改性VOx/Al2O3催化剂催化氧化甲醇的固体核磁共振研究

采用固体核磁共振研究了NaOH 和HNO₃改性的VO_x/Al₂O₃上甲醇选择性催化氧化反应. 实验结果表明: 在甲醇的氧化反应中, 酸位对二甲氧基甲烷的生成起了重要作用. 与VO_x/Al₂O₃催化剂相比, 酸改性的VO_x/Al₂O₃上的强的Bronsted酸位对二甲氧基甲烷的选择性较高, 没有Bronsted酸位的碱改性的VO_x/Al₂O₃上生成的不是二甲氧基甲烷而是甲酸盐.     

三硼酸钾的合成、表征及其振动光谱的研究

借助自行设计的沸腾反应器,采用碳酸钾和硼酸通过控制适宜的原料配比、反应温度和脱水温度合成出三硼酸钾。通过化学分析确定合成物分子式为一水三硼酸钾(KB₃O₅·H₂O),通过粉末X射线衍射光谱(XRD)、傅里叶变换红外光谱(FTIR)、拉曼光谱(Raman)和热重分析(TG)等手段对其进行了表征,由粉末X射线衍射光谱分析确定合成物物质形态为无定形态,由傅里叶变换红外光谱和拉曼光谱分析确定合成物分子中存在三配位硼氧键B₍₃₎—O、四配位硼氧键B₍₄₎—O、羟基及三硼酸根离子,由热重分析确定合成物分子中存在能够失去一分子水的基团,并推出合成物三硼酸钾的结构式为K[B₃O₄(OH)₂]。研究了合成物的振动光谱,包括红外光谱和拉曼光谱,考察了其中硼原子的主要存在形式三配位硼氧键B₍₃₎—O和四配位硼氧键B₍₄₎—O以及其他基团的振动情况,对振动频率进行了归属。     

PTCDA/ITO表面和界面的X射线光电子能谱分析

利用X射线光电子能谱对PTCDA/p-Si有机/无机光电探测器中PTCDA/ITO表面和界面进行了测试分析。结果表明,苝环上的C原子的结合能为284.6 eV,酸酐中的C原子的结合能为288.7 eV,并存在来源于ITO膜中的氧对C原子的氧化现象,界面处C(1s)谱中较高结合能峰消失,且峰值向低结合能发生化学位移;CO键中O原子的结合能为531.5 eV,C—O—C键中的O原子的结合能为533.4 eV。     

硬质合金表面Ti系涂层退除后的界面性能研究

采用电弧离子镀技术(AIP)在YW2合金基体表面制备了TiAlN涂层,通过化学方法退除基体上的涂层,分析了硬质合金表面退除涂层后和镀覆涂层前成分和元素存在形态的变化。发现当样品在30%H₂O₂、草酸钾COOK(1.5mol·L-1)、缓蚀剂葡萄糖酸钠GA和NaOH,V_NaOH溶液∶V_30%H2O2∶V_COOK溶液=1∶1∶1,45 ℃时,45 min可以退除涂层,肉眼未观察到基体表面受腐蚀。涂层退除后样品表面光亮,呈现合金未镀覆涂层前颜色。通过对退镀后YW2基体和基体镀覆涂层前的表面XPS定性及定量分析发现,退除涂层后,基体表面W元素结合能和N元素主峰结合能与XPS结合能与参照表上对应结合能变化很小,元素的价态没有发生变化;镀覆TiAlN涂层时扩散到合金浅表层的Al,Ti,N元素,造成表面Al,Ti,N元素含量较镀覆涂层前增加,结合能位置偏移,形成AlN和TiN,有利于重新镀覆的涂层与合金基体的结合。     

Bi2Sr2CaCu2-xLixOy体系的光电子能谱研究

采用X射线光电子能谱对Bi₂Sr₂CaCu_2-xLi_xO_y体系在真空中获得的清洁表面进行了研究。结果表明:Li的掺入对Bi和Sr的化学键性质几乎没有影响,而Ca,Cu,O的化学键性质有较大的变化,其结合能随着Li含量x的增加向高能方向移动。同时对真空中获得的清洁表面和普通表面样品O1s进行了比较,结果发现真空中获得的清洁样品O1s有一个峰(528.4eV),而普通表面样品O1s有两个峰(528.4eV)和(531eV),这表明O1s的高能峰是由污染产生的。 关键词：     

ICP-AES法测定石膏中的多元素含量

分别采用酸溶和碱熔两种样品前处理方法处理样品,ICP-AES测定石膏中多元素。酸溶法适用于样品中CaO,SO₃,Al₂O₃,Fe₂O₃,MgO,K₂O,Na₂O,TiO₂,P₂O₅,MnO,SrO,BaO的同时测定。碱熔法适用于样品中CaO,SO₃,SiO₂,Al₂O₃,Fe₂O₃,MgO,TiO₂,P₂O₅,MnO,SrO,BaO,B₂O₃的同时测定。根据各个元素的性质、含量高低和基体因素配制了不同的系列标准溶液,确定了各个元素的最佳分析谱线和相应分析谱线下方法的检出限和定量限。结果表明,除酸溶法测定TiO₂的回收率略低外(81%～87%),两种前处理方法测定石膏样品中各元素的整体回收率为93%～110%,RSD(n=6)为0.70%～3.42%。但CaO和SO₃测定的准确度还比不上化学分析方法。采用本方法测定石膏中的CaO和SO₃仅适用于对测定结果准确度要求相对较低的情况。本方法操作简单,分析速度快,测定结果可靠,可以同时测定石膏中的多元素,综合酸溶和碱熔两种处理方法,可以实现石膏样品的全元素分析。     

The fluorescence and thermoluminescence characteristics of α-Al2O3:C ceramics

This paper reports that polycrystalline α-Al₂O₃:C ceramics are fabricated by conventional ceramics process. The excitation, emission spectra, thermoluminescence (TL) and optical stimulated luminescence (OSL) of α-Al₂O₃:C polycrystalline ceramics are investigated. There exists 410nm maximum emission peak which is caused by recombination of an electron with F⁺ centre to produce an excited F centre. The samples show three clear TL glow peaks at 405, 493 and 610K. The attenuation constant of exponentially decaying fast component (τ₁) and slow component(τ₂) of OSL curve are 8.43s and 41.73s, respectively. Those fluorescence and thermoluminescence characteristics are similar with α-Al₂O₃:C crystal.     

X射线荧光光谱法同时测定煤灰中的12种成分

采用熔融制样法,用X射线荧光光谱法同时测定煤灰中的常量、少量和微量成分SiO₂,Al₂O₃,Fe₂O₃,CaO,SO₃,TiO₂,K₂O,Na₂O,P₂O₅,Mg_O,MnO,BaO。选用混合熔剂并加入氧化剂的方式降低熔融温度,解决了硫的准确测量问题。同时通过选用土壤等标准样品解决了煤灰成分标准样品不足的问题。应用可变理论α系数及固定α系数法进行基体效应校正,所得结果与化学法的分析结果相符合。     

FTIR和XPS光谱分析Co—V—O催化剂的丙烷氧化脱氢活性氧物种

制备了正钒酸钴Co₃V₂O₈,焦钒酸钴Co₂V₂O₇和偏钒酸钴CoV₂O₆三种催化剂,进行了XRD,TEM,BET,FTIR,XPS,H₂-TPR和电导等表征, 并测试了他们的丙烷氧化脱氢(ODH)制丙烯催化性能。对各催化剂的FTIR主要吸收峰做了经验归属, 并对其O(1s) XPS谱进行了分峰拟合,计算了催化剂表面不同氧物种的含量。制得的催化剂晶粒均匀,平均粒径为20～30 nm,Co₃V₂O₈和Co₂V₂O₇具有p-型半导体性质,CoV₂O₆表现n-型半导体性质。p-型半导体Co₃V₂O₈和Co₂V₂O₇的丙烷ODH催化性能优于n-型半导体CoV₂O₆,当丙烷的转化率在10%时,在Co₃V₂O₈,Co₂V₂O₇,CoV₂O₆催化剂上丙烯选择性分别为48.12%,47.82%,35.24%。FTIR,XPS,H₂-TPR和电导的研究结果表明,正、 焦钒酸钴催化剂内各种价态钒之间易于进行氧化还原反应和形成氧缺位,钴含量的增加有利于丙烷转化的未充分还原的氧物种O-₂,O2-₂,O-等增加,可以判断未充分还原的氧物种Oδ-(0＜δ＜2)是丙烷ODH活性氧物种。     

Micromorphology of epicuticular wax structures of the garden strawberry leaves by electron microscopy: Syntopism and polymorphism

Ultrastructural aspects of leaf epicuticular wax structures were investigated in the garden strawberry Fragaria × ananassa by scanning and transmission electron microscopy. Both the adaxial and abaxial surfaces of two cultivars (Maehyang and Red Pearl) were collected and subjected to surface observations and ultrathin sections. The most prominent leaf epicuticular wax structures included membraneous platelets and angular rodlets. Most wax platelets were membraneous, and appeared to protrude from the surface at an acute angle. Angular rodlets were usually bent and had rather distinct facets in the abaxial surface of the two cultivars. Membraneous platelets were predominant on the adaxial surface of Maehyang, whereas the adaxial surface of Red Pearl was characterized by angular rodlets. However, both cultivars possessed angular rodlets on the abaxial surface, simultaneously. The combination of air-drying without vacuum and in-lens imaging of secondary electron signals with a field emission gun could impart the superb resolution at low electron dose with minimal specimen shrinkage. In vertical profiles of the leaf epidermis, epicuticular waxes were observed above the cuticle layer, and measured approximately as 50 nm in thickness. The natural epicuticular waxes were seemingly mixtures of electron-dense microfibrils, and heterogeneous in shape on ultrathin sections. Distinct crystal-like strata could be hardly discernable in the wax structures. These results suggest that the garden strawberry has the nature of syntopism within one plant and polymorphism within the same species in the formation and occurrence of leaf epicuticular waxes.     

Spectral indices to assess the carotenoid/chlorophyll ratio from adaxial and abaxial leaf reflectance

The ratio between the carotenoid and chlorophyll concentrations can indicate the physiology and phenology of plants. Most of the vegetation indices related to the ratio between the carotenoid and chlorophyll contents only consider the reflectance from the adaxial leaf surface. In this study, it was found that the leaf reflectance from the abaxial surface is lower than that of the adaxial surface in the visible wavelength region. On the contrary, the reflectance is higher on the adaxial surface in the near-infrared wavelength region. The difference ratio index resulted in the best correlation with the carotenoid/chlorophyll ratio and was the most robust among all the spectral indices studied when the spectral information on the adaxial and abaxial surfaces was pooled. The result indicated that this index can accurately estimate the carotenoid/chlorophyll ratio because of the insensitivity to the differences between adaxial and abaxial leaf surfaces.     

高光谱成像技术的柚类品种鉴别研究

柚类种质和品种资源繁多,现有的柚类品种鉴别方法检测时间长,费用高。旨在利用高光谱成像技术探索主要柚类品种快速识别的可行性。试验选用4个具有代表性的柚类品种,利用高光谱成像技术,采集240个叶片样本(60个/品种)上表面和下表面的高光谱图像。高光谱图像标定后,提取样本感兴趣区域平均光谱信息作为样本的光谱进行分析。利用Kennard-Stone法将样本划分为校正集(192个)和验证集(48个)。采用多元散射校正(MSC)和标准正态变量变换(SNV)对原始光谱曲线进行预处理后,分别采用主成分分析 (PCA)和连续投影算法 (SPA )提取最佳主成分和有效波长,并将其作为最小二乘支持向量机(LS-SVM)的输入变量,建立基于叶片上表面和下表面光谱信息的PCA-LS-SVM和SPA-LS-SVM 模型。结果显示,基于叶片上表面光谱信息建立的PCA-LS-SVM和SPA-LS-SVM 模型对建模集样本的识别正确率分别为99.46%和98.44%,对预测集样本的识别正确率均为95.83%。基于叶片下表面光谱信息建立的PCA-LS-SVM和SPA-LS-SVM模型对建模集样本和预测集样本的识别正确率皆为100%。表明,利用高光谱成像技术结合PCA-LS-SVM和SPA-LS-SVM可实现柚类品种的快速鉴别,叶片下表面光谱信息鉴别效果优于叶片上表面。该研究为柚类的品种快速鉴别提供了一种新方法。     

利用叶片正反面反射光谱估算叶绿素含量

叶片叶绿素含量的快速无损估算方法对研究植被生长和环境胁迫都具有重要意义。传统叶绿素光谱估测方法,主要是基于叶片正面光谱信息。而在实际遥感观测中,传感器不仅会接收植被叶片正面光谱信息,植被叶片反面光谱信息也会同时被接收。该研究主要目的是找到在同时考虑叶片正反面光谱信息时也能精确估算叶片叶绿素含量的分析方法。对比了简单差值植被指数(SD),简单比值植被指数(SR),归一化植被指数(ND)与偏最小二乘(PLS)建模方法,并对检验样本集进行了精度比较。结果发现用PLS方法估算两种植被正反面叶片的叶绿素含量与真实叶片叶绿素含量的拟合精度更高,R2为0.91,RMSE为5.21 μg·cm-2。因此可以认为PLS方法在同时考虑植被叶片的正反面光谱信息时对植被叶片叶绿素含量的估算更准确。     

6H-SiC（0001）-6[KF（]3[KF）]×6[KF（]3[KF）]R30°重构表面的同步辐射角分辨光电子能谱研究

利用同步辐射角分辨光电子能谱（SRARPES）对6H-SiC（0001）-6[KF（]3[KF）]×6[KF（]3[KF）] R30°重构表面的电子结构和表面态进行了研究.通过鉴别价带谱中来自于体态的信息,可以推断出重构表面的费米能级位于体态价带顶之上（2.1±0.1）eV处.实验测出的体能带结构与理论计算的结果较为符合.在重构表面上发现三个表面态,分别位于结合能-0.48 eV（S₀）,-1.62 eV（S₁）和-4. 关键词： 角分辨光电子能谱 碳化硅（SiC） 电子结构 表面态     

紫外辐射加速老化高温硫化硅橡胶的X射线光电子能谱研究

高温硫化硅橡胶具有优良的电气性能、机械性能、憎水性而广泛应用于特高压输电线路,但亦会受外界环境的影响而老化,其抗紫外老化性能受到关注。课题组模拟户外紫外辐射环境,设计搭建了可调式紫外辐射加速老化试验箱,对A、B两个厂家的高温硫化硅橡胶样品进行了紫外辐射(0,500和1 000 h)加速老化实验,重点对辐射前后的试样进行X射线光电子能谱全谱扫描和窄区谱分析、确定元素化学位移及相对含量,分析紫外辐射对高温硫化硅橡胶表面化学态的影响,进而判断紫外辐射加速高温硫化硅橡胶老化机制。结果表明：高温硫化硅橡胶主要元素为O_1S,C_1S,Si_2p,其中O_1S主要以O-Si-O（532.4 eV）的形式存在,紫外辐射后,拟合分峰观察到534 eV的-OH的小峰,积分面积随辐照时间延长而增加;C_1S为C-H,C-C（284.8 eV）或C-O（286.3 eV）,随着辐射时间的延长,C-H和C-C结合能峰积分面积减小,C-O结合能峰的积分面积略微增加;Si_2p为Si-C（102.39 eV）,紫外辐射后新增SiO_x（x=3～4）结合能峰（103.6 eV）且积分面积随辐射时间延长而增加。分析认为紫外辐射加速老化的机理是紫外线切断硅橡胶中键能较低的部分Si-C,C-C和C-H键,裂解后的自由基可相互结合发生交联反应形成SiO_x（x=3～4）;辐射产生高活性的臭氧氧化自由基生成-COOH。XPS技术能够探究高温硫化硅橡胶的表面化学态从而促进其老化机理的研究。     

有机分子PTCDA在P型Si单晶(100)晶面的生长机理

对PTCDA的分子结构及其化学键的形成进行了分析,并讨论了晶面指数（100）Si单晶的晶格结构。在此基础上,评述了PTCDA分子在P-Si单晶（100）晶面上生长的机理,并制备了样品PTCDA/P-Si（100）。利用XRD对样品测试得出,在P-Si（100）晶面上沉积的PTCDA薄膜中仅存在α物相。利用XPS对样品测试得出,在其界面层中PTCDA酸酐中的4个羟基O原子与C原子结合,其结合能为532.4 eV;苝核基团外围的8个C、H原子以共价键结合,其结合能为289.0 eV;在界面处,悬挂键上的Si原子与PTCDA酸酐中的C、O原子结合,形成C-Si-O键及C-Si键,构成了界面层的稳定结构。     

Si 2p and O 1s photoemission from oxidized Si(0 0 1) surfaces depending on translational kinetic energy of incident O2 molecules

The influence of translational kinetic energy of incident O₂ molecules for the passive oxidation of the partially oxidized Si(0 0 1) surface has been studied by photoemission spectroscopy. The incident energy of O₂ molecules was controlled up to 3 eV by a supersonic molecular beam technique. Two incident energy thresholds (1.0 and 2.6 eV) were found out in accordance with the first-principle calculations. Si 2p and O 1s photoemission spectra measured at representative incident energies showed the incident energy induced oxidation at the backbonds of the dimer and the second layer (subsurface) Si atoms. Moreover, the difference of oxygen chemical bonds was found out to be as the low and the high binding energy components in the O 1s photoemission spectra. They were assigned to bridge sites oxygen and dangling bond sites oxygen, respectively.     

Maleated wood-fiber/high-density-polyethylene composites: Coupling mechanisms and interfacial characterization

Chemical coupling of maleated polyethylene (MAPE) copolymers at the interface in wood-fiber/high-density-polyethylene (HDPE) composites was investigated in this study. FTIR and ESCA analyses presented the evidence of a chemical bridge between the wood fiber and polymeric matrix through esterification. The feature peak of esterification occurred in the range between 1800 and 1650 cm^?1 at FTIR spectra. Succinic and half succinic esters were the two primary covalent bonding products to cross-link the wood fiber and thermoplastic matrix. Maleated composites had a remarkable shift on most O1s and C1s spectra in respect to the wood, HDPE, and untreated composites. The binding energy of maleated composites at C1s and O1s spectra was around 282 eV and 530 eV, respectively. The mass concentration of chemical components at the interface was related to the coupling agent type, structure, and concentration. According to the FTIR and ESCA analyses, the coupling mechanisms of MAPEs were proposed. The interfacial morphology in wood-fiber/HDPE composites was illustrated with the pinwheel models based on SEM observations.