, {001 } facets and { 105 } facets, one-dimensional ZnO and SnO2 nanorods/nanowires, MoS2 nanosheets as well as GaP, InP, and GaAs nanowires via HTGR approach. Although these research works were currently carried out on experimental scale, it is worth to note that the industrial importance of this HTGR approach for design and fabri- cation of well-defined crystals in the future owing to its advantages of continuous and scalable production with controlled dimensions and low cost.     

2—溴羧酸气相热消除反应及其取代基效应的理论研究

用半经验分子轨道方法ＡＭ１对２－溴－丙酸与２－溴－３－甲基－丁酸的气相热消除反应的微观机理进行了细致的讨论，同时研究了不同取代基对α－溴代酸气相热消除反应的影响。研究结果表明：α－溴代酸气相热消除反应的机理均为２步反应，具有五元环过渡态的第一步过程是整个反应的速控步骤，这与实验工作者的预测一致，计算的取代基效应与有机电子论的预测相一致。     

磷杂硫烯酮及相关分子的结构和气相酸性的理论研究

使用Gaussian 98量子化学计算程序包中的HF法、密度泛理论(B3LYP)和MP2法,在6 311++G(d,p)和AUG CC PVTZ基组水平下,对磷杂硫烯酮及其相关分子进行了全优化几何构型的量子化学计算.计算结果表明:磷杂硫烯酮为累积双烯结构,其异构体有C≡P三键,二者的去质子负离子为累积双烯结构,中性分子和相关负离子都具有弯曲几何构型.计算的气相酸性表明;磷杂硫烯酮比异构体(Ⅱ)较难去质子化.     

滴流床小颗粒催化剂气相传质系数的研究

采用NaOH-SO_2-空气系统,在液相中进行瞬时不可逆反应,研究了滴流床小颗粒的气相容积传质系数k_Gα。实验结果表明:气液间的传质过程与液体的流型有着密切关系。实验得到工况条件下滴流区和脉动区k_Gα与气速、液速、颗粒大小及液相物性的关联式。     

方管内气固两相湍流气相速度的非线性特征识别

为了深入了解气固两相湍流中气相脉动的非线性特征,用相平面不变量法对竖直方管内气固两相流场的气相瞬时速度的实验数据和运用随机分布方法得到的模拟数据进行对比研究。结果表明:流动行为相似的流场有着相似的相平面不变量曲线,流动行为差异较大的流场相平面不变量曲线呈现不同的趋势;在模拟数据和实验数据的统计分布基本相同时,采用不考虑变量相关性随机分布的模拟数据和实验数据的相平面不变量曲线存在非常大的差异,而在考虑变量相关性随机分布时符合较好,但在曲线两端存在一定的差异。     

TiO2多孔性薄膜的制备及其环境净化性能研究

采用溶胶-凝胶工艺，以聚乙二醇（PEG）为造孔剂，不锈钢丝网为金属基底，制备了TiO₂多孔性薄膜。通过IR，SEM，BET，Raman光谱等测试方法对TiO₂多孔性薄膜进行了表征。实验结果表明,通过控制制备条件得到的TiO₂薄膜具有锐钛矿晶型和多孔性结构。TiO₂多孔性薄膜的光催化性能与煅烧温度和镀膜次数密切相关。450℃热处理、镀膜4次的TiO₂多孔性薄膜具有较高的活性和稳定性，其对气相甲醛的降解率比普通TiO₂薄膜高28.8%，在TiO₂多孔性薄膜连续使用4次后，甲醛的降解率仍维持在80%以上。     

弱紫外光下NOx气相光催化氧化研究

弱紫外光下(室内自然光及太阳光),利用TiO2薄膜对NOx气相光催化氧化降解进行研究.太阳光下,当相对湿度小于80%、流量为0.5L*min-1时,NOx光催化氧化降解率很高,最高达到97%.对弱紫外下NOx光催化氧化降解量子产率进行了较详细的研究与讨论,同时考察了气流湿度对NOx光催化氧化活性的影响.红外分析表明反应产物为硝酸,催化剂失活是由于反应产物硝酸吸附在催化剂表面而造成.研究结果表明,TiO2光催化氧化技术对大气中NOx净化具有良好的应用前景.     

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.