Structure and catalytic properties of magnesia-supported copper salts of molybdovanadophosphoric acid

The structure and stability of magnesia-supported copper salts of molybdovanadophosphoric acid (Cu2PMo11VO40) were characterized by different techniques. The catalyst was prepared in ethanol by impregnation because this solvent does not hurt texture of the water-sensitive MgO and Cu2PMo11VO40. The Keggin-type structure compound may be degraded partially to form oligomerized polyoxometalate when supported on MgO. However, the oligomers can rebuild as the Keggin structure again after thermal treatment in air or during the reaction. Meanwhile, the V atoms migrate out of the Keggin structure to form a lacunary structure, as observed by Fourier transform IR spectroscopy. Moreover, the presence of Cu2+ as a countercation showed an affirmative influence on the migration of V atoms, and the active sites derived from the lacunary species generated after release of V from the Keggin anion. The electron paramagnetic resonance data imply that V5+ autoreduces to V4+ in the fresh catalyst, and during the catalytic reaction a large number of V4+ ions are produced, which enhance the formation of O2- vacancies around the metal atoms. These oxygen vacancies may also improve the reoxidation function of the catalyst. This behavior is correlated to higher catalytic properties of this catalyst. The oxidative dehydrogenation of hexanol to hexanal was studied over this catalyst.

用硼泥制备大尺寸氧化镁单晶及其性能研究

介绍用废渣硼泥制取高纯氧化镁粉末来制备大尺寸氧化镁单晶的生长方法。实验结果表明各项性能指标优良。而且 ,MgO原料的纯度及SiO2 和CaO材料的配比与晶体生长技术是我们获得优质晶体的关键因素。同时探讨了晶体的加工和应用前景

常温一氧化碳气敏元件制备及气敏机理研究

介绍了以SnO2 为主 ,掺入Al2 O3 ,MgO ,InO ,Pd等添加剂的常温CO气敏元件的制备方法。根据其晶体结构特点对气敏机理进行了探讨。论述了传感器的信息传感机制 ,即晶界势垒控制和晶粒大小控制机制同时存在。为获得性能良好的气敏元件 ,需要最佳的制备方法和最好的添加剂

Catalytic reduction of NO, by CO on hydrotalcites-derived mixed oxides CoAlM and MgAlM (M = Cr, Mn, Fe, Co, Ni, Cu)

Two series of mixed oxides, CoAlM and MgAlM (M = Cr, Mn, Fe, Co, Ni, Cu), were prepared by calcining their corresponding hydrotalcite-like compounds (HTLc). The ratio of Mg: Al: M (or Co: Al: hi) was 3:1:1. The catalytic activity of all samples for the reaction of NO + CO was investigated. The results showed that the activity of CoAlM was much higher than that of MgAlM. The structure and the property of redox were characterized by XRD and H-2-TPR. The results indicated that only MgO phase was observed after calcining MgAlM hydrotalcites, and the transition metals became more stable. The spinel-like phase appeared in all of CoAlM samples after the calcination, and the transition metals were changed to be more active, and easily reduced. The activities of three series of mixed oxides CoAlCu obtained from different preparation methods, different ratio of Co:Al: Cu and at different calcination temperatures, were studied in detail for proposing the mechanism of reaction. The ability of adsorption of NO and CO were investigated respectively for supporting the mechanism.

STUDY ON THE ACTIVE-CENTERS OF METHANE COUPLING CATALYSTS BY MEANS OF FLUORESCENCE EMISSION OF EU3+

Eu3+ ion was adopted as a probe to detect the probability of entrance of alkali elements into the crystal lattice of MgO, CaO and La2O3 by means of its characteristic emission. Based on the experimental data it is concluded that Li+ and Na+ ions can substitute Mg2+ and Ca2+ ions and only a small amount of K+ ion can enter into the lattice of CaO. Whilst Li+ ion can not enter into the lattice of lanthana. The conclusion of this investigation is in good agreement with that obtained by Lunsford by ESR studies.

用自动元素分析仪测定含氟化合物中的碳、氢

本文介绍用兰州化物所制备的Ag_2WO_4,MgO/AgVO_3催化剂分析含氟量很高的高分子化合物中的碳、氢的方法。该法的优点是快速、简便、燃烧温度低。测定的绝对误差不大于0.3%。 2 仪器和试剂: Carlo Erba 1106型元素分析仪,精度为lμg的天平,锡箔压制的样品小舟。Ag_2WO_4,MgO/AgVO_3兰州化物所制,镀银还原铜自制。氧气、氦气的纯度为99.999％。

碱-碱土-稀土催化剂发射光谱的研究

用Eu~(3+)的发射光谱探讨了O~-物种的形成。对M/MgO、M/CaO体系(M为碱金属)的研究发现,Li~+、Na~+可进入MgO晶格;Li~+、Na~+、K~+可进入CaO晶格。由于Li~+不能进入La_2O_3晶格,故不能形成O~-物种,表明不同的催化剂体系在甲烷氧化偶联反应中会形成不同的活性中心。

硼酸盐玻璃中Gd~(3+)、Dy~(3+)、Bi~(3+)对Tb~(3+)发光性质的影响

本文研究了单掺和双掺(Tb~(3+)、Tb~(3+)+Gd~(3+)、Tb~(3+)+Dy~(3+)、Tb~(3+)+Bi~(3+)约四十余种不同成份的硼酸盐玻璃。探讨了玻璃成份对Tb~(3+)发光性质的影响和Gd~(3+)、Dy~(3+)、Bj~(3+)对Tb~(3+)的胜化作用。在B_2O_2-BaO-M_mO_n(M_mO_n=Li_2O、Na_2O、K_2O、MgO、CaO、SrO、Al_2O_3、La_2O_3和Bi_2O_3)玻璃体系中,当M_mO_n分别为MgO和Al_2O_3时,Tb~(3+)的发光强度最强;M_mO-n为Bi_2O_3时,Tb~(3+)的发光强度最弱。Tb~(3+)的特征发射峰分别随着碱金属、碱土金属和三价金属的离子半径增加而红移。Gd~(3+)、Dy~(3+)、Bi~(3+)对Tb~(3+)均有敏化作用。特别是Gd~(3+),使Tb~(3+)的发光强度增加1～3.8倍,其最佳敏化浓度,因基质玻璃成份而异。

Sm~(3+)在硼酸盐玻璃中的发光及Bi~(3+)对Sm~(3+)的敏化作用

早在六十年代,人们为了寻找较好的激光玻璃,曾对Sm~(3+)离子掺杂的玻璃中的光谱进行过研究。为了探寻新型的激光,发光玻璃,又进一步研究了Sm~(3+)在玻璃中的发光和敏化。我们以寻找一种高亮度,低成本的发光玻璃为目的,研究了基质玻璃组成,敏化离子及其浓度对Sm~(3+)发光性质的影响。 选择B_2O_3-BaO-M_mO_n(M_mO_n=Li_2O,Na_2O,K_2O,MgO,CaO,SrO)玻璃体系,所用原料的纯度皆为分析纯以上,用陶瓷坩埚在1250℃掺杂氧化钐(纯度均大于99％),玻璃的荧光谱和激发光谱,用MPF-4型荧光分光光度计测定。

Geochemical properties of the variolitic andesite from Susong in the Dabie orogenic belt, China

The variolitic andesite from the Susong County in the Dabie Mountains implies that it was erupted in water. The mineralogy of the varioles is primarily radiate plagioclase (albite sind oligoclase), with little pyroxene, hornblende and quartz (derived from alteration). The pyroxene, hornblende and quartz are in the interstices between plagiocalse. The matrix consists of glass, hornblende, chlorite, epidote and zoisite. It is clearly subjected an extensive alteration. The andesite has an uncommon chemical composition. The SiO2 content is about 56.8%, TiO2 = 0.9%, MgO = 6.4%, Fe2O3 (tot) = 6.7%similar to 7.6%, 100Mg/(Mg + Fe) = 64.1 similar to 66.2. Mg-# is significantly high. The andesite has high abundances of large-lithophile trace elements (e.g. K, Ba. Sr, LREE), e.g. La/Nb = 5.56 similar to 6.07, low abundances of high-strength-field elements (HFSE e.g. Ta, Nb, P, Ti), particularly Ta and Nb strongly depleted. These are consistent with the characteristics of subduction-related magmas. In the spider diagram of trace elements, from Ce to right hand, the abundances of elements decrease quickly, showing a character of the continental margins. There has a strong punishment of light-rare-earth elements, with a significant diffraction of REEs (the mean value of (La/Yb)(N) is 32.84). No Eu anomaly, but there are anomaly high (La/Yb)(N) = 28.63 similar to 36.74, (La/Y)(N) = 70.33 similar to 82.4. The elements Y and Yb are depleted greatly, Y<20 g/g, Y-N = 2.74 similar to 2.84, Yb-N = 2.18 similar to 2.35. From the La-(La/Sm) diagram, the andesite is derived from partial melting. But the epsilone value of Nd is - 18.7 similar to -19.2, so that the material source may be the mantle materials affected by the crustal materials. The Nd model age is 1.9 Ga indicating that the variolitic basaltic andesite was resulted from the mantle wedge of North China block, which had the Nd model age of 2.5Ga, when the Yangze block which had the Nd model age of 1.7Ga subducted beneath it. So the variolitic andesite has characteristics of the island-are volconic rocks oil a continental basement in the vicinity of the destructive continental margin.

Geochemistry of the lava and its implications in Musicians Seamounts

Chemical and isotopic data of the lava samples dredged in the southern Bach Ridge and the northern Italian Ridge of the Musicians Seamounts province, northeast of Hawaii. Although most of the samples analyzed are generally altered, a few are fresh. The latter exhibits similar geochemical and isotopic characteristics to normal MORB (Mid-Ocean Ridge Basalts). There are systematic geochemical trends from hotspot to mid-ocean ridge in the province. Incompatible element and isotopic variations suggest that the flow field had at least two distinct parental magmas, one with higher and one with lower MgO concentrations. The two parental magmas could be related by a magma mixing model. The major and trace element modeling shows that the two parental magmas could not have been produced by different degrees of melting of a homogeneous mantle source, but they are consistent with melting of a generally depleted mantle containing variable volumes of embedded enriched heterogeneity enriched interbeds.

Periodical mixing of MORB magmas near East Pacific Rise 13N: evidence from modeling and zoned plagioclase phenocrysts

Thirty-six basalt samples from near East Pacific Rise 13N are analyzed for major and trace elements. Different types of zoned plagioclase phenocrysts in basalts are also backscatter imaged, and major element profiles scanned and analyzed for microprobe. Basalts dredged from a restricted area have evolved to different extents (MgO=9.38wt%-6.76wt%). High MgO basalts are modeled for crystallization to MgO of about 7wt%, and resulted in the Ni contents (28 ppm) that are generally lower than that in observed basalts (> 60 ppm). It suggests that low MgO basalts may have experienced more intensive magma mixing. High MgO (9.38wt%) basalt is modeled for self-"mixing-crystallization", and the high Ni contents in low MgO basalts can be generated in small scale and periodical self-mixing of new magma (high MgO). "Mixing-crystallization" processes that low MgO magmas experienced accord with recent 226Ra/230Th disequilibria studies for magma residence time, in which low MgO magmas have experienced more circles of "mixing-crystallization" in relatively longer residence time. Magma mixing is not homogeneous in magma chamber, however, low MgO magmas are closer to stable composition produced by periodical "mixing-crystallization", which is also an important reason for magma diversity in East Pacific Rise. Zoned plagioclase phenocrysts can be divided into two types: with and without high An# cores, both of which have multiple reversed An# zones, suggesting periodical mixing of their host magmas. Cores of zoned plagioclase in low MgO (7.45wt%) basalt differ significantly with their mantle in An#, but are similar in An# with microlite cores (products of equilibrium crystallization) in high MgO (9.38wt%) basalt, which further shows that plagioclase phenocryst cores in low MgO basalts may have formed in their parental magmas before entering into the magma chamber.

Genesis of Th-230 excess in basalts from mid-ocean ridges and ocean islands: Constraints from the global U-series isotope database and major and rare earth element geochemistry

Based on Th-230-U-238 disequilibrium and major element data from mid-ocean ridge basalts (MORBs) and ocean island basalts (OIBs), this study calculates mantle melting parameters, and thereby investigates the origin of Th-230 excess. (Th-230/U-238) in global MORBs shows a positive correlation with Fe-8, P (o), Na-8, and F-melt (Fe-8 and Na-8 are FeO and Na2O contents respectively after correction for crustal fractionation relative to MgO = 8 wt%, P (o)=pressure of initial melting and F (melt)=degree of melt), while Th-230 excess in OIBs has no obvious correlation with either initial mantle melting depth or the average degree of mantle melting. Furthermore, compared with the MORBs, higher (Th-230/U-238) in OIBs actually corresponds to a lower melting degree. This suggests that the Th-230 excess in MORBs is controlled by mantle melting conditions, while the Th-230 excess in OIBs is more likely related to the deep garnet control. The vast majority of calculated initial melting pressures of MORBs with excess Th-230 are between 1.0 and 2.5 GPa, which is consistent with the conclusion from experiments in recent years that D (U)> D (Th) for Al-clinopyroxene at pressures of > 1.0 GPa. The initial melting pressure of OIBs is 2.2-3.5 GPa (around the spinel-garnet transition zone), with their low excess Ra-226 compared to MORBs also suggesting a deeper mantle source. Accordingly, excess Th-230 in MORBs and OIBs may be formed respectively in the spinel and garnet stability field. In addition, there is no obvious correlation of K2O/TiO2 with (Th-230/U-238) and initial melting pressure (P (o)) of MORBs, so it is proposed that the melting depth producing excess Th-230 does not tap the spinel-garnet transition zone. OIBs and MORBs in both (Th-230/U-238) vs. K2O/TiO2 and (Th-230/U-238) vs. P (o) plots fall in two distinct areas, indicating that the mineral phases which dominate their excess Th-230 are different. Ce/Yb-Ce curves of fast and slow ridge MORBs are similar, while, in comparison, the Ce/Yb-Ce curve for OIBs shows more influence from garnet. The mechanisms generating excess Th-230 in MORBs and OIBs are significantly different, with formation of excess Th-230 in the garnet zone only being suitable for OIBs.

Geochemical and isotopic characteristics of volcanic rocks from the northern East China Sea shelf margin and the Okinawa Trough

Volcanic rocks both from the northern East China Sea (NECS) shelf margin and the northern Okinawa Trough are subalkaline less aluminous, and lower in High Field Strength Elements (HFSE). These rocks are higher in Large Ion Lithophile Elements (LILE), thorium and uranium contents, positive lead anomalies, negative Nb-Ta anomalies, and enrichment in Light Rare Earth Elements (LREE). Basalts from the NECS shelf margin are akin to Indian Ocean Mid-Ocean Ridge Basalt (MORB), and rhyolites from the northern Okinawa Trough have the highest Pb-207/Pb-208 and Pb-208/Pb-204 ratios. The NECS shelf margin basalts have lower Sr-87/Sr-86 ratios, epsilon(Nd) and sigma O-18 than the northern Okinawa Trough silicic rocks. According to K-40-Ar-40 isotopic ages of basalts from the NECS shelf margin, rifting of the Okinawa Trough may have been active since at least 3.65-3.86 Ma. The origin of the NECS shelf margin basalt can be explained by the interaction of melt derived from Indian Ocean MORB-like mantle with enriched subcontinental lithosphere. The basalts from both sides of the Okinawa Trough may have a similar origin during the initial rifting of the Okinawa Trough, and the formation of basaltic magmas closely relates to the thinning of continental crust. The source of the formation of the northern Okinawa Trough silicic rocks was different from that of the middle Okinawa Trough, which could have been generated by the interaction of basaltic melt with an enriched crustal component. From the Ryukyu island arc to East China, the Cenozoic basalts have apparently increasing trends of MgO contents and ratios of LREE to Heavy Rare Earth Elements (HREE), suggesting that the trace element variabilities of basalts may have been influenced by the subduction of the Philippine Sea plate, and that the effects of subduction of the Philippine Sea plate on the chemical composition of basaltic melts have had a decreasing effect from the Ryukyu island arc to East China.

冲绳海槽西南端中全新世以来的沉积特征及其物源与环境意义

作为大陆向大洋的过渡带，由于享有得天独厚的沉积环境，具有独特的构造特征以及与黑潮主流之间的密切关系，一直以来，冲绳海槽都是中外学者研究的重点靶区。2005年5月，由我国与法国联合主持的IMAGES 航次在台湾东北海域获取MD05-2908柱状岩芯（24º48.04′N,122 º29.35′E,水深为1275米），该柱状岩芯为一34.17米长高质量的连续沉积记录，岩性以深灰色粘土质粉砂为主，含水量较高，粘性、可塑性强，含有数层厚度不等的夹层。岩芯年龄模式依据17个AMS 14C定年数据建立，岩芯底部年代约6.8ka，为中全新世以来的沉积。在实验室对样品按照2cm的间隔进行分割后分别进行了粒度分析、粘土矿物提取与测试、碎屑矿物提取与鉴定、常微量元素和稀土元素分析等实验。 粒度分析结果显示，MD05-2908岩芯沉积物粒度垂向上总体比较均一，以细颗粒的粘土与粉砂质为主，但不同层位也稍有差别，表现为底部层位粒度较粗，含砂量较高，说明底部沉积环境比较复杂。粘土粒级（<2µm）矿物主要由四种粘土矿物和少量石英、长石碎屑组成。其中，粘土矿物相对含量变化中，伊利石（～68％）与绿泥石（～17%）构成主要成分，含有蒙皂石（～10％）和高岭石（～5％）。结合台湾东北外海表层沉积物的研究，利用粘土矿物伊利石/蒙皂石和绿泥石/高岭石比值得出岩芯粘土矿物主要为陆源碎屑粘土矿物，其源岩主要为台湾中央山脉的变质岩与台湾东部的沉积岩。重矿物分析共选取了41个层位，对63~250μm粒级的样品在实体镜和偏光显微镜下进行鉴定，结果显示，岩芯重矿物主要由绿泥石（29%）、普通角闪石（22%）、白云石（10%）、黑云母（8%）、绿帘石（7%）、白云母（7%）、褐铁矿（5%）等组成。稳定矿物少，矿物成熟度低。碎屑矿物风化程度低，磨蚀不明显，分选较差，表明沉积物来自于近源，后期改造作用不明显。常量元素分析结果表明，SiO2 、Al2O3和Fe2O3是岩芯沉积物中的最主要组分，这三种组分占沉积物总量的82%左右。 整个岩芯自下而上各常量组分变化不大，其平均值与东海陆架沉积物基本接近。微量元素变化比较明显， Ba、Cr、Cu、Zn元素的含量比东海陆架沉积物中的含量要高，而Sr的含量明显低于东海陆架。对常微量元素的R型因子分析表明，常量元素SiO2、Al2O3、Fe2O3、MgO和K2O，微量元素Cr、Cu、Ni、Zn、Pb、Rb和Mn可代表陆源物质；常量元素CaO和微量元素Sr、Ba可代表生物源物质。岩芯沉积物以陆源物质为主，生源物质的贡献起次要作用。岩芯沉积物中稀土元素总量平均为169.87×10-6，并且轻稀土含量均高于重稀土，LREE/HREE平均值为10.14，表明了轻稀土对稀土总量的贡献远高于重稀土，沉积物富集轻稀土，反映了沉积物的陆源特征。 岩芯MD05-2908中全新世以来平均5m/ka的高沉积速率主要源于丰富的物质供应和适宜的沉积环境。岩芯细粒级沉积物中，地球化学特征表明沉积物主要来源于陆源碎屑物质，粘土矿物特征与台湾东部陆源物质相同；粗粒级沉积物中，重矿物含量及矿物特征也表明岩芯沉积物粗颗粒组分主要来自于近源沉积。台湾宜兰境内的兰阳溪每年携带约一千万吨冲积物入海成为研究区重要的物质来源。由于受到黑潮的强烈影响，逆时针涡流及底层反向流的存在是岩芯高沉积速率重要控制因素。因此，利用动力分选的粉砂组分可以用来示踪古洋流强度，结果显示，6.8ka以来黑潮的强弱波动频繁，并表现出一定的旋回性变化，频谱分析表明，其具有的千年尺度周期（1500a）、百年尺度周期（604a、242a、192a、153a、133a）与十年尺度周期（22a）的周期性变化均与太阳辐射量变化有密切关系，因此，黑潮的强弱变化在大背景上是由太阳活动所控制的。 根据测年资料可以识别出岩芯存在5期快速堆积事件，这与区域性降水增加有关，降雨量增加导致陆源物质输入的增加。另外，岩芯位于大陆斜坡区，附近存在有三支海底峡谷，并且地震活动频繁，沉积在宜兰陆架及东海陆架处的浅海沉积物由于受到地震、风暴等活动的影响而受扰动崩塌、因重力作用而向低处输送，产生二次侵蚀并经由海底峡谷搬运到冲绳海槽南段堆积,使得沉积环境更为复杂，但同时也为冲绳海槽提供了丰富的物质供应。