用X射线光电子能谱对热处理的四苯基钴卟啉修饰电极的表面表征

本文用XPS、DTA和TG分析了四苯基钴卟啉化学修饰电极的热分解行为,它不同于四苯基铁卟啉.由XPS谱图揭示了四苯基钴卟啉与玻璃碳电极之间的相互作用,进而阐述了经热处理的四苯基钴卟啉化学修饰电极的表面结构与电催化稳定性的关系.从Co2p_3/2和2p_(1/2)能级的自旋分裂间距及其Shake-up伴峰,了解经热处理后的四苯基钴卟啉修饰电极中钴自旋态变化,并且从Co的L_3VV俄歇跃迁计算出Co的双电离能,其双电离能与电催化活性有一定关系。

INVESTIGATION OF MICROSTRUCTURE AT IRON TETRAPHENYLPORPHYRIN MODIFIED CLASSY CARBON ELECTRODE BY XPS

Microstructure of the glassy carbon surface modified with iron tetraphenyfporphyrin (FeTPP) by heat treatment has been studied by XPS,, DTA and TG. XPS spectra of Fe 2P_3\2 level in FeTPP and iron tetraphenylporphyriu/glassy carbon (FeTPP/GC) have shown that a bond can be formed between the glassy carbon surface and both the central metal iron ion and the macrocyclic, ligand, which loses its four phenyl groups during the beat treatment. The relationship between the surface mierostructure of FeTPP/GC and the...

铕和铽与3,4-呋喃二甲酸双核配合物的合成、表征及其晶体结构

本文首次合成了铕(Ⅲ)和铽(Ⅲ)与3,4-呋喃二甲酸配合物,研究了它们的IR、DTA、TG、DTG和荧光光谱等性质,并完成了单晶的晶体分析。结果表明,配合物为〔Ln·HL_2(H_2O)_2〕_2·2H_2O(Ln=Eu(Ⅲ),Tb(Ⅲ);H_2L=3,4-呋喃二甲酸),属单斜晶系,P2/c空间群,Z=2,晶胞参数对铕和铽配合物分别为α=10.842(1),10.801(4);b=8.725(2),8.664(2);c=16.366(4),16.308(6)A;β=93.50(1),93.67(3)°;V=1545.3(5),1523.0(8)A~3。

用X-光电子能谱对热处理的四苯基铁卟啉化学修饰电极的研究

本文用XPS、DTA、和TG分析了解四苯基铁卟啉和四苯基铁卟啉化学修饰电极的热分解行为。由XPS谱图揭示了玻璃炭与四苯基铁卟啉之间的相互作用,进而阐述了经热处理的四苯基铁卟啉化学修饰电极的表面结构与电催化稳定性的关系。从四苯基铁卟啉化学修饰电极的XPS价态谱发现Fe中心离子的3d电子在电极的电催化活性中的作用。

中新世以来中国北方风尘堆积的粘土矿物组成及其古环境意义

In northern China, the loess-soil sequence of the last 2.6 Ma, the Hipparion Red-Earth of eolian origin and recently reported Pliocene-Miocene loess-soil sequence provide a near continuous continental eolian record of climatic history for the past 22.0 Ma. This work aims to investigate the composition and structure of clay minerals contained in deposits, and to explore their implications for environmental evolutions over the last 22.0 Ma. Clay minerals, which were extracted from eolian samples collected at Xifeng (0-6.2 MaBP) and Qinan (6.2-22.0 MaBP) sections, were analyzed qualitatively and semi-quantitatively by using X-ray diffraction (XRD), differential thermal analysis (DTA), thermogravimetric analysis (TG) and chemical analysis. The main conclusions are as follows: Over the last 22.0 Ma, the clay mineral assemblage among Quaternary loess-soils, Hipparion Red-Earth, and Miocene loess-soils shows similar components, mainly consisting of illite (55-80%), kaolinite (7-20%), chlorite (4-13%), smectite (2-23%) as results calculated by comparing major peak areas. There are no obvious differences in both types and amounts of clay minerals between loess and interbedded soils, suggesting that overwhelming part of the clay minerals is derived from the source. According to the components of clay minerals, the whole sequence of eolian deposits in the Loess Plateau can be divided into ten clay mineral assemblage zones over the last 22.0 Ma, whose corresponding ages are: 22.0-21.0 MaBP, 21.0-18.0 MaBP, 18-16.2 MaBP, 16.2-13.0 MaBP, 13.0-10.0 MaBP, 10.0-5.5 MaBP, 5.5-4.4 MaBP, 4.4-2.8 MaBP, 2.8-1.0 MaBP, 1.0-0 MaBP, respectively. This may imply that dust supply changed at least nine times over the past 22.0 Ma. The loess illite has a better crystaliinity, higher value of the FWHM and IC, than the interbedd soils. Previous studies indicated that irregular mixed layer minerals could form under relatively warm and humid conditions (Han, 1982). According to the general distribution of clay minerals of zonal soil (Chamley, 1989), the clay mineral assemblage of eolian deposits in Xifeng and Qinan sections is typical of temperature-humid and warm-subarid environment. Therefore, our results indicate climatic environment in Loess Plateau did not change remarkably since 22.0 Ma, and fluctuated between temperature-humid and warm-subarid climate. 4. The illite generally presents poorer crystaliinity during the period of 22.0 to 2.8 MaBP than in the last 2.8 Ma BP, especially at the intervals of 3.5-4.5 Ma BP, 14.0-17.0 MaBP and 20.0-22.0 Ma BP, which indicates that the weathering intensity was stronger in Neogene than in Quaternary. 5. The relatively low ice volume and high global temperature may be responsible for the strange weathering intensity during the interval of the 3.5-4.5 Ma BP, 14.0-17.0 Ma BP and 20.0-22.0 Ma BP.

高温高压条件下泥质岩变质脱水作用的实验研究

泥质岩是地球上广泛分布的一种表壳沉积岩石，与上地壳平均化学组成接近，是俯冲带沉积物的典型代表。本文以赣北双桥山群泥质板岩为主要研究对象，对泥质岩（KFMASH体系）进行了热力学计算、高压差热（HP－DTA）和榴辉岩相温压条件下变质脱水作用的实验研究。研究结果表明，俯冲沉积物在冷、热俯冲带其变质脱水作用的深度范围分别是95～155 km 和48～84 km。泥质岩经历了一个区域进变质作用过程。该过程可以被分为三个阶段：① 绿泥石变质脱水阶段；② 角闪石、白云母变质脱水阶段；③ 黑云母变质脱水阶段。在各阶段中，随含水矿物的变质脱水作用不断进行，流体被逐渐从体系中释放出来。最后以黑云母的消失为标志，指示了泥质岩体系变质脱水作用的结束。在俯冲带深部温度压力条件下，泥质岩所释放出的流体以富集Cu、Pb、Nd、Ba等流体活动性元素为主要特征。俯冲带沉积物（岩）在进入到俯冲带深部前，受海水浸染而富集Cl，这导致其在俯冲带深部变质脱水过程中，所释放出的流体中富集Cu、Pb、Rb、Sr、Cs、La、Ba、Ce、Pr、Nd、Sm、Eu等微量元素。而未受到海水浸染或浸染程度较弱俯冲带沉积物，在俯冲带变质脱水过程中所释放出的变质流体中，上述微量元素的富集程度则相对较弱。

伊/蒙不规则间层粘土的矿物学特征及其层柱化研究

该文首先详细而系统地介绍了一类新型纳米矿物材料——层柱粘土.论文以贵州大方I/S不规则有序间层粘土为例,在采用多种测试手段了解该矿物的组成、结构及性能的基础上,首次对I/S不规则间层粘土进行了较系统的铝、锆、钛的层柱化研究.XRD、HRTEM、FTIR及DTA-TG共同揭示了大方I/S间层粘土是以Rl型为主的I/S不规则有序间层粘土,化学分析数据计算表明结构中的八面体为二八面体,蒙皂石为钠型蒙脱石.通过对大方I/S不规则间层粘土的铝层柱研究发现,较低的初始铝浓度有利于形成较多的Keggin离子,产物层间距可达3.2～3.5nm,N<,2-BET比表面积达110m<'2>/g.首次对I/S不规则间层粘土进行了钻、钛层柱化研究,所获产物层间距都大于铝层柱者,分别为3.3～4.0nm和3.5~4.7nm.文章首次对层柱I/S不规则间层粘土进行了除层间距以外的孔结构、表面酸性、(水)热稳定性和显微形貌的表征.探讨了层与柱之间、颗粒与颗粒之间的排列和连接对层柱产物性能的影响,比较成功地用IR证据解释了层在机理中四面体的反转问题.最后初步试验了层柱I/S不规则间层粘土对水中重金属pb<'2+>和垃圾淋滤液中COD的去除效果,结果表明卫Ti-I/S对Pb<'2+>的吸附容量可达8.39mg/g,对COD的去除率可高达76.71%.

Low temperature synthesis of perovskite oxide using the adsorption properties of cellulose

La-0.8Sr(0).2CoO(3) (LSCO) oxide powder was prepared using the adsorption properties of cellulose. The preparation process was studied by XRD, FTIR, TG-DTA and CO2-TPD techniques. The results of XRD, IR and TG-DTA testified that cellulose could successfully reserve the homogeneity of the solution system to the solid precursor. During the early stage of pyrolysis, cellulose was partially oxidized, and some COO- groups appeared in its texture, which were then complexed with the adsorbed metal ions, and effectively suppressed the aggregation of metal ions. Formation of a pure perovskite and the properties of the powder resulted were found to be significantly influenced by the cellulose to metal nitrate ratio. Also the properties of the resulting powder were greatly influenced by the calcination conditions. If the produced carbon dioxide could not be eluted in time, carbonate would be formed in the bulk. Hence, a high calcination temperature (> 800 degreesC) was needed to acquire a pure phase LSCO. At optimized conditions, nano-crystal LSCO could be obtained at as low as 500 degreesC.

A novel method to synthesize amorphous silica-alumina materials with mesoporous distribution without using templates and pore-regulating agents

In this study, a novel sol-gel method is used to synthesize amorphous silica-alumina materials with a narrow mesoporous distribution and various Si/Al molar ratios without using any templates and pore-regulating agents. During the preparation procedure, only inexpensive inorganic salts were used as raw materials, instead of expensive and harmful alkoxides. The precursor sol was dried at room temperature in a vacuum box kept at 60 mmHg until it began to form the gel. The results of a nitrogen sorption experiment indicate that the synthesized materials with different Si/Al molar ratios have similar mesoporous distributions (within 2-12 nm). Moreover, it was found that the material's pore size distribution remains at a similar value during the heat treatment from room temperature to 550 degreesC. On the basis of the nitrogen sorption, TEM, and AFM characterization results, a formation mechanism of mesopores which accounts for the experimental data is also suggested. This suggested mechanism involves rearrangement of the primary particles during the drying process to form the precursors of the similarly sized mesopores. The synthesized materials were characterized by XRD, thermal analysis (TG/DTA), Al-27 and Si-29 MAS NMR spectroscopy, SEM, TEM, and AFM. The results of Al-27 and 29Si MAS NMR indicate that the distribution of silicon and aluminum in the synthesized materials is more uniform and homogeneous than that in the mixed oxides prepared via the traditional sol-gel method even at high alumina contents. The type and density of the acid sites were studied using pyridine adsorption-desorption FTIR spectroscopy. It was shown that the acidity of the synthesized materials is higher than that of the silica-alumina materials prepared by conventional methods.

Synthesis of nanometric-size magnesium nitride by the nitriding of pre-activated magnesium powder

Magnesium nitride (Mg3N2) was synthesized by the reaction of magnesium in the highly reactive form (Mg*) with nitrogen at 450 degrees C under normal pressure. The effect of doping with nickel dichloride on the nitridation of Mg* was investigated. Differential thermal analysis (DTA) of Mg* systems and transmission electron microscopy (TEM) measurement of the product formed were carried out. TEM measurement showed that the particle size of the Mg3N2 synthesized was in the nanometric range. The dependence of nitridation of the NiCl2-doped Mg* on temperature was investigated at temperatures ranging from 300 to 500 degrees C. The nitridation of NiCl2-doped Mg* could occur even at temperature as low as 300 degrees C. (C) 1999 Kluwer Academic Publishers.

Characterization and thermodynamic study of ultra-fine particle of Ni-B amorphous alloy

Ultra-fine particle of Ni-B amorphous alloy was prepared by chemical reduction of Ni2+ with NaBH4 and characterized with TEM and XRD. The heat capacity and thermal stability were measured with a high-precision automatic adiabatic calorimeter and DTA. The upper limit of applied temperature of the substance was found to be 684 K for use as catalyst. (C) 1999 Elsevier Science B.V. All rights reserved.

The role of Sn in Pt-Sn/CeO2 catalysts for the complete oxidation of ethanol

The structural features and catalytic properties of Pt-Sn/CeO2 catalysts prepared by modified polyol method were extensively investigated for the complete oxidation of ethanol. CO chemisorption, TPR, DTA and XPS measurements identically indicated that the electronic configuration of Pt by Sn as well as the formation of PtSn alloy were the key factors in determining the nature of the active sites, A strong Pt/Sn atomic ratio dependence of catalytic perfortmances was observed. which was explained in terms of the change., in the Surface structure of metal phases and the electronic Pt-Sn interaction. (c) 2005 Elsevier B.V. All rights reserved.

Uniformly carbon-covered alumina and its surface characteristics

Uniformly carbon-covered alumina (CCA) was prepared via the carbonization of sucrose highly dispersed on the alumina surface. The CCA samples were characterized by XRD, XPS, DTA-TG, UV Raman, nitrogen adsorption experiments at 77 K, and rhodamine B (RB) adsorption in aqueous media. UV Raman spectra indicated that the carbon species formed were probably conjugated olefinic or polycyclic aromatic hydrocarbons, which can be considered molecular subunits of a graphitic plane. The N(2) adsorption isotherms, pore size distributions, and XPS results indicated that carbon was uniformly dispersed on the alumina surface in the as-prepared CCA. The carbon coverage and number of carbon layers in CCA could be controlled by the tuning of the sucrose content in the precursor and impregnation times. RB adsorption isotherms suggested that the monolayer adsorption capacity of RB on alumina increased drastically for the sample with uniformly dispersed carbon. The as-prepared CCA possessed the texture of alumina and the surface properties of carbon or both carbon and alumina depending on the carbon coverage.