配合物改性蒙脱石及其对直接大红染料的吸附性

利用蒙脱石的层间活性,用过渡金属离子与配位体生成的配合物改性蒙脱石,通过测定改性蒙脱石对直接大红染料的脱色性及XRD图,研究配合物的中心离子种类、配位体种类、制备方法等对蒙脱石层间结构及吸附较大分子化合物性能的影响。结果表明,带正电的配合物离子能够有效进入蒙脱石层间、增大层间距;4或6配位数的配合物改性蒙脱石能明显提高对染料的吸附性;采用金属离子为先驱体,先插入蒙脱石层间,再原位生成配合物的两步法效果较好。     

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.     

蒙脱石对赖氨酸和壳聚糖的吸附实验研究

粘土矿物对有机质的吸附是自然界重要的过程之一。科学界对于有机质与粘土矿物的相互作用过程和机制研究仍处 于一个比较薄弱的阶段。该文采用天然有机质赖氨酸（左旋） 和壳聚糖与蒙脱石进行室内合成模拟实验,通过X射线衍 射、化学分析和红外光谱分析的手段对反应产物进行系统研究。结果表明,蒙脱石对赖氨酸和壳聚糖的吸附均存在两种机 制：阳离子交换和有机分子间的相互吸引。赖氨酸在蒙脱石层间的排布有三种构型,随着赖氨酸浓度的增加分别以倾斜 式、垂直呈“之”字形排列,最后形成第二排并可能生成简单肽;氨基酸的净电荷是影响吸附过程的重要因素,主要与pH 值相关。壳聚糖能在蒙脱石层间形成分层结构,溶液的pH值和无机盐的存在都会影响吸附过程。壳聚糖-蒙脱石复合体在 常温常压下水溶液中能稳定存在,而相同条件下赖氨酸易从蒙脱石层间释放,这主要是由有机质本身的性质以及有机质和 蒙脱石的结合方式决定的。     

不同粘土矿物对赖氨酸的吸附行为对比研究

以皂石、高岭石、绿泥石和伊利石为原材料,分别与赖氨酸进行反应,研究赖氨酸在上述粘土矿物上的吸附行为, 并运用粉末X-射线衍射技术（XRD）、傅里叶变换红外吸收光谱术（FTIR）和热重（TG）等分析方法,表征反应前后粘土 矿物的变化。实验结果表明,不同粘土矿物对赖氨酸的吸附等温线均符合Freundlich等温方程,且不同粘土矿物对赖氨酸的 饱和吸附量大小顺序为：皂石>蒙脱石>绿泥石>高岭石>伊利石;XRD结果表明皂石对赖氨酸的吸附发生在矿物层间,而绿 泥石、高岭石和伊利石对赖氨酸的吸附主要在矿物表面进行;FTIR和TG结果表明赖氨酸主要取代粘土矿物层间吸附水,以 氢键的形式与Si-O-Si(IVAl)键合。实验结果将有助于进一步探明环境中粘土矿物对有机质的吸附机理。     

Factors affecting the association of fatty acids with mineral particles in sea water

Certain factors influencing the incorporation, transport and release of fatty acids by clay minerals, calcite and marine sediments have been investigated.Salinity was found to be an important factor. The adsorption of heptadecanoic acid by bentonite clay at 4%. was nearly triple that at 0%.. However, from 4%. to 35%., only a minor adsorption increase occurred. This behavior is believed to be related to flocculation of the clay at the lower salinity range. The pH over the range of 6.0–8.5 has a small influence on fatty acid-clay association, depressing it somewhat as the basicity increases.When the temperature of the fatty acid solution was increased from 0°C to 50°C, a decrease in adsorption on to clay was found. This effect may be due to increased water solubility of the acid at higher temperatures, since solubility is very important in controlling the degree of fatty acid-mineral interaction. Furthermore, apparent solubilization of fatty acids by indigenous dissolved organic matter in sea water reduces adsorption on to clay minerals.Based upon the heat of adsorption of ?14.6 kcal/mole, fatty acids are physically bound to clay minerals by weak van der Waals forces and hydrogen bonds.Bentonite and kaolinite were found to be the most adsorptive minerals investigated, followed in order by illite, montmorillonite and calcite. Sediments from Narragansett Bay were found to lie between illite and montmorillonite in adsorptive capacity after indigenous sediment organic matter had been removed. Sediment organic matter reduced fatty acid uptake by a factor of 1.6.     

有机粘土的特性及其对肥料养分的缓释作用

本研究表明 ,表面活性剂 2号不仅可以吸附在蒙脱石、高岭石和凹凸棒石的表面上 ,还可进入蒙脱石的层间 ,将其晶层撑开 ,并以双层小于 65°角斜交于蒙脱石的晶片之间 ,同时有极少量的表面活性剂 2号以单层方式直立于晶片上 ,形成石蜡质构型。由于粘土矿物对表面活性剂 2号的吸附作用 ,使其热性质发生变化 ,去除吸附水的温度降低并出现放热峰。此外 ,还使得有机粘土的含水量和吸湿率较原土有显著降低。有机粘土应用于肥料工业的复混肥生产中 ,不仅可以使其有效成粒率提高 3 0 % ,还可使其养分释放具有显著的缓释效果。     

天然黏土矿物和腐殖酸对纳米乳化油吸持的实验研究

为探讨天然黏土矿物及有机质对纳米乳化油在多孔介质中迁移滞留的影响，本文选取高岭石和蒙脱石这两种黏土矿物以及有机质的典型代表腐殖酸，开展了单一矿物、有机质及有机矿质复合物对纳米乳化油的吸持批实验研究，并运用比表面积全分析、扫描电镜(SEM)、傅里叶红外光谱(FTIR)、X射线衍射(XRD)等技术手段探讨了吸持机理。实验结果表明，介质对纳米乳化油的吸持均符合Freundlich模型；单一矿物及腐殖酸对纳米乳化油的吸持能力表现为：蒙脱石>腐殖酸>高岭石，有机矿质复合样品的吸持能力表现为：蒙脱石-腐殖酸>高岭石-腐殖酸，且均大于其对应的单一样品，出现了“1+1>2”的现象，表明介质组成越复杂，对纳米乳化油的吸持滞留程度越大。进一步分析证实，纳米乳化油主要通过氢键和疏水作用吸持在矿物和腐殖酸表面，表面结构性质是高岭石和蒙脱石吸持过程中的主导因素，因此蒙脱石具有更强的吸持能力，而腐殖酸的吸持主要通过颗粒间聚集作用来实现；对于复合样品，吸持主要通过氢键、配体交换和疏水作用结合来实现。腐殖酸与矿物的复合会增加吸持位点并且增强矿物表面疏水性，从而促进吸持。腐殖酸与纳米乳化油的共吸...     

有机粘土化学研究进展与展望

有机粘土化学是研究粘土矿物与有机化合物之间相互作用的一门学科,其内容包括粘土矿物对有机化合物的吸附作用,粘土矿物对有机化合物转化的催化作用以及有机化合物对粘土矿物的合成与风化的影响。着重阐述了近20年来有机粘土化学的研究进展,并就这一学科领域的研究作了展望。     

Role of the Interlayer Space of Montmorillonite in Hydrocarbon Generation: A Combined Study by TG-FTIR and High Temperature-Pressure Pyrolysis

The interlayer clay-organic complex is an important clay-organic association in sedimentary environments. The interlayer region of clay minerals not only provides storage space for organic matter, but also possesses solid acid sites; and these acid sites were proposed to be involved with the transformation of organic matter into liquid and gaseous hydrocarbons. However, the effect of the organic matter storage in the interlayer space of clay minerals on the hydrocarbons generation has not been made clear. In this study, the interlayer complex of 12-aminolauric acid (ALA) and Na+-montmorillonite (Na+-Mt), labeled as ALAinter-Mt (Na), was synthesized to investigate the role of the interlayer space of montmorillonite in hydrocarbon generation. Simply mixed ALA-Mt complex [ALA-Mt (Na)] was also prepared for comparison. The pyrolysis of ALA and ALA-Mt complexes was studied using thermogravimetry coupled with Fourier transform infrared spectroscopy (TG-FTIR) and a high temperature-pressure system (a confined gold capsule-autoclave system).     

Thermally induced cation migration in Na and Li montmorillonite

In order to determine whether Li⁺ cations penetrate into the octahedral layers of montmorillonites upon mild heating (Hofmann-Klemen effect) ⁵⁷Fe Mössbauer spectra of Na⁺ and Li⁺ exchanged montmorillonite were obtained before and after treatment at 220 ° C. The ⁵⁷Fe nucleus was used as a remote probe to detect electronic perturbations which would occur if a Li cation was to move into the octahedral layer from the interlayer after heating. The ambient Mössbauer spectra showed that a high charge density interlayer cation such as Li⁺ is effective in reducing the phonon energy of ^VIFe²⁺. In addition the EFG at octahedral sites can be significantly modified by interlayer cations as evidenced by the larger quadrupole splitting value measured for the Li⁺-exchanged sample with respect to the Na⁺-sample. Interlayer collapse and migration of exchange cations into the montmorillonite lattice after heating to 220 ° C resulted in the oxidation of the ^VIFe²⁺ and a decrease in site distortion for ^IVFe³⁺. Similar spectral parameters for the Fe³⁺ resonances of both Na⁺ — and Li⁺-heated samples suggested the interlayer cations do not penetrate as far as the octahedral layers. In order to utilize the enhanced sensitivity of ^VIFe²⁺ Δ values to changes in EFG the Fe³⁺ in the heated montmorillonites was reduced to Fe²⁺ with hydrazine. Similar spectral parameters for both the Na⁺ — and Li⁺-exchanged montmorillonite were observed giving further evidence that Li cations do not migrate into vacant octahedral sites.     

蛭石的有机改性研究进展

本文综述了国内近十年关于粘土矿物和蛭石表面性质及表面改性的资料,分析了粘土矿物和蛭石表面改性的原理、方法和影响因素,研究了烷基季铵盐阳离子在粘土矿物和蛭石层间的排布模式,总结了有机粘土和有机蛭石吸附有机物的吸附理论和机理,为有机粘土和有机蛭石在废水处理和聚合物填充增强改性中的应用提供理论依据。     

高岭石和蒙脱石吸附胡敏酸的对比研究

高岭石和蒙脱石分别是暖湿和冷干气候带内典型土壤的代表性矿物,对二者吸附胡敏酸特点的对比研究可以为探索不同地带土壤中重金属的环境行为提供重要的依据。笔者通过一系列实验研究了pH值、离子强度和胡敏酸初始浓度对胡敏酸在高岭石和蒙脱石上吸附量的影响,重点剖析了引起高岭石和蒙脱石在吸附胡敏酸方面表现出的共性和差异的原因。研究结果表明:1)在pH=5条件下,胡敏酸在高岭石和蒙脱石上的吸附量均随着胡敏酸初始浓度和离子强度的升高而逐渐增加;2)胡敏酸在高岭石和蒙脱石上的吸附量均随着pH值的升高而降低;3)pH<6时,高岭石吸附的胡敏酸量多于蒙脱石,pH>6时则相反。这是由高岭石和蒙脱石在不同pH条件下吸附胡敏酸的机制不同造成的。在pH<6时,高岭石与胡敏酸之间的静电引力起主导作用,其次是配位交换作用和氢键作用。此时,蒙脱石以氢键作用为主要吸附机制。在pH>6时,高岭石和蒙脱石的主要吸附机制分别是疏水性作用和阳离子键桥。     

交换液酸碱度对OTAC在蒙脱石中吸附及复合物凝胶粘度影响

在蒙脱石有机改性体系中,交换液酸碱度对蒙脱石荷电性以及十八烷基三甲基氯化铵(OTAC)的电离度影响很大,进而影响OTAC在蒙脱石中的吸附以及制备复合物的凝胶粘度。研究发现,在pH=3的强酸性交换体系中,蒙脱石端面可变电荷为正电荷,OTAC阳离子和蒙脱石之间静电斥力的存在不利于OTAC在蒙脱石上的吸附,吸附量和吸附率分别是0.943CEC和85.7%,制备复合物的凝胶粘度最低,分别是μ0min为45.67Pa·s,μ30min为16.52Pa·s;在pH=10的弱碱性交换体系中,由于蒙脱石层面和端面均带有负电荷,静电引力更有利于OTAC阳离子在蒙脱石层间交换及表面吸附,其吸附量和吸附率最高,分别为1.097CEC和99.71%,制备复合物的凝胶粘度也较高,分别是μ0min为95.93Pa·s,μ30min为37.67Pa·s;在强碱性交换体系中,当pH=11和13时,蒙脱石对OTAC的吸附量和吸附率降低明显,吸附量分别为1.08CEC和1.058CEC,吸附率分别降到98.20%和96.18%,对应复合物的μ0min分别为96.52Pa·s和93.52Pa·s,μ30min分别为36.57Pa·s和36.53Pa·s,究其原因由于交换液中OTAC阳离子和高浓度的钠离子在蒙脱石层间和表面存在竞争吸附导致蒙脱石层间钠离子的交换难度加大。     

粘土矿物保存海洋沉积有机质研究进展及其碳循环意义

海洋沉积物吸附有机质的量和有机质循环周期与粘土矿物类型和吸附方式密切相关,并在全球碳循环中扮演着不同的角色。粘土吸附有机质有物理吸附和化学吸附之分,前者主要存在于粘土的微孔隙中,参与年、十年或百年尺度的循环;后者主要存在于粘土矿物层间和外表面,稳定性较好,有机质易于保存,可参与百万年或更长时间的循环,这种不同时间尺度内的碳循环,将会改写海洋沉积物有机碳“源”、“汇”的关系。不同类型粘土矿物的性质存在差异,决定了吸附有机质量的多寡,蒙脱石的吸附量远大于伊利石的吸附量,这可能是造成全球不同海域中有机碳“源”、“汇”变化的原因。海洋沉积物处于水圈、生物圈和岩石圈的交汇地带,有机碳的差异和变化,都会对全球碳循环及气候变化产生重要的影响。     

The Structure of Montmorillonites Modified with Zwitterionic Surfactants and Their Sorption Ability

In the past four decades, there is a growing use of surfactant modified clay complexes in wide range of applications. The mostly used surfactants to modify the swelling clay minerals are cationic surfactants, such as quaternary ammonium, which consists of two distinct moieties, a hydrophilic head, where the positive charge is concentrated, and a hydrophobic hydrocarbon chain tail. During the surface modification, this kind of surfactant molecules attach on the inner and outer surface of clay minerals, the hydrophilic surface of raw clay minerals may changed into hydrophobic surface. The changes of organophilicity and hydrophobicity of clay minerals enable them used in more wide fields, such as adsorbents for organic contaminant, geotechnical barriers, filling of nanocomposite, etc.     

蒙脱石等粘土矿物对重金属离子吸附选择性的实验研究

矿物质与重金属离子间的相互作用已是当今环境科学、矿物学,土壤化学等学科领域研究的热点。通过蒙脱石,伊利石和高龄石在一定的介质条件下对Ｃｕ＾２＋、Ｐｂ＾２＋、Ｚｎ＾２＋、Ｃｄ＾２＋、Ｃｒ＾３＋五种重金属离子的竞争吸附实验研究,阐明了三种粘土矿物对五种重金属离子的吸附选择性。     

Amino acid adsorption by clay minerals in distilled water

The adsorption of 15 protein amino acids from dilute (~ 10 μM) distilled water solutions onto organic-free kaolinite and montmorillonite clay minerals (1 wt% suspensions) was determined at room temperature over a 48 hour period. The systems came to steady state within 2 hours. Basic (positively charged) amino acids were strongly adsorbed (40–80% removal) by both clay minerals. Neutral (uncharged) amino acids were taken up appreciably (10–15%) by montmorillonite, but little if any (<5%) by kaolinite. Acidic (negatively charged) amino acids were adsorbed (20–35%) only by kaolinite. These adsorption patterns appear to be related in part to electrostatic interactions between the clay mineral surfaces and the different amino acid types. The measured extents and selectivities of adsorption onto these clay minerals are sufficiently great to potentially affect the distributions and reactions of free amino acids in natural environments.     

锂改性蒙脱石矿物中锂的化学状态研究

采用XRD、IR、XPS等测试方法,对锂改性蒙脱石矿物中锂 的化学状态进行分析,发现锂改性过程中,Li+离子不仅与蒙脱石层间吸附阳离子进行交 换,还能置换蒙脱石晶格八面体中的阳离子和进入间隙位置。Li+离子是以三种化学状态 存在于蒙脱石晶格结构中。     

镉在蒙脱石等粘土矿物上的吸附行为研究

研究了土壤中主要硅酸盐粘土矿物蒙脱石、伊利石、高岭石、海泡石对重金属镉的吸附行为.结果表明:硅酸盐粘土矿物吸附镉受酸度和离子强度的影响;吸附反应是快反应,能很好地符合Lagergren二级吸附速度方程;优化条件下的高岭石对镉吸附很弱,蒙脱石、伊利石、海泡石对镉的实验饱和吸附容量分别为2.88、1.08、2.82 mg/g,蒙脱石吸附镉更适合Freundlich拟合,伊利石、海泡石对镉的吸附结果更适合Langmuir拟合;相关性分析表明,硅酸盐粘土矿物对镉的饱和吸附容量大小与其理化性质有关,其中矿物中氧化锰含量高低与其对镉饱和吸附容量大小的相关性达到极显著水平.     

海洋粘土矿物与颗石藻Emiliania huxleyi共培养的实验研究

颗石藻是海洋中广泛分布的超微型浮游藻,经生物矿化作用形成的碳酸钙质颗石,在古海洋学研究中具有重要意义。海洋粘土矿物与有机质的有机-无机相互作用在全球碳循环中扮演着重要角色。本文选取广泛分布于海洋的赫氏颗石藻Emiliania huxleyi与海洋粘土矿物中具有代表性的伊利石和蒙脱石共培养。通过对颗石藻生长曲线和Sr/Ca、Mg/Ca元素比值、颗石藻与粘土矿物样品的紫外可见光吸收光谱、红外吸收光谱和矿物物相等分析,研究海洋粘土矿物与颗石藻的相互作用规律。通过研究表明伊利石对颗石藻的影响较小,蒙脱石因对营养元素的吸附和颗石藻的絮凝作用对颗石藻的生长和Sr/Ca、Mg/Ca元素比值影响较大。颗石藻代谢分泌的生物分子未能通过层间插层作用进入伊利石层间,颗石藻分泌的生物分子可通过插层作用进入并储存于蒙脱石层间,海洋粘土矿物中的蒙脱石与海洋微生物的相互作用值得地球微生物家关注,可能有助于对古海洋环境的认识。