氯铝酸离子液体的酸性及其催化烷基化反应研究

分别采用吡啶探针和乙腈探针红外光谱法研究了氯铝酸离子液体的酸性,结合固体酸表征方法,研究了离子液体的酸性对吡啶探针各振动模式的影响。发现当氯铝酸离子液体AlCl₃的摩尔分数x为0.4～0.5时,离子液体显弱Lewis酸性,强碱性吡啶探针分子能很好地表征离子液体的酸性,而弱碱性乙腈探针分子只适用于表征酸性较强的离子液体。考察了氯铝酸离子液体酸强度对苯与长链烯烃烷基化反应的影响,结果发现,AlCl₃的摩尔分数x≤ 0.5时,离子液体没有催化活性;x>0.55时,随着离子液体酸性的增强,烯烃转化率升高,但2位烷基苯选择性下降。结合离子液体的酸强度对烷基化反应机理进行初步分析认为具有催化活性的物质是强Lewis酸Al₂Cl-₇。     

基于反应论模型的指数型环境因子点估计

已知指数型产品在环境S下的定数截尾数据(Ti,ri)，i=1，…，k(其中Ti为环境Si下的累积试验时间，ri为环境Si下的关联故障总数)，考虑产品在环境S2下相对于环境S1，的环境因子点估计问题。     

High-mobility two-dimensional electron gases at oxide interfaces： Origin and opportunities

Our recent experimental work on metallic and insulating interfaces controlled by interfacial redox reactions in SrTiO3-based heterostructures is reviewed along with a more general background of two-dimensional electron gas(2DEG)at oxide interfaces.Due to the presence of oxygen vacancies at the SrTiO3surface,metallic conduction can be created at room temperature in perovskite-type interfaces when the overlayer oxide ABO3has Al,Ti,Zr,or Hf elements at the B sites.Furthermore,relying on interface-stabilized oxygen vacancies,we have created a new type of 2DEG at the heterointerface between SrTiO3and a spinelγ-Al2O3epitaxial film with compatible oxygen ion sublattices.This 2DEG exhibits an electron mobility exceeding 100000 cm2·V 1·s 1,more than one order of magnitude higher than those of hitherto investigated perovskite-type interfaces.Our findings pave the way for the design of high-mobility all-oxide electronic devices and open a route toward the studies of mesoscopic physics with complex oxides.     

Photoluminescence and thermoluminescence properties of SnO2 nanoparticles embedded in Li20-K20-B203 with Cu-doping

Cu-doped borate glass co-doped with SnO2 nanoparticles is fabricated by melt quenching. The structure and morphology of the samples are examined by X-ray diffraction and field emission scanning electron microscopy. Up-conversion enhancement is observed in the photoluminescence （PL） and thermolumines- cence （TL） intensities of the glass. PL emission spectra are identified in the blue and green regions, and a fourfold increase in emission intensity may be observed in the presence of embedded SnO2 nanoparticles. The glow curve is recorded at 215℃, and fourfold increases in TL intensity are obtained by addition of 0.1 mol% SnO2 nanoparticles to the glass. Higher TL responses of the samples are observed in the energy range of 15-100 KeV. At energy levels greater than -0.1 MeV, however, flat responses are obtained. The activation energy and frequency factor of the second-order kinetic reaction are calculated by the peak shape method.     

Towards understanding the carbon trapping mechanism in copper by investigating the carbon-vacancy interaction

We propose a vacancy trapping mechanism for carbon-vacancy (C-V) complex formation in copper (Cu) according to the first-principles calculations of the energetics and kinetics of C-V interaction. Vacancy reduces charge density in its vicinity to induce C nucleation. A monovacancy is capable of trapping as many as four C atoms to form CnV (n=1,2,3,4) complexes. A single C atom prefers to interact with neighboring Cu at a vacancy with a trapping energy of 0.21 eV. With multiple C atoms added, they are preferred to bind with each other to form covalent-like bonds despite of the metallic Cu environment. For the CnV complexes, C2V is the major one due to its lowest average trapping energy (1.31 eV). Kinetically, the formation of the CnV complexes can be ascribed to the vacancy mechanism due to the lower activation energy barrier and the larger diffusion coefficient of vacancy than those of the interstitial C.     

基于激光光解诱导荧光技术实现燃烧反应区及中间产物CH_3瞬态可视化

实现火焰反应区和不同中间组分的在线二维瞬态成像,在湍流燃烧的基础研究中具有十分重要的意义。用Nd∶YAG激光器的5倍频输出(212.8nm)作为光源,通过激光光解诱导荧光技术在甲烷/空气预混火焰中,成功实现了火焰反应区的瞬态成像,并首次采用该技术实现了CH_3的在线瞬态成像测量。分析了该方法同其他荧光标示物在反应区二维瞬态成像方法的优势,并研究了火焰燃烧过程中其他燃烧中间产物和不同燃空比对CH_3单脉冲成像的影响,讨论了现有条件下该技术的应用范围。根据实验结果,在燃空比Φ=1.2的条件下,在反应区我们获得了信噪比约为8的单脉冲成像,分析火焰中CH_3的单脉冲成像结果可知火焰燃空比在1.0~1.4之间时,或者火焰中CH_3的浓度大于9.3×1015 molecules·cm-3信噪比较好。该项技术在动力机械及其他研究领域的应用有十分重要的参考价值。     

SERS传感器间接检测蛋白质的研究进展

蛋白质在生命体中发挥着重要的作用,蛋白质的检测对于了解生命体系及在生物医学领域都有基础性的应用价值。表面增强拉曼光谱(SERS)技术对研究化学和生物传感应用前景很有优势,是由于其高灵敏度以及很好的选择性,并且已被运用于生物分子检测,特别是在蛋白质检测方面。综述了SERS探针技术用于蛋白质检验的研究现状,如免疫胶体金技术、基于纳米材料探针的SERS研究、基于酶促技术和基于试剂技术的蛋白质研究进展。     

金属原子修饰石墨烯体系催化性能的理论研究

采用基于密度泛函理论的第一性原理方法研究了单个CO 和O2气体分子在金属原子修饰石墨烯表面的吸附和反应过程. 结果表明: 空位缺陷结构的石墨烯能够提高金属原子的稳定性, 金属原子掺杂的石墨烯体系能够调控气体分子的吸附特性. 通入混合的CO和O2作为反应气体, 石墨烯表面容易被吸附性更强的O2分子占据, 进而防止催化剂的CO 中毒. 此外, 对比分析两种催化机理(Langmuir-Hinshelwood和Eley-Rideal)对CO氧化反应的影响. 与其它金属原子相比, Al原子掺杂的石墨烯体系具有极低的反应势垒(< 0.4 eV), 更有助于CO氧化反应的迅速进行.