海泡石,人造沸石吸附性质的实验

在室温、常压条件下、运用兰德利胥公式开展海泡石、人造沸石对Ｃａ＾２＋、ＮＨ４＾＋，Ｆ＾－的吸附性质实验研究，分别获得它们的吸附等温曲线，计算出它们的Ｋ值，比较吸附能力大小。用不同方法分别对海泡石、人造沸石进行预处理。实验结果表明，预处理后的海泡石、人造沸石的吸附能力明显增强，对进一步开发，利用海泡石、人造沸石具有实际的意义。     

海泡石对碱金属离子的吸附性能研究

本文对湖南浏阳、北京延庆地区热液型海泡石的物化性能、活化处理工艺条件及其对Na^ ,K^ ,Ca^2 离子的吸附作用进行了研究。实验表明，酸处理的方法可以有效地提高海泡石对Na^ ,K^ ,Ca^2 离子的吸附能力，并且通过正交实验得到最佳酸化工艺条件为：酸化时间为2h，酸的浓度为5％，液固比为35：1，经酸处理的海泡石可以有效地降低饱和Ca(OH)2溶液中Na^ 含量，这为海泡石作为掺和料吸附混凝土细孔中游离的碱性阳离子，抑制混凝土的碱－骨料不良反应的发生提供了实验依据。     

磷酸盐对纳米二氧化钛吸附水体中重金属离子行为的影响和机理分析

纳米二氧化钛(nTiO₂)被广泛应用于去除水体中的重金属。磷酸盐作为水体中普遍存在的无机阴离子,能够对重金属离子在nTiO₂上的吸附特征产生影响。本文聚焦磷酸盐存在条件下nTiO₂胶体颗粒对典型重金属离子(Zn²⁺和Cd²⁺)的吸附行为,以电感耦合等离子体发射光谱法(ICP-OES)测定吸附平衡后水相中重金属离子的浓度。通过批量吸附实验考察不同水化学条件下(离子强度和共存阴离子),磷酸盐对nTiO₂胶体颗粒吸附水体中Zn²⁺和Cd²⁺特征的影响规律。采用经典吸附等温线模型对实验数据进行拟合,并结合纳米颗粒的Zeta电位和粒径变化等表征手段揭示了相关吸附机制。研究发现：(1)磷酸盐的存在能有效地增强重金属在nTiO₂上的吸附,Zn²⁺和Cd²⁺的最大吸附量分别由121.1mg/g和84.7mg/g增加至588.3mg/g和434.8mg/g,增加了3...     

二氧化钛表面键合配位体固相萃取填料的制备及其吸附性能研究

有机配位体/无机纳米复合材料作为固相萃取填料用于重金属离子分离富集是当前分析化学研究的热点课题。本文将含有N、S配位原子的氨基硫脲通过缩合反应接枝于纳米二氧化钛表面,制备了一种新型纳米Ti O2/TSC复合固相萃取填料。通过红外光谱、X射线衍射、X射线光电子能谱和扫描电镜表征,此填料与共混法制备的聚合物包覆纳米二氧化钛复合填料相比,二氧化钛粒子(尺寸200~300 nm)分布更均匀,结构更稳定。用该填料制备的固相萃取小柱静态吸附Sb3+、Cd2+和Ba2+在30℃时饱和吸附量分别为13.9mg/g、12.9 mg/g和11.2 mg/g,在优化的实验条件下三种金属离子的吸附回收率分别达到97.94%、95.65%和94.04%,实验数据重现性高(RSD5.5%),吸附性能优于聚苯乙烯-甲基丙烯醛-氨基硫脲包覆纳米二氧化钛和纳米二氧化钛两种填料。本填料结合ICP-MS测定水样中以上三种离子的检出限分别为0.061μg/L、0.013μg/L和0.075μg/L。     

前言

海泡石(Meerschaum)这一名词由德国人威尔纳于1789年提出,这是由于海泡石的色浅质轻,能浮于海水之上,形似海的泡沫而命名。海泡石的化学分子式为Mg_8〔Si_(12)O_(30)〕(OH)_4·8H_2O,其中有四个为结晶水(OH_2),其余为沸石水及结构水(OH),属S单斜晶系或斜方晶系。通常呈光滑致密的块状体,也有呈纤维状者。在电子显微镜下可见其由细小的纤维杂乱堆积而成。颜色     

海泡石改性及吸附Zn2+研究

金属离子型无机抗菌剂具有安全性好、抗菌广谱、时效长和耐热等许多优良性能,在许多领域有广泛的应用价值。金属离子型无机抗菌剂由金属抗菌离子和无机载体材料组成,其抗菌性能与载体材料对抗菌金属离子的吸附量有关。本文初步研究了对海泡石进行酸改性及用海泡石载抗菌锌离子(Zn2+)的两种工艺方式对海泡石结构及载Zn2+量的影响。通过原子吸收发射光谱、X射线衍射、扫描能谱电子显微镜及傅立叶变换红外光谱等技术的分析表明,用体积浓度为5%的HCL,在70℃温度下对海泡石进行酸处理,在提高海泡石纯度,分散海泡石纤维束、使海泡石结构中孔隙扩大,进而达到更多载入Zn2+目的等方面都是十分必要和有效的方法;采用干湿循环方式将Zn2+载于海泡石能提高海泡石的载Zn2+量,但干湿循环方式操作更复杂,能耗更大,应视具体情况酌情选择使用。     

海泡石对有机染料的吸附行为研究

以热酸活化过的海泡石为吸附剂，研究其对亚甲基蓝、结晶紫和甲基绿3种染料的吸附动力学过程，并分析了浓度、温度等因素对海泡石吸附效果的影响。结果表明，温度的变化对吸附的影响较小，而染料溶液浓度的改变则会对吸附产生很大的影响，由此确定出较适合的反应条件。采用傅立叶红外光谱技术对吸附前后海泡石的结构进行了分析，发现亚甲基蓝由于分子体积较小可以进入海泡石内部通道，而大体积的结晶紫和甲基绿的吸附主要发生在海泡石外表面，且一价有机阳离子会在中性位置发生吸附，形成带电或中性复合物。     

地下水化学组成对Fe2+氧化产生羟自由基的影响

羟自由基(·OH)是自然环境中氧化活性最强的物种,对物质转化具有重要影响.前期研究发现地下水接触O₂可产生·OH,其中Fe2+氧化起主导作用,但地下水化学组成对Fe2+氧化产生·OH的影响尚不清楚.通过室内模拟实验,探究了地下水中常见组分(Ca2+、Mg2+、腐殖酸(HA)和磷酸根)对Fe2+氧化产生·OH的影响.结果表明,pH 6.5时0.357 mM Fe2+在5 h内氧化完全,产生约1.8 μM的·OH;Ca2+(1~6 mM)、Mg2+(1~4 mM)对Fe2+氧化和·OH产生无明显影响;HA(10~30 mg/L)促进Fe2+氧化和·OH产生,促进效果随pH降低而增强;磷酸根(0.01~0.03 mM)抑制Fe2+氧化,对·OH产生的影响为先抑制后促进.      

蒙脱石负载型零价铁纳米颗粒吸附水体中Cr(Ⅵ)污染物实验研究

零价铁纳米颗粒具有许多异于本体物质的独特性质,在废水处理方面应用潜力巨大。以蒙脱石为载体和分散剂,通过硼氢化钠液相还原法制备了零价铁纳米颗粒。采用电镜及多种谱学技术手段对所得铁纳米颗粒进行了表征。结果表明,铁纳米颗粒大致呈球状形貌,平均粒径约为55 nm,在蒙脱石表面分散良好,具有零价铁内核-铁氧化物外壳结构,提高了纳米铁在空气氛中的稳定性。通过批次实验考察了负载型铁纳米颗粒净化Cr(Ⅵ)的效率、过程及机理。净化效果受p H值影响显著,在最优p H值为1.0条件下,零价铁内核因其表面氧化膜酸溶而出露,可作为有效成分快速高效去除水体中Cr(Ⅵ)污染物,机理为零价铁将吸附至其表面的Cr(Ⅵ)异相还原为Cr(Ⅲ)而去除。属自发放热吸附过程,动力学行为符合准二级模型,吸附等温线可用Langmuir方程较好拟合。研究成果为新型纳米零价铁材料的制备及其铬污染治理提供了理论支撑。     

国内外海泡石族粘土资源概况

海泡石族矿物包括海泡石、凹凸棒石和坡缕缟石,是一组具链式层状结构的富镁硅酸盐粘土矿物。海泡石(Sepiolite)发现于1789年,原名是“Meerschaum”,指一种色白质轻的致密土状硅酸镁矿物,它可浮在水面,即德文“海的泡沫”意思,1847年正式叫海泡石。海泡石的典型化学式为Mg_8Si_(12)O_(30)(OH)_4(OH_2)_4·8H_2O其中化学组成变化较大,普遍存在Al对Si和A1、Fe、Ni对Mg的类质同象置换,结果形成不同类型的海泡石:     

Morphological, geochemical composition and origins of near-surface atmospheric dust in Changsha city of China

Near-surface atmospheric dust in Changsha city of China was analyzed in terms of morphological and geochemical composition. Morphological and chemical composition of the dust particles were analyzed by environmental scanning electron microscopy coupled with an energy-dispersive X-ray analyzer. Results indicated that the atmospheric dusts were mainly composed of spherule, plate, irregularly shaped and agglomerate, which contains variable sizes and amounts of particles. The dust particles could be categorized into five groups based on their chemical characteristic: Al-, Si-, Ca-, C-rich particles and aggregate. These particles and aggregate could be directly related to nearby polluting activities, such as building construction, traffic emission and coal combustion. The X-ray diffraction results show that the main minerals for atmospheric dust are gypsum, quartz and calcite. Mica, halloysite, montmorillonite, hematite, brushite, zeolite, sepiolite, feldspar, alite, dickite, SiS₂, Fe₆(OH)₂CO₃, FeSO₄, CdSO₄, Pb(NO)₂O₃, Al₂SO₄(OH)₄, As₂O₃SO₃, (NH₄)₂SO₄, NH₄Cl, K(NH₄)·Ca(SO₄)₂·H₂O are also detected in samples. The identification of heavy metals shows that the concentrations of Cr (403.5?mg?kg^?1), Cu (126?mg?kg^?1), Zn (1541.5?mg?kg^?1), Cd (2.5?mg?kg^?1) and Pb (348?mg?kg^?1) in the atmospheric dust are much higher compared to background value of soil. It indicates that the heavy metal (Cr, Cu, Zn, Cd and Pb) in the atmospheric dust is mainly due to human activities. The identification of main sources of atmospheric dust collected in typical areas can help to control the polluting sources in urban area.     

Photodegradation of dimethyl phthalate (DMP) by UV–TiO<Subscript>2</Subscript> in aqueous solution: operational parameters and kinetic analysis

In this paper, the adsorption and degradation phenomenon involved in the photocatalytic degradation of dimethyl phthalates (DMPs) by titanium dioxide (TiO₂) was studied. A variety of operating variables were selected firstly. Then, it was proved that even for such weak adsorption properties molecules as DMP, adsorption was still an important prerequisite for photolysis. A surface-mediated reaction process was proposed that the photodegradation of DMP assisted by TiO₂ particles occurred primarily at the surface of the photocatalyst rather than in the homogeneous phase. According to Langmuir–Hinshelwood model, the adsorption constant determined from the dark adsorption was far less than that obtained in the light condition. Enhanced DMP adsorption on the surface of TiO₂ under irradiation was the possible reason for the improvement of photodegradation efficiency. Under the irradiation of light, a synergistic mechanism of adsorption and photocatalysis was responsible for DMP degradation. The quantitative analysis by adding scavengers indicated that ^·OH radical was primarily responsible for the photodegradation of DMP. It was further verified that ^·OH was produced much more from conduction band electrons rather than valance band holes toward photodegradation of DMP by adding foreign Cu²⁺.     

雪硅钙石的矿物学特征研究

研究发现,雪硅钙石是一种硅酸钙水化物.根据电子探针分析结果计算得到的化学式为（Ca_4.424K_0.021Mg_0.003）_4.448（Si_5.731Al_0.728）_6.465O₁₆（OH）₂·4H₂O,与经典化学式Ca₅Si₆O₁₆（OH）₂·4H₂O基本一致.通过X射线粉晶衍射结果分析认为,该雪硅钙石属于1.4 nm类型雪硅钙石.雪硅钙石矿物呈放射状纤维集合体,颗粒大小为0.2 mm×0.5 mm×0.3 mm,黄褐色,正低突起,最高干涉色为Ⅰ级黄,二轴晶正光性,光轴角为53°.     

On the transition between 2D and 3D dunes

Sediment transport in sand-bedded alluvial channels is strongly conditioned by bedforms, the planimetric morphology of which can be either two- or three-dimensional. Experiments were undertaken to examine the processes that transform the bed configuration from two-dimensional (2D) dunes to three-dimensional (3D) dunes. A narrowly graded, 500 μm size sand was subjected to a 0·15 m deep, non-varying mean flow ranging from 0·30 to 0·55 m sec⁻¹ in a 1 m wide flume. Changes in the planimetric configuration of the bed were monitored using a high-resolution video camera that produced a series of 10 sec time-lapsed digital images. Image analysis was used to define a critical value of the non-dimensional span (sinuosity) of the bedform crestlines that divides 2D forms from 3D forms. Significant variation in the non-dimensional span is observed that cannot be linked to properties of the flow or bedforms and thus appears random. Images also reveal that, once 2D bedforms are established, minor, transient excesses or deficiencies of sand are passed from one bedform to another. The bedform field appears capable of absorbing a small number of such defects but, as the number grows with time, the resulting morphological perturbations produce a transition in bed state to 3D forms that continue to evolve, but are pattern-stable. The 3D pattern is maintained by the constant rearrangement of crestlines through lobe extension and starving downstream bedforms of sediment, which leads to bifurcation. The experiments demonstrate that 2D bedforms are not stable in this calibre sand and call into question the reliability of bedform phase diagrams that use crestline shape as a discriminator.     

纳米TiO2光催化降解亚甲基蓝

在以钛酸丁酯为钛源,采用溶胶-凝胶法合成制备纳米TiO2催化剂样品的基础上,将其用于在紫外光照射和无光照射条件下进行亚甲基蓝降解的实验研究,并与P-25纳米TiO2进行光催化降解对比研究。对在不同条件下合成制备样品的光催化降解率的差异,通过X射线粉晶衍射、扫描电镜等从物相组成、微观结构等因素上进行了分析和探讨。结果表明,采用溶胶-凝胶法在450℃焙烧2 h所得到的纳米TiO2具有很好的光催化降解亚甲基蓝的能力,当催化剂样品质量浓度为2.5 g/L,亚甲基蓝初始浓度为5.0 mg/L时,室温下光催化反应3 h,其降解率达98%以上,其光催化降解率比P-25纳米TiO2高;光催化降解率与催化剂样品的制备条件、物相组成、颗粒尺寸等因素有关。     

Interlayer proton transfer in brucite under pressure by polarized IR spectroscopy to 5.3 GPa

In order to investigate the behaviour of proton in brucite under pressure, polarized IR absorption spectra and polarized absorbance distributions of (001) and (110) oriented single crystal of brucite under high pressure were measured by Fourier transform polarized infrared microspectroscopy with diamond anvil cell. A pressure-induced absorption peak at 3645 cm⁻¹ observed under pressures over 2.9 GPa was confirmed to be due to a secondarily formed OH dipole. Polarized absorbance distribution measured under pressure of (110) suggests that the secondary OH dipole is oriented 136.0° to c-axis under 5.3 GPa. Isotropic absorbance distribution of (001) suggests that the secondary OH dipole is disorderly trifurcated. Abrupt onset of the secondary peak and its reverse pleochroism suggest that the process of secondary OH dipole formation is due to proton transfer between layers in brucite. The calculated orientation of the secondary OH dipole consistent with the O-H···O′ angle revealed by neutron diffraction supports the existence of proton transfer along H···O′. The secondary OH dipole implies a new site of proton in brucite under pressure. Received: 6 March 1997 / Revised, accepted: 9 June 1997     

Experimental Petrology of the 1991-1995 Unzen Dacite, Japan. Part II: Cl/OH Partitioning between Hornblende and Melt and its Implications for the Origin of Oscillatory Zoning of Hornblende Phenocrysts

High-temperature–pressure experiments were carried outto determine the chlorine–hydroxyl exchange partitioncoefficient between hornblende and melt in the 1992 Unzen dacite.Cl in hornblende and melt was analyzed by electron microprobe,whereas OH in hornblende and melt was calculated assuming anionstoichiometry of hornblende and utilizing the dissociation reactionconstant for H₂O + O = 2(OH) in water-saturated melt, respectively.The partition coefficient strongly depends on the Mg/(Mg + Fe)ratio of hornblende, and is expressed as ln K₁ = (Cl/OH)_hb/(Cl/OH)_melt= 2·37 – 4·6[Mg/(Mg + Fe)]_hb at 2–3kbar and 800–850°C. The twofold variation in Cl contentin the oscillatory zoned cores of hornblende phenocrysts inthe 1991–1995 dacite cannot be explained by the dependenceof the Cl/OH partition coefficient on the Mg/(Mg + Fe)_hb ratio,and requires c. 80% variation of the Cl/OH ratio of the coexistingmelt. Available experimental data at 200 MPa on Cl/OH fractionationbetween fluid and melt suggest that c. 1·2–1·8wt % degassing of water from the magma can explain the required80% variation in the Cl/OH ratio of the melt. The negative correlationbetween Al content and Mg/(Mg + Fe) ratio in the oscillatoryzoned cores of the hornblende phenocrysts is consistent withrepeated influx and convective degassing of the fluid phasein the magma chamber. KEY WORDS: chlorine; element partitioning; hornblende; oscillatory zoning; Unzen volcano     

九连墩楚墓青铜器锈蚀产物的拉曼光谱分析

利用拉曼光谱对几件九连墩楚墓出土青铜器的腐蚀产物进行了测试。结果表明,九连墩楚墓出土的青铜器上主要的锈蚀产物为孔雀石[CuCO_3·Cu(OH)_2],存在部分蓝铜矿[2CuCO_3·Cu(OH)_2]和少许副氯铜矿[Cu_2(OH)_3Cl];此批青铜器锈蚀情况比较复杂,锈蚀种类比较丰富。在此基础上,探讨了科学保护此批青铜器的方法。     

Hydrogen bonding interactions in phase A [Mg7Si2O8(OH)6] at ambient and high pressure

Neutron powder diffraction data of phase A (Mg₇Si₂O₈(OH)₆) were collected at ambient pressure and 3.2?GPa (calculated from the compressibility of phase A) from the deuterated compound, and the structure was refined using the Rietveld method. The derived crystal structure implies that hydrogen atoms occupy two distinct sites in phase A, both forming hydrogen bonds of different lengths with the same oxygen atom. This picture is supported by IR spectra, which exhibit two absorption bands at 3400 and 3513?cm^?1 corresponding to OH stretching vibrations, and proton NMR spectra, which display two peaks with equal intensities and isotropic chemical shifts of 3.7 and 5?ppm. The D-D distance [D(1)-D(2) distance] at ambient pressure was found to be 2.09?±?0.02?Å from the neutron diffraction data and 2.09?±?0.05?Å from the NMR spectra. At 3.2?GPa, there is no statistically significant increase in the O-D interatomic distance while the hydrogen bonding interaction D···O appears to increase for one of the hydrogen sites, D(1), which has the stronger hydrogen bonding interaction compared with the other hydrogen, D(2), at ambient pressure. The O-D bond valences, determined indirectly from the D···O distances were 0.86 and 0.91 at ambient pressure, and 0.83 and 0.90?at 3.2?GPa, for D(1) and D(2), respectively.     

多孔结构无机材料比表面积和孔径分布对调湿性的影响

测试海泡石、沸石、硅藻土和坡缕石粘土的孔径和比表面积,研究其孔径和比表面积与吸放湿能力的对应关系.利用氮气等温吸附对孔隙结构进行测试、分析,通过BET法计算得出其比表面积分别为81.56、2.46、1.68和187.70 m2/g,平均孔径分别为8.53、18.20、31.57和11.79 nm.在温度25℃相对湿度分别为75%和35%的条件下进行吸放湿试验,4种样品的最大吸湿量分别为5.6%、2.2%、1.8%和6.0%,放湿量分别为4.4%、1.8%、1.6%、5.0%.数据对比发现,比表面积大且孔径分布符合在相应温湿度下以Kelvin公式计算出的孔径分布特点的矿物材料,如海泡石,吸放湿能力强.