BiOBr/铁改性蒙脱石对罗丹明B的光催化降解性能研究

在低温条件下通过铁改性蒙脱石与BiOBr复合成功合成了一种新型的光催化材料,称为BiOBr/Fe-Mt。运用X射线粉末衍射(XRD)、透射电镜(TEM)、傅立叶转换红外光谱(FTIR)、紫外可见漫反射光谱(UV-Vis DRS)对BiOBr/Fe-Mt材料进行表征。同时以λ400 nm的可见光为光源,开展该催化剂对罗丹明B(Rh B)的光催化降解实验以评估其光催化活性。结果表明,支撑材料投加量被固定在2.5 g的条件下,采用铁改性蒙脱石制备的BiOBr/Fe-Mt材料对Rh B的光催化降解活性高于采用钠基蒙脱石制备的BiOBr/Na-Mt。光催化活性的显著提高,主要归因于:1 BiOBr/Fe-Mt的禁带宽度降低至2.46 e V,或可能形成了BiOBr/铁氧化物异质结结构;2 BiOBr/Fe-Mt上仅发生较少的十六烷基三甲基溴化铵有机分子残留。这些结构因素均可以有效促进BiOBr/Fe-Mt上Rh B的光催化降解。     

H2O2在α-Fe2O3表面非均相氧化SO2机理的模拟研究

通过密度泛函理论模拟了H_2O_2和SO_2气体在矿物氧化物(α-Fe_2O_3)表面上的非均相反应,研究了H_2O_2和SO_2在α-Fe_2O_3(001)表面的吸附机制和氧化机制。研究结果表明,SO_2、H_2O_2均在α-Fe_2O_3(001)表面通过Fe原子进行吸附,H_2O_2相比于SO_2优先吸附在α-Fe_2O_3(001)表面,且H_2O_2在表面的赋存形式趋向于两个·OH形式吸附。通过二者共吸附的局域态密度、差分电荷密度、Mulliken电荷布局分析结果发现,SO_2和H_2O_2的共吸附形式是通过H_2O_2产生的·OH吸附在α-Fe_2O_3(001)表面,同时SO_2被H_2O_2产生的·OH氧化[S(SO_2)-电荷布局:0. 79 e→1. 32 e; O(H_2O_2)-电荷布局:-0. 77 e→-1. 11 e]形成·OH+SO_2团簇。模拟结果表明大气微量气体H_2O_2能够在矿物氧化物表面介导SO_2吸附并促进SO_2的转化,为理解H_2O_2在大气中非均相氧化SO_2的反应过程提供了理论依据。     

CO2全球循环及其同位素示踪研究

极地冰盖气泡研究表明,工业革命前大气圈天然ＣＯ₂浓度约为２８０×１０－６,天然ＣＯ₂浓度变化反映了冰期－间冰期循环这一长期气候变化固有特征。工业革命后,大量人为ＣＯ₂进人大气圈,人为ＣＯ₂收支明显不平衡,一个大于２．６ＧＴＣ／ａ的未知陆地生态汇很可能存在于北半球中纬度地带。土壤、岩溶作用、河流作用、地球化学作用、干旱－半干旱环境等系统以及海洋内部ＣＯ₂循环的同位素示踪研究,可为人为ＣＯ₂未知汇即“ＭｉｓｓｉｎｇＳｉｎｋ”的探求提供线索。     

HONO在γ-Al2O3(110)表面非均相氧化SO2机理的第一性原理研究

为研究亚硝酸(HONO)在γ-Al_2O_3(110)表面非均相氧化SO_2的机理,基于密度泛函理论(density functional theory,DFT)的第一性原理计算了SO_2和HONO在γ-Al_2O_3(110)表面的吸附机制和氧化机制。结果表明,SO_2以分子的形式吸附在完整或缺陷的γ-Al_2O_3(110)表面,而HONO仅在完整表面上以分子的形式存在。表面氧缺陷的存在不仅会增强SO_2和HONO的吸附强度,而且能诱导HONO在含氧缺陷表面的分解(HONO→NO+·OH)。通过局域态密度(partial density of states,PDOS)和Mulliken电荷布局分析表明,HONO的分解遵循Haber-Weiss机制。当SO_2和HONO共同吸附在氧缺陷表面时,HONO分解产生·OH,氧化SO_2形成HOSO_2团簇分子。该研究不仅有助于理解HONO在矿物氧化物表面氧化SO_2的作用,而且为解释大气硫酸盐气溶胶的形成提供了理论依据。     

云贵高原湖泊CO2的地球化学变化及其大气CO2源汇效应

湖泊是大气CO₂的源还是汇,长期以来一直都存有争议。云贵高原地区的湖泊由于受流域碳酸盐岩风化作用的影响,使这一问题就显得更特殊,也更复杂。本次研究通过化学平衡计算和气相色谱测定两种方法得到了比较一致的湖水CO₂浓度结果。研究发现,在夏季强烈的光合作用消耗了湖水CO₂,致使湖水中CO₂浓度降低。在贵州草海、百花湖以及云南的泸沽湖、杞麓湖,表层湖水CO₂分压(为便于与大气CO₂比较,文中湖水CO2用分压单位表示)小于200μatm,远低于大气CO₂分压,湖泊正不断地从大气中吸收CO₂,从而构成大气CO₂的汇。     

BrF5法氧同位素实验系统中CO2转换器的改进及意义

硅酸盐、氧化物的氧同位素测定分析,是成岩成矿物质 源区鉴定、矿物岩石形成温度确定、成岩成矿地球化学机理 推测的重要手段之一^[1]。在固体地球科学的诸多学科^{[2]以 及环境科学、水文、古气候、天体化学等其他学科均有着广泛 的应用。因此,随着样品量的增加,提高实验室的BrF5法氧 同位素实验系统的工作效率颇有意义。 图1为BrF₅法氧同位素实验系统装置。当系统真空抽 至3×10-3Pa时,充入氩气。分别将已称好的200目干燥样 品12mg加入各反应器,经2小时200℃去气抽真空后,将化 学计算量}     

采空区对CO2置换开采海域天然气水合物置换效果影响的实验研究

为揭示固体开采形成的采空区对CO₂置换开采天然气水合物置换效果的影响,开展了含采空区储层与完整储层的CO₂/N₂置换开采不同天然气水合物饱和度对比实验研究。结果表明：对于水合物饱和度分别为30%和45%的试样,含采空区储层较完整储层的CH₄置换率分别提高了5.5%和9%,单位体积CO₂封存量分别提高了26.5%和39.8%。采空区的存在提高了置换介质与天然气水合物的摩尔比率,从而提供了更高的置换驱动力;且在较高水合物饱和度试样中采空区还会提高置换介质的扩散作用,导致含采空区储层的置换效果好于完整储层。因此,在固体开采后进一步进行CO₂置换开采,可以提高置换开采效率,同时有助于碳封存与地层稳定,是一种潜在的海域天然气水合物安全、绿色开采模式。     

高温下TiO2的相转变动力学及后期颗粒生长研究

利用原位高温XRD方法测量了锐钛矿相TiO2在不同温度下(850、863、875、888、900℃)时间与转化率之间的关系,证实锐钛矿-金红石相转变为一级反应。计算的相转变活化能为432.788±25.657 kJ/mol,指前因子为4.847 454×1015 s-1。利用ESEM观察了样品在相转变完成后,经历不同温度(888、900、930、960、1 000℃)相同烧结时间(10 h),和相同温度(1 000℃)不同烧结时间(0、5、10、15、20 h)下颗粒晶型变化和颗粒长大情况。在1 000℃以下时,温度对颗粒粒度的影响并不明显,并且不出现完好的晶型。1 000℃时,随着时间的延长,颗粒粒度不断增大,并在10 h以后出现完好晶型。根据lnDt(Dt为t时间下颗粒的平均粒度)和lnt的关系图,认为颗粒生长应经过两个不同时期。     

The rise of trees and their effects on Paleozoic atmospheric CO2 and O2

The rise of large vascular plants during the mid-Paleozoic brought about a major increase in the rates of weathering of silicate minerals that induced a drop in the level of atmospheric CO₂ and contributed, via the atmospheric greenhouse effect, to global cooling and the initiation of the most long lived and a really extensive glaciation of the past 550 million years. Sedimentary burial of the microbiologically resistant remains of the plants resulted during the Permo-Carboniferous in both further lowering of CO₂ and in elevation of atmospheric O₂. Evidence of changes in CO₂ and O₂ are provided by mathematical models, studies of paleosols, fossil plants, fossil insects, and the effects of modern plants on silicate weathering, and by laboratory studies of the effects of changes in O₂ on plants and insects. To cite this article: R.A. Berner, C. R. Geoscience 335 (2003).     

嫦娥一号干涉成像光谱仪数据再校正与全月铁钛元素反演

月球表面的元素和物质成分分布是理解月球成岩与地质演化历史的重要线索。嫦娥一号干涉成像光谱仪(IIM)是我国首台月球探测成像光谱仪器,其获得的大量月球高光谱数据已成为我国未来探测月球成分与地质演化研究的宝贵基础数据。本文利用探月工程地面应用系统发布的IIM B版本2C级数据,开发出一套数据再定标流程,获得了较为可靠的月表相对反射率数据。我们在新校正数据的基础上开展月球表面FeO、TiO_2的反演建模,获得了全月FeO和TiO_2分布图,这些图件是进行月球地质填图的基础。校正数据反演的FeO和TiO_2分布与前人对Clementine UVVIS数据的反演结果相近,表明干涉成像光谱仪数据具有较大的应用潜力。高地的低铁岩石成分(一般小于8%)佐证了月球月壳形成的过程中的岩浆洋分异假说,而月海玄武岩的TiO_2成分变化范围较大(0~13%)则表明月海玄武岩来源于不同的月幔源区。根据嫦娥一号干涉成像光谱仪全月FeO分布图,可将月球表面物质类型总体划分为高地斜长岩和月海玄武岩,而根据TiO_2分布可以进一步将月海玄武岩划分为5种不同钛含量的玄武岩岩石类型。FeO和TiO_2在全月范围内的分布表明Apollo和Luna返回的月球样品不能够代表全月范围内的矿物成分多样性,月球岩浆演化历史比前人认为的要复杂。未来月球样品返回任务(如嫦娥五号)如能赴这些特殊地区进行取样,将很有可能返回重要的月球科学研究发现和成果。     

Laboratory study of self-potential signals during releasing of CO2 and N2 plumes

Carbon Capture Sequestration (CCS) projects require, for safety reasons, monitoring programmes focused on surveying gas leakage on the surface. Generally, these programmes include detection of chemical tracers that, once on the surface, could be associated with CO₂ degassing. We take a different approach by analysing feasibility of applying electrical surface techniques, specifically Self-Potential. A laboratory-scale model, using water-sand, was built for simulating a leakage scenario being monitored with non-polarisable electrodes. Electrical potentials were measured before, during and after gas injection (CO₂ and N₂) to determine if gas leakage is detectable. Variations of settings were done for assessing how the electrical potentials changed according to size of electrodes, distance from electrodes to the gas source, and type of gas. Results indicated that a degassing event is indeed detectable on electrodes located above injection source. Although the amount of gas could not be quantified from signals, injection timespan and increasing of injection rate were identified. Even though conditions of experiments were highly controlled contrasting to those usually found at field scale, we project that Self-Potential is a promising tool for detecting CO₂ leakage if electrodes are properly placed.     

Flue gas and pure CO2 sorption properties of coal: A comparative study

Presently many research projects focus on the reduction of anthropogenic CO₂ emissions. It is intended to apply underground storage techniques such as flue gas injection in unminable coal seams. In this context, an experimental study has been performed on the adsorption of pure CO₂ and preferential sorption behavior of flue gas. A coal sample from the Silesian Basin in Poland (0.68% V Rr), measured in the dry and wet state at 353 K has been chosen for this approach. The flue gas used was a custom class industrial flue gas with 10.9% of CO₂, 0.01% of CO, 9% of H₂, 3.01% of CH₄, 3.0% of O₂, 0.106% of SO₂ and nitrogen as balance.Adsorption isotherms of CO₂ and flue gas were measured upto a maximum of 11 MPa using a volumetric method. Total excess sorption capacities for CO₂ on dry and wet Silesia coal ranged between 1.9 and 1.3 mmol/g, respectively. Flue gas sorption capacities on dry and wet Silesia coal were much lower and ranged between 0.45 and 0.2 mmol/g, respectively, at pressures of 8 MPa. The low sorption capacity of wet coal has resulted from water occupying some of the more active adsorption sites and hence reducing the heterogeneity of adsorption sites relative to that of dry coal. Desorption tests with flue gas were conducted to study the degree of preferential sorption of the individual components. These experiments indicate that CO₂ is by far the prefered sorbing component under both wet and dry conditions. This is followed by CH₄. N₂ adsorbs very little on the coal in the presence of CO₂ and CH₄. It is also observed that the adsorption of CO₂ onto coal is not significantly hindered by the addition of other gases, other than dilution effect of the pressure.In addition to the sorption experiments, the density of the flue gas mixture has been determined up to 18 MPa at 318 K. A very good precision of these measurements were documented by volumetric methods.     

低硅埃达克岩和高硅埃达克岩问题

低硅埃达克岩(low-SiO2adakites,LSA,SiO2<60%)和高硅埃达克岩(high-SiO2adakites,HSA,SiO2>60%)的术语是Martin等(2005)提出来的。本文不赞同上述分类,因为,他们的低硅埃达克岩是赞岐岩而不是埃达克岩。赞岐岩是幔源的,埃达克岩是壳源的,虽然埃达克岩可以与地幔混合形成高镁的埃达克岩,但仍然是壳源的。不应当把壳源的岩浆和幔源的岩浆混淆起来。     

中国东部CO2气地球化学特征及其气藏分布

中国东部CO₂气田(藏)发育广泛,分布复杂。本文对中国东部松辽、渤海湾、苏北、三水、东海、珠江口、莺琼、北部湾等盆地和内蒙古商都地区以及部分现代构造岩浆活动区CO₂气田(藏)和气苗中CO₂的地球化学特征进行了分析和研究,探讨了中国东部CO₂气的成因、来源及分布。中国东部CO₂气的含量主要分布区间为0~10%,其次为90%~100%,呈现典型的U字型。δ¹³C_CO2值则呈现典型的单峰式分布,峰值区间为-6‰~-4‰。CO₂含量、δ¹³C_CO2值和R/Ra值综合表明,中国东部高含CO₂气以幔源无机成因为主,混有部分有机成因气和(或)壳源无机气。中国东部已发现的36个无机成因CO₂气田(藏)在空间分布上与新近纪及第四纪北西西向玄武岩活动带展布一致,深大断裂和岩浆活动是无机成因CO₂富集、运移和分布最重要、最直接的两大主控因素。     

Primary cracking of kerogens. Experimenting and modelling C1, C2–C5, C6–C15 and C15+ classes of hydrocarbons formed

Mathematical models of hydrocarbon formation can be used to simulate the natural evolution of different types of organic matter and to make an overall calculation of the amounts of oil and/or gas produced during this evolution. However, such models do not provide any information on the composition of the hydrocarbons formed or on how they evolve during catagenesis.From the kinetic standpoint, the composition of the hydrocarbons formed can be considered to result from the effect of “primary cracking” reactions having a direct effect on kerogen during its evolution as well as from the effect of “secondary cracking” acting on the hydrocarbons formed.This report gives experimental results concerning the “primary cracking” of Types II and III kerogens and their modelling. For this, the hydrocarbons produced have been grouped into four classes (C₁, C₂–C₅, C₆–C₁₅ and C₁₅₊). Experimental data corresponding to these different classes were obtained by the pyrolysis of kerogens with temperature programming of 4°C/min with continuous analysis, during heating, of the amount of hydrocarbons corresponding to each of these classes.The kinetic parameters of the model were optimized on the basis of the results obtained. This model represents the first step in the creation of a more sophisticated mathematical model to be capable of simulating the formation of different hydrocarbon classes during the thermal history of sediments. The second step being the adjustment of the kinetic parameters of “secondary cracking”.