Na_2O-TiO_2-SiO_2氧化物玻璃微结构研究

利用IR以及XPS等测试手段研究了Na2 O -TiO2 -SiO2 体系玻璃样品 .结果表明 :该体系玻璃中Ti4+ 离子存在 [TiO4] ,[TiO6 ]等几种不同的微结构单元 ,并且随着玻璃中TiO2 含量的增加 ,该体系玻璃中四方双锥结构的 [TiO6 ]的含率呈现急剧增加后缓慢增加再急剧增加的反常现象 ;当TiO2 的摩尔分数超过 2 0 %后 ,[TiO6 ]又呈现急剧增大的反常现象 ;相反 ,随着玻璃中TiO2 的含量的增大 ,具有正四面体结构[TiO4]的含率则逐步减少 ,并且 ,TiO2 的含量越高 ,减少的趋势越慢     

Rapid and direct lodine value and saponification number determination of fats and oils by attenuated total reflectance/fourier transform infrared spectroscopy

A simple, rapid and reproducible method of determining the iodine value (IV) and saponification number (SN) for fats and oils was developed with an attenuated total reflectance/Fourier transform infrared spectrometer and commercially available triglycerides as calibration standards. Partial least squares was used to determine the spectral regions correlating with the known chemical IV and SN values, and the calibration set was augmented with additional standards generated by spectral co-adding techniques. The calibration model obtained was used to analyze commercially available fats and oils with a wide range of IV and SN values, and the results were compared to the values obtained by American Oil Chemists’ Society methods. With the spectrometer calibrated and programmed, IV and SN results could be obtained within 2–3 min per sample, a major improvement over conventional wet chemical methods.     

Origin of rate bistability in Mn–O/Al2O3 catalysts for carbon monoxide oxidation: role of the Jahn–Teller effect

Peculiarities in catalytic activity in carbon monoxide oxidation as well as some structure, electronic and magnetic properties of the three oxide catalysts, Mn³⁺–O/Al₂O₃ (1), Mn³⁺–O–Fe/Al₂O₃ (Mn-substituted spinel, 2) and -Fe₂O₃/Al₂O₃ (3), were studied by kinetic measurements and by Mössbauer spectroscopy. The catalysts 1 and 2 showed a kinetic bistability with a sharp transition towards more reactive state at 200°C (ignition point). In contrast, for catalyst 3, at 200–250°C, the behavior of reaction rate against temperature did not display noticeable hysteresis. On cooling the catalysts 1 and 2, extinction was observed at about 170 and 120°C, respectively, i.e., at 30–80°C lower than the corresponding ignition points. Proximity of activation energy for the high and low activity (15–19 kJ/mol) for both Mn-containing catalysts suggests an increase in the number of active sites at high temperature with no changes in the reaction mechanism. The considerable difference between Mn-containing catalysts 1, 2 and Fe-containing catalyst 3 may be caused by Jahn–Teller (JT) type distortions of the oxygen polyhedron around Mn³⁺. A significant spontaneous axial bond stretching within the local polyhedron seems to diminish Mn–O binding energy, facilitate the participation of surface oxygen species, O_S, in the oxidation of CO by a redox mechanism and promote oxygen vacancies at the surface that would cause considerable effect on the activity. An increase in the width of the counterclockwise hysteresis loop for the catalyst 2 compared to the catalyst 1 indicates that clusters of mixed spinel provide more active sites and more labile O_S species than clusters of the binary Mn oxide.     

The role of oxygen vacancies in the CO2 methanation employing Ni/ZrO2 doped with Ca

The Ni/ZrO₂ catalyst doped with Ca and Ni/ZrO₂ were employed in the CO₂ methanation, a reaction which will possibly be used for storing intermittent energy in the future. The catalysts were characterized by X-ray photoelectron spectroscopy (XPS, reduction in situ), X-ray diffraction (XRD, reduction in situ and Rietveld refinement), electron paramagnetic resonance (EPR), temperature-programmed surface reaction, cyclohexane dehydrogenation model reaction, temperature-programmed desorption of CO₂ and chemical analysis. The catalytic behavior of these catalysts in the CO₂ methanation was analyzed employing a conventional catalytic test. Adding Ca to Ni/ZrO₂, the metallic surface area did not change whereas the CO₂ consumption rate almost tripled. The XRD, XPS and EPR analyses showed that Ca⁺² but also some Ni²⁺ are on the ZrO₂ surface lattice of the Ni/CaZrO₂ catalyst. These cations form pairs which are composed of oxygen vacancies and coordinatively unsaturated sites (cus). By increasing the number of these pairs, the CO₂ methanation rate increases. Moreover, the number of active sites of the CO₂ methanation rate limiting step (CO and/or formate species decomposition, rls) is enhanced as well, showing that the rls occurs on the vacancies-cus sites pairs.     

高温下煤焦表面含氧官能团对NO_煤焦还原反应的影响

在固定床反应器上考察了高温下不同氧浓度气氛下NO-煤焦还原反应的还原效果,并采用XPS分析了不同氧浓度预处理后的煤焦表面的含氧官能团.研究结果表明,高温下氧气对于NO-煤焦还原反应依然有显著的促进作用,也同样存在临界氧浓度(0.25％)的现象,比低温下临界氧浓度(1％)有所提前.由XPS分析结果发现,高温下氧气对煤焦表面的影响是产生促进NO还原的表面含氧官能团(C(O)),适量的氧气浓度能形成饱和的C(O)活性位,使得还原效果达到最佳.随着温度的升高,C(O)的总量略有减少.有可能是温度过高致使煤焦表面的C(O)极易达到饱和,多余的氧气以O的形式排出.     

FTIR 发射/透射光谱对含颗粒气流的温度测量

在改进的FTIR和自制的微量给粉加热／燃烧实验装置上，对粘土颗粒气流和煤粉火焰进行了FTIR发射／透射测量。通过发射／透射光谱可以得到颗粒温度和气体温度，其相对误差小于5%，满足实验室和工业测温要求。当被测样品中存在碳黑和其它颗粒时，基于碳黑的吸收特性，给出了消除碳黑辐射影响的一种近似处理方法，即将吸收光谱外推至0cm^-1，以0cm^-1处的数值为准对整个光谱进行校正，所得光谱就认为是去除碳黑影响后的吸收光谱．对于CO2气体温度，研究表明，可以用通过CO2峰值的黑体理论曲线来简单估计．研究还发现炭粒温度可以高出气体温度200—300K，一个可能的原因是CO在颗粒边界层点燃引起了颗粒温度突然升高并高于气体温度，对这种现象的理论解释和更多的实验验证尚需进一步展开。     

基于可调谐激光吸收光谱技术(TLAS)的内燃机排放组分浓度测试技术研究

开展基于可调谐激光吸收光谱(tunable laser absorption spectroscopy,TLAS)的内燃机排放中气体组分浓度检测技术研究。选取NO气体作为试验室静态测试的目标气体,利用可调谐带间级联激光器(interband cascade lasers,ICL)作为探测光源,采用直接探测法及谐波探测法对4种不同浓度的标准NO气体进行测试,结果与标准气真实浓度吻合度较高。直接探测法中,探测相对误差均方根为2.6%,体积浓度的最大绝对误差为18.6×10~(-6),理论探测极限可达2×10~(-6);谐波探测相对误差均方根为1.4%,最大绝对误差为13×10~(-6),理论探测极限可达10~(-7)。数据处理过程中引入温度修正算法,可实现温度波动下的准确测量。同时,对不同流速下的标准气体进行了在线测量,结果表明气体的流动性对测试结果并无影响。本研究表明:TLAS方法动态响应特性好,环境适应性强,可根据瞬态环境参数进行实时修正,可以在复杂的测试环境下实现高精度、高灵敏度瞬态测量。     

γ-Al2O3表面结构的红外光谱研究

采用原位红外光谱技术对不同温度(100～500℃)脱水γ-Al2O3的表面羟基进行了研究,同时应用吡啶吸附原位红外光谱法对γ-Al2O3表面上路易斯酸(L酸)进行了研究.实验结果表明,在升高脱水温度的过程中,在γ-Al2O3表面共出现五个羟基谱带,分别为3785,3762,3725,3697,3674 cm-1.在γ-Al2O3表面上存在三种L酸性位,分别对应于五配位(酸性最弱)、四配位(酸性中等)和三配位的Al3+(酸性最强).这三种Al3+的数量随脱水温度升高而增大,而且γ-Al2O3表面上的L酸性位均有羟基与其相连.     

Efficient electrochemical decomposition of perfluorocarboxylic acids by the use of a boron-doped diamond electrode

The electrochemical decomposition of environmentally persistent perfluorooctanoic acid (PFOA) was achieved by the use of a boron-doped diamond (BDD) electrode. The PFOA decomposition follows pseudo-first-order kinetics, with an observed rate constant (k₁) of 2.4 × 10^− 2 dm³ h^− 1. Under the present reaction conditions, k₁ increased with increasing current density and saturated at values over 0.60 mA cm^− 2. Therefore, the rate-limiting step for the electrochemical decomposition of PFOA was the direct electrochemical oxidation at lower current densities. In the proposed decomposition pathway, direct electrochemical oxidation cleaves the C-C bond between the C₇F₁₅ and COOH in PFOA and generates a C₇F₁₅ radical and CO₂. The C₇F₁₅ radical forms the thermally unstable alcohol C₇F₁₅OH, which undergoes F⁻ elimination to form C₆F₁₃COF. This acid fluoride undergoes hydrolysis to yield another F⁻ and the perfluorocarboxylic acid with one less CF₂ unit, C₆F₁₃COOH. By repeating these processes, finally, PFOA was able to be totally mineralized to CO₂ and F⁻. Moreover, whereas the BDD surface was easily fluorinated by the electrochemical reaction with the PFOA solution, medium pressure ultraviolet (MPUV) lamp irradiation in water was able to easily remove fluorine from the fluorinated BDD surface.