镍铝基柱撑蒙脱石的制备及孔道结构研究

以钠基蒙脱石为原料,采用共聚法合成镍铝柱化剂,利用离子交换法制备镍铝基柱撑蒙脱石。通过研究不同镍铝物质的量比例和不同NaOH的量对柱撑蒙脱石制备的影响,并对其孔道结构进行探讨。XRD结果表明,当镍铝物质的量比为1∶6、加入75mlNaOH时,可得到(001)面网层间距达1.8940nm的镍铝基柱撑蒙脱石。FT-IR显示,镍铝基聚合羟基阳离子进入蒙脱石层间,柱撑蒙脱石的基本结构并未发生改变。对柱撑前后蒙脱石的比表面积和孔径结构进行分析,发现镍铝基柱撑蒙脱石比表面积为169.68m2/g,平均孔径为4.120nm,说明镍铝基柱撑蒙脱石具有较大的比表面积,较小且均匀的孔径分布,是一种合适的催化和吸附材料。     

柱撑剂中Al3+形态转化对柱撑蒙脱石微结构的影响

以钠基蒙脱石为原料,结合电位滴定曲线及特征临界点,将Al3+的转化划分为4种形态,并制备相应的柱撑蒙脱石。并采用X射线衍射分析、红外光谱分析及热分析对各柱撑蒙脱石进行表征,研究各柱撑蒙脱石的微结构变化及热稳定性。结果表明,Ⅲ区柱撑蒙脱石层间距d(001)值由原矿的12. 408 1 nm增加到18. 317 5 nm,同时,Ⅲ区柱撑蒙脱石Si—O伸缩振动峰强度减弱较明显,在542℃附近的蒙脱石八面体结构的脱羟基反应与原矿相比向低温区发生偏移,说明Ⅲ区柱撑蒙脱石发生了成键反应且柱撑效果最佳。     

柱撑粘土的晶体结构模型

根据X射线衍射、电子探针等实验数据综合分析和理论计算，讨论了柱撑基团[Al13O4(OH)24(OH2)12]^7 和[Ti20O32(OH)12(OH2)18]^4 在粘土矿物结构单元层层间的分布，铝基和钛基的笼状离子作用范围分别相当于粘土矿物的10个和6个晶胞。羧基铝柱撑蒙脱石层间孔道高度为0.9-1.2nm，直径为1.5nm；理论孔道率为84％，有效孔道率为56％。钛基柱撑蒙脱石的层间孔道高度为1.34-1.60nm，直径为1.0nm，理论也道率为75％，有效孔道率为50％。根据柱撑离子基团的两种类型，可把柱撑粘土分为Keggin型柱撑粘土和Dawson型柱撑粘土。     

铁盐水解法制备铁层柱蒙脱石及其结构特性研究

利用低角度X射线衍射、红外光谱、喇曼光谱及孔结构分析,研究了用铁盐水解法制备的铁层柱蒙脱石的结构与性质。所制得的铁层柱蒙脱石以介孔型层离结构为主,微孔型柱撑结构为辅。前者为蒙脱石片层与铁离子水解产生的聚合羟基铁簇合物堆垛而成的卡房状结构,与d值为6.4±1.0nm的X射线衍射宽峰相对应;微孔型柱撑结构则与d值约1.5nm的(001)衍射峰相对应。所合成的系列铁层柱蒙脱石中最大的比表面积和孔容分别为215.7m2/g和0.291mL/g。500℃热处理后,仍保存铁层柱蒙脱石的介孔结构。铁层柱蒙脱石富含阴离子(NO3-),并作为平衡铁水解聚合物正电荷的反离子而稳定存在,可为磷钨酸离子[PW12O40]3-所交换。铁层柱蒙脱石的新型结构和特殊性质在催化剂、载体与吸附剂等领域具新的应用前景。     

柱撑蒙脱石制备与表征

本文采用多种方法制备keggin离子，并探索出制备稳定keggin离子的适宜酸碱度，用此柱化剂制备出层间距为2．4～2．5nm的柱撑蒙脱石。应用X射线走向衍射技术、红外光谱、差热分析对往撑蒙脱石进行表征，用BET、吡啶吸附考察了其表面物理化学性质。结果表明，用Keggin离子制备出的柱撑蒙脱石其层间距在自然状态下为2．4～2．5nm，350C灼烧，层间距稳℃定在1．8nm，且具有耐热性能好、较大的比表面积和较强的Lewis酸位中心等特点．     

钛基柱撑累托石矿物材料的研究

在氮气环境中用TiCI4和HCI制成钛基柱撑液，采用离子交换法，用[Ti20O32(OH)12(OH2)18]^4 Dawson型Ti多核阳离子，交换累托石蒙皂石质晶层中的Na等阳离子，制成钛基柱撑累托石。通过电子探针定量分析、X射线衍射、红外光谱、热分析及魔角旋转核磁共振等方法，对钛基柱撑累托石的成分、结构和热稳定性进行了表征。钛基柱撑累托石具1．6nm的层孔隙，是一种很有应用前途的柱撑粘土矿物材料，有望在催化剂载体及环保材料领域中得到广泛的使用。     

锆铝基柱撑蒙脱土的制备研究

以钠基蒙脱土为原料,采用共聚法合成锆铝基柱撑蒙脱土,并研究不同锆铝摩尔比例和不同NaOH的量对柱撑蒙脱土制备的影响。XRD研究表明,当锆铝摩尔比例为1：6、加入70ml0．4mol／LNaOH时,可得到（001）面网层间距达1．9343nm的锆铝基柱撑蒙脱土。通过FT—IR发现,锆铝聚合羟基阳离子进入蒙脱土层间,形成Si-O-Al和Si-O-Zr。对柱撑前后蒙脱土的比表面积和孔径结构进行分析,发现锆铝基柱撑蒙脱土具有较大的比表面积,较为均匀的孔径分布,是一种合适的催化和吸附材料。     

二氧化钛柱撑蒙脱石对铅、铬和铜离子的吸附性能研究

以钛酸丁酯为前驱体,钠基蒙脱石为载体,应用溶胶-凝胶法制备了二氧化钛(TiO2)柱撑蒙脱石纳米复合材料(TiO2-MMT)。采用X射线衍射、扫描电子显微镜、X-射线能量散色谱和透射电子显微镜等分析手段对样品进行了表征。结果表明,样品晶相主要由锐钛矿型TiO2和蒙脱石组成;TiO2-MMT呈层片状结构,TiO2柱撑到蒙脱石(MMT)层间,且MMT的(001)晶面间距明显增大;钛与蒙脱石比例、柱撑温度、柱化剂陈化时间、烘干温度、煅烧温度仅对蒙脱石(001)面的晶面间距有影响,且随着钛与蒙脱石比值的增大、柱化温度的升高,陈化时间的延长,晶面间距也逐渐增大。应用静止浸渍法测试了TiO2-MMT对铅、铬和铜离子的吸附性能。结果表明,TiO2-MMT对铅离子的吸附率达到99.8%,吸附固化效果优于钠基蒙脱石。     

煅烧铝柱撑蒙脱石材料结合态Fe(Ⅱ)对邻硝基苯酚的还原转化研究

通过铝盐与蒙脱石(Na-Mt)反应制备了铝柱撑蒙脱石(Al-Mt),同时采用X射线衍射(XRD)、红外光谱(FTIR)对在不同温度(200~600℃)下煅烧获得的铝柱撑蒙脱石产物(At-Mt-X)进行表征。探讨Fe(Ⅱ)与Al-Mt-X所形成的复合系统对邻硝基苯酚(2-NP)的吸附-还原降解行为,包括铝柱撑蒙脱石的煅烧温度、煅烧铝柱撑蒙脱石的表面酸位变化以及溶液pH值等条件对邻硝基苯酚还原转化的影响。结果表明,由于随着煅烧温度的升高,煅烧铝柱撑蒙脱石表面酸性位点会逐渐减少,使得其对Fe(Ⅱ)的还原性能增强;煅烧温度高于500℃时,煅烧改性产物与Fe(Ⅱ)形成的Fe(Ⅱ)/煅烧铝柱撑蒙脱石复合系统显著提高了Fe(Ⅱ)物种的还原活性,因而有效增强对2-NP的还原降解。此外,Fe(Ⅱ)/煅烧铝柱撑蒙脱石复合系统对2-NP的还原降解符合准一级反应动力学方程,表观速率常数(k)随pH值和铝柱撑蒙脱石煅烧温度的升高而增大。作为一种功能性矿物材料,煅烧铝柱撑蒙脱石在缺氧环境下能有效促进吸附态Fe(Ⅱ)物种对污染物的还原降解,煅烧温度与pH值是其中两个重要的制约因素。     

TDTMA+-柱撑蒙脱石吸附硝基苯的实验研究

以阳离子表面活性剂(十四烷基三甲基溴化铵,TDTMBA)为柱撑剂,在不同浓度条件下(0.2 CEC～2.5 CEC)制备了一系列柱撑蒙脱石,并通过XRD对有机蒙脱石进行表征,研究季铵盐离子在层间的排列结构.同时针对TDTMA -柱撑蒙脱石对硝基苯的吸附进行研究.实验结果表明,吸附去除率受硝基苯的初始浓度、反应时间等因素的影响,而与pH值没有太大的关系.经过柱撑改性后,粘土对硝基苯的吸附能力较原土有了明显的提高.随着层间柱撑浓度的增大,柱撑蒙脱石对硝基苯的吸附量也增大.另外钙基蒙脱石和平卧双层,倾斜单层以及倾斜双层的结构的TDTMA -柱撑蒙脱石对硝基苯的吸附等温线符Freundlich和Langmuir等温方程,假三层结构的TDTMA -柱撑蒙脱石对硝基苯的吸附等温线符合Linear等温方程,这表明前者是以表面吸附为主,后者是以分配作用为主.     

The terrestrial fauna of the Late Triassic Pant-y-ffynnon Quarry fissures,South Wales,UK and a new species of Clevosaurus (Lepidosauria: Rhynchocephalia)

Pant-y-ffynnon Quarry in South Wales yielded a rich cache of fossils in the early 1950s, including articulated specimens of new species (the small sauropodomorph dinosaur Pantydraco caducus and the crocodylomorph Terrestrisuchus gracilis), but no substantial study of the wider fauna of the Pant-y-ffynnon fissure systems has been published. Here, our overview of existing specimens, a few described but mostly undescribed, as well as freshly processed material, provides a comprehensive picture of the Pant-y-ffynnon palaeo-island of the Late Triassic. This was an island with a relatively impoverished fauna dominated by small clevosaurs (rhynchocephalians), including a new species, Clevosaurus cambrica, described here from a partially articulated specimen and isolated bones. The new species has a dental morphology that is intermediate between the Late Triassic Clevosaurus hudsoni, from Cromhall Quarry to the east, and the younger C. convallis from Pant Quarry to the west, suggesting adaptive radiation of clevosaurs in the palaeo-archipelago. The larger reptiles on the palaeo-island do not exceed 1.5?m in length, including a small carnivorous crocodylomorph, Terrestrisuchus, and a possible example of insular dwarfism in the basal dinosaur Pantydraco.     

The effect of water on accessory phase solubility in subaluminous and peralkaline granitic melts

The solubilities of columbite, tantalite, wolframite, rutile, zircon and hafnon were determined as a function of the water contents in peralkaline and subaluminous granite melts. All experiments were conducted at 1035 °C and 2 kbar and the water contents of the melts ranged from nominally dry to approximately 6 wt.% H₂O. Accessory phase solubilities are not affected by the water content of the peralkaline melt. By contrast, solubilities are affected by the water content of the subaluminous melt, where the solubilities of all the accessory phases examined increase with the water content of the melt, up to 2 wt.% H₂O. At higher water contents, solubilities are nearly constant. It can be concluded that water is not an important control of accessory phase solubility, although the water content will affect diffusivities of components in the melt, thus whether or not accessory phases will be present as restite material. The solubility behaviour in the subaluminous and peralkaline melts supports previous spectroscopic studies, which have observed differences in the coordination of high field strength elements in dry vs. wet subaluminous granitic glasses, but not for peralkaline granitic glasses. Lastly, the fact that wolframite solubility increases with increasing water content in the subaluminous melt suggests that tungsten dissolved as a hexavalent species.     

Quaternary stresses revealed by calcite twinning inversion: insights from observations in the Savonnières underground quarry (eastern France)

Calcite samples were extracted both from the rock matrix and the superficial coating of a karstified fault plane of an underground quarry, located in the eastern border of the Paris basin. The karstification is dated as Quaternary. Analysis of mechanical calcite twinning reveals that only the calcite matrix has also undergone a compression trending WNW that can be attributed to the Mio-Pliocene alpine collision. Both coating and matrix have undergone a strike-slip regime with σ₁ roughly trending north–south, that could correspond to the regional present-day state of stress, a strike-slip compression rather trending NNW, modified by local phenomena. To cite this article: M. Rocher et al., C. R. Geoscience 335 (2003).     

HYDROGEOLOGY

正20141756 Chen Ruige(Mathematical College,China University of Geosciences,Beijing100083,China);Zhou Xun Numerical Simulation of Groundwater Level Fluctuation in a Coastal Confined Aquifer with Sloping Initial Groundwater Level Induced by the Tide(Geological Bulletin of China,ISSN1671-2552,CN11-4648/P,32(7),2013,p.1099-1104,6 illus.,16 refs.) Key words:confined water,groundwater level     

METAMORPHIC PETROLOGY

正20141408 Cai Jia(Institute of Geology,Chinese Academy of Geological Sciences,Beijing100037,China);Liu Fulai Petrogenesis and Metamorphic P-T Conditions of Garnet-Spinel-Biotitebearing Paragneiss in Danangou Area,Daqingshan-Wulashan Metamorphic Complex Belt(Acta Petrologica Sinica,ISSN1000-0569,CN11-1922/P,29(7),     

SERIALS

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GEOPHYSICAL EXPLORATION

正20142386An Guoying(China Aero Geophysical Survey and Remote Sensing Center for Land and Resources,Beijing 100083,China)Application of Satellite Remote Sensing in Regional Hydrogeological Investigation:Taking Cenozoic Strata in Wenquan Sheet(1∶250 000)of Karakoram Range as an Example(Geosci-     

QUATERNARY GEOLOGY & GEOMORPHOLOGY

正20141016An Chengbang(Key Laboratory of Western China’s Environmental Systems,Ministry of Education,Lanzhou University,Lanzhou 730000,China);Zhao Yongtao Lake Records during the Last Glacial Maximum from Xinjiang,NW China and Their Climatic Impli-     

PETROLEUM GEOLOGY

正20141538 Cao Qing(School of Earth Sciences and Engineering,Xi’an Petroleum University,Xi’an 710065,China);Zhao Jingzhou Characteristics and Significance of Fluid Inclusions from Majiagou Formation,Yichuan Huangling Area,Ordos Basin(Advances in Earth Science,ISSN1001-8166,CN62-1091/P,28(7),2013,p.819-828,7 illus.,3 tables,43 refs.)     

GEOCHEMISTRY

正20142002 Wei Hualing(Institute of Geophysical and Geochemical Exploration,Chinese Academy of Geological Sciences,Langfang065000,China);Zhou Guohua Element Content and Mineral Compositions in Different Sizes of Soil in Tongling Area,Anhui Province(Geological Bulletin of China,ISSN1671-2552,CN11-4648/P,32(11),2013,p.1861