不同氧化物硼负载体吸附锰离子的特性研究

以人工合成针铁矿（Goethite，简写为G），水锰矿（Manganite，简写为M），经硼砂处理的吸附态针铁矿（简写为Ad—B-G），吸附态水锰矿（简写为Ad—B-M），经硼酸处理的包被态针铁矿（简写为Oc—B—G），包被态水锰矿（简写为Oc-B—M）等6种氧化物为研究对象，在等温条件下，用吸附平衡法研究了6种硼负载体对Mn^2＋的吸附解吸行为。结果表明，吸附Mn^2＋能力：Oc—B—G〉Ad—B—G〉G；Ad—B—M和Oc—B—M吸附Mn^2＋量最大，M吸附能力最弱。6种硼负载体Mn^2＋吸附量随pH升高而增加,但铁氧化物和锰氧化物之间有差别。不同形态锰氧化物吸附Mn^2＋前后溶液pH变化不同，吸附等量Mn^2＋离子时，Ad—B—M向溶液中释放H^＋量最多，Oc—B—M最少。上述结果说明，硼的参与不仅可改变氧化物吸附Mn^2＋离子的行为，而且对反应体系的影响也不尽相同。     

针铁矿和针铁矿—胡敏酸复合体对Se(Ⅳ)吸附机制

研究了针铁矿和针铁矿—胡敏酸复合体对Se(Ⅳ)的吸附机制。结果表明:针铁矿和复合体对Se(Ⅳ)的最大吸附容量分别为0.202 mmol g-1和0.159 mmol g-1。针铁矿的等温吸附数据适合用Langmuir模型拟合,而Freundlich模型更适合描述复合体的等温吸附过程。针铁矿的等电点(IEP)在7.0附近,复合体的IEP3.0;当p H=4.0时,它们的表面电位分别为46.6 m V和-40.5 m V。X—射线光电子能谱(XPS)分析显示,针铁矿和复合体表面Fe2p3/2的电子结合能(B.E.)分别为711.4e V和711.5 e V,复合体表面C1s的B.E.值为284.8 e V。初始p H=4.0时,样品与Se(Ⅳ)相互作用后的主要变化体现在:(1)针铁矿和复合体的悬浮液p H分别升高至4.4和4.2,表面电位分别降低了39.08 m V和升高了1.8 m V;(2)针铁矿表面Fe(Ⅲ)的B.E.值降低了0.4 e V,但吸附态Se(Ⅳ)的B.E.值无明显变化;(3)复合体表面Fe(Ⅲ)的B.E.值降低了0.3 e V,表面C-O中C的B.E.值由285.7 e V升高至286.5e V,吸附态Se(Ⅳ)的B.E.值升高了0.6 e V。针铁矿和复合体吸附Se(Ⅳ)的主要机制包括表面配合反应(复合体表面铁羟基与HSe O3-之间存在双齿配位)、静电引力、氢键等作用。此外,复合体表面吸附态Se(Ⅳ)同时与针铁矿和胡敏酸发生了作用,形成了针铁矿—Se(Ⅳ)—胡敏酸三元体。     

锰掺杂对针铁矿的结构、表面性质及吸附硒的影响

水热条件下制备了针铁矿(Goe)和不同含量锰掺杂产物(G-Mn0.1、G-Mn0.2、G-Mn0.3和G-Mn0.5),用X-射线衍射(XRD)、透射电镜(TEM)、氮气物理性吸附、Zeta电位分析、酸碱滴定等手段对样品进行了表征,并研究其对亚硒酸盐(Se(Ⅳ))和硒酸盐(Se(Ⅵ))的吸附特性。结果表明:低比例的锰掺杂(锰/铁的摩尔比RMn/Fe=0.1~0.2)显著促进了针铁矿晶体沿b轴方向生长,导致针铁矿颗粒的长径比增大,形貌由短纺锤体形变为大长径比的扁平针状;当RMn/Fe=0.3~0.5时,样品中出现了大量的掺锰磁铁矿,且针铁矿晶体的b轴方向生长受到严重的抑制而a轴方向生长受到一定程度的促进并导致针铁矿颗粒呈纤细状。Goe、G-Mn0.2和G-Mn0.5的比表面积分别为36.78、53.22和71.33 m2·g–1,表面分形度分别为2.31、2.53和2.59,平均孔径分别为13.73、15.59、6.92 nm,Zeta电位零点分别为7.36、6.58和5.31,pH5.0时的Zeta电位分别为40.5、35.3和4.92 mV。3种样品的表面活性羟基密度表现为Goe相似文献   

硼酸共沉淀法合成含硼氧化铁的结构状况解析

在水合法制备针铁矿过程中添加H3BO3,对合成的样品作红外光谱和比表面积分析,结果表明,共沉淀法合成的样品在1343 cm-1处有特征吸收峰,说明在针铁矿形成过程中,如果有H3BO3参与,则形成的氧化铁中存在Fe—O—B键结构,可能在氧化铁内部有一种新硼铁化合物生成。比表面积测定表明,含硼氧化铁比表面积增加4倍以上,反映了氧化铁与H3BO3并非机械混合物,其表面性质因为Fe与B反应而发生改变,B阻止氧化铁向高聚合态转变。     

有机酸对针铁矿和膨润土吸附Cd2+、Pb2+的影响

用平衡吸附法研究了不同浓度的有机酸（乙酸、酒石酸和柠檬酸）对针铁矿和膨润土吸附Cd^2＋、Pb^2＋的影响。结果表明：（1）低浓度（〈0．6mmolL^-1）有机酸促进供试矿物吸附Cd^2＋和Pb^2＋，随着有机酸浓度增加，吸附逐渐被抑制。高浓度（〉1．0mmolL^-1）有机酸对Pb^2＋吸附的抑制作用比对Cd^2＋的强。有机酸浓度的变化对针铁矿Cd^2＋、Pb^2＋吸附率的影响大于对膨润土的。（2）不同Cd^2＋浓度下，有机酸对膨润土Cd^2＋吸附强度的影响大于针铁矿。加入高浓度Cd^2＋（8．0mmolL^-1）时，低浓度有机酸对膨润土吸附Cd^2＋的促进作用比加入低浓度Cd^2＋（0．4mmolL^-1）时明显，高浓度有机酸对膨润土吸附Cd^2＋的抑制作用与低浓度Cd^2＋时相近。（3）低浓度有机酸（〈0．6mmolL^-1）时，酒石酸、柠檬酸对针铁矿吸附Cd^2＋的促进作用大于乙酸，而它们对膨润土吸附Cd^2＋的促进作用相似；在三种有机酸高浓度（〉1．0mmol L^-1）时，针铁矿对Cd^2＋的吸附都趋于稳定，而柠檬酸对膨润土吸附Cd^2＋的抑制作用比乙酸和酒石酸的明显。不同种类有机酸下，矿物对Pb^2＋吸附率大小的变化基本一致。     

镉在针铁矿、针铁矿-腐植酸复合胶体中吸附解吸行为比较研究

采用批平衡试验法,比较研究了重金属镉在针铁矿和针铁矿-腐植酸复合胶体中的吸附热力学和动力学行为。结果表明,在试验浓度范围内,两种吸附剂对Cd2＋的等温吸附特征均可用Langmuir、Freundlich和Linear方程加以描述。其中以Langmuir方程的拟合效果最佳,线性相关系数为：0.991、0.999,由此推导出的最大吸附量分别为41.667和45.455mg·g^-1,表明腐植酸与针铁矿复合胶体较单一针铁矿的吸附力有所提高,且所吸附的镉均难以解吸,平均解吸率分别为5.871%和1.068%。胶体对Cd^2＋的吸附是一个快速反应过程,4h达到吸附平衡。Elovich方程是拟合吸附动力学过程的最优方程（相关系数分别为0.987和0.997）。通过计算镉在针铁矿和针铁矿-腐植酸复合胶体中的吸附自由能变化量（ΔG的绝对值均〈40kJ·mol^-1）,推测镉在两种胶体中的吸附为物理吸附过程,其吸附机理可能有氢键、偶极作用力和范德华力等作用,而不存在化学键合作用。     

温度对硼在三种矿物上吸附-解吸特性的影响

在实验室对天然Ca 蒙脱进行了纯化 ,并在一定条件下人工合成了针铁矿、水锰矿 ,以此作为实验材料 ,用吸附—解吸平衡法和反应动力学方法研究了温度对硼在Ca 蒙脱 ,针铁矿 ,水锰矿上的吸附、解吸特性的影响。结果表明 :随温度升高 ,Ca 蒙脱对硼的吸附量升高 ,其对硼的解吸滞后性下降 ,水锰矿和针铁矿对硼的吸附量下降 ,其对硼的解吸滞后性加强。计算表明 ,在常温下 ,硼在Ca 蒙脱上的吸附热为 63.0 8kJmol- 1 ,在针铁矿和水锰矿上分别为 - 1 2 2 .45和 - 93 .91kJmol- 1 ,硼在Ca 蒙脱、针铁矿和水锰矿上的解吸热分别为- 31 .0 2 ,53 .95和 46 .30kJmol- 1 。上述结果说明 ,硼在Ca 蒙脱上的吸附为吸热过程 ,解吸为放热过程 ;硼在针铁矿、水锰矿上的吸附为放热过程 ,解吸为吸热过程。随着温度的升高 ,硼与矿物的初始反应速率明显加快 ,而整体反应速率略有下降。     

铁铝氧化物–层状硅酸盐矿物互作对Cr (Ⅵ)和As (Ⅴ)吸附的影响

以高岭石、蒙脱土、针铁矿和三水铝石四种单一典型土壤矿物以及针铁矿-蒙脱石和三水铝石-蒙脱石（质量比为1:1）两种代表性土壤矿物复合体为吸附材料，采用吸附平衡实验、能谱分析（(EDS）、红外光谱、扫描电镜、酸碱滴定和zeta电位测定等方法，研究了铁铝氧化物与层状硅酸盐矿物之间的相互作用对Cr(Ⅵ)和As(Ⅴ)吸附的影响及其机制。吸附平衡实验和EDS实验结果表明，两种复合体对Cr(Ⅵ)和As(Ⅴ)的吸附容量均小于其两种组成矿物单一体系吸附量的平均值，即铁铝氧化物与蒙脱石的互作降低了这些氧化物对Cr(Ⅵ)和As(Ⅴ)的吸附能力。表面性质表征结果表明，与蒙脱石复合后，针铁矿与三水铝石表面的正电荷均被完全中和，电荷符号发生反转。与理论值相比，三水铝石-蒙脱石复合体的表面位点总浓度无明显变化，比表面积减小。针铁矿-蒙脱石复合体的比表面积与理论值无明显差异，但矿物表面位点浓度减小，表面羟基红外吸收峰强度减弱。氧化物与层状硅酸盐矿物互作改变了矿物表面性质，这可能是导致氧化物对Cr(Ⅵ)和As(Ⅴ)的吸附能力降低的主要原因。当评估污染元素在土壤中有效性时应当考虑土壤固相组分间的互作对离子吸附的影响。     

硼酸共沉淀法合成含硼氧化铁的结构状况解析

在水合法制备针铁矿过程中添加HBO3,对合成的样品作红外光谱和比表面积分析.结果表明,共沉淀法合成的样品在1343 cm处有特征吸收峰,说明在针铁矿形成过程中,如果有H3BO3参与,则形成的氧化铁中存在Fe-O-B键结构,可能在氧化铁内部有一种新硼铁化合物生成.比表面积测定表明,含B氧化铁比表面积增加4倍以上,反映了氧化铁与H3BO3并非机械混合物,其表面性质因为Fe与B反应而发生改变,B阻止氧化铁向高聚合态转变.     

几种常见矿物与硼作用的红外光谱特性研究

对几种常见矿物及其与硼反应的红外光谱比较发现 ,硼在供试矿物上解吸的图谱更接近硼在矿物上吸附的图谱 ,而与无硼矿物图谱相差较大 ,故硼在几种常见矿物上都表现出不同程度的滞后性。针铁矿吸附硼后 ,在 1 40 0～ 1 44 0cm- 1 和 1 0 0 0～ 1 2 0 0cm- 1 范围处谱峰有不同程度的增强 ;水锰矿、三羟铝石和Ca 蒙脱石吸附硼后 ,此处谱峰却减弱 ,而在30 0 0～ 360 0cm- 1 处的谱峰 ,也随硼的吸附而明显减弱 ;Ca 蒙脱、三羟铝石吸附硼后 ,其图谱在 1 40 0～ 1 44 0cm- 1 和 1 62 0～ 1 670cm- 1 处的谱峰变化相似 ;水锰矿吸附硼的图谱在 1 0 0 0cm- 1 和 1 40 0～ 1 44 0cm- 1 处与三羟铝石吸附硼的图谱也有相似之处。     

Effect of porosity of goethite on the sorption of six heavy metal ions

Seven different samples of goethite with differing crystallinity were prepared and the rate of reaction of six metal ions was measured for up to 4 weeks. The ions used were: Cu²⁺, Pb²⁺, Cd²⁺, Mn²⁺, Ni²⁺ and Cr³⁺. For Cu, decreasing goethite crystallinity, and therefore increasing porosity, increased the rate of reaction. In contrast, for Pb there was no effect. Hydrothermal treatment, which was used to induce ‘healing’ in one of the goethites, did not prevent the continuing reaction. It decreased the rate of reaction for Cu, Mn and Cd, but had no effect on Ni and Cr. This suggests that the main route for Ni and Cr is not via pores, but by lattice diffusion. The presence of silicate in the goethite decreased the reaction of Mn and Cd. We suggest that silicate decreased the spaces between goethite domains and that these spaces are the pathways largely used by these two ions. These observations show that metallic cations differ amongst themselves, and differ from anions such as phosphate, in the pathways they follow when they penetrate materials such as goethite subsequent to an initial adsorption reaction.     

Atomic force microscopy (AFM) investigations of the surface topography of a multidomain porous goethite

A multidomain goethite was analysed with atomic force microscopy (AFM) to obtain information about the size and shape of pores on the surface, which are important for sorption processes of cations and anions. Wedge-shaped pores > 100 nm long at the surface occurred at the domain boundaries. They were 20-30 nm wide, becoming narrower towards the interior of the crystals to 2 nm and less. The AFM showed these pores to be at least 4–6 nm deep. The shape of the pores suggests that smaller pores continue much further into the interior of the crystals. Besides the irregularities between domains, randomly distributed steps of < 1 nm occurred. Hydrothermal treatment did not change crystal size, but made the surfaces smoother and reduced both the size and number of the pores and also the BET surface area (from 75.3 to 35.1 m² g^?1). The existence of meso- (2–30 nm width) and micropores (< 2 nm width) in goethite crystals explains the slow diffusion of heavy metals, phosphate and other ions into goethite particles. Therefore, the external and internal surfaces of goethite crystals and their spatial heterogeneity have to be taken into account in models of ion adsorption by goethite.     

Effects of crystallinity of goethite: I. Preparation and properties of goethites of differing crystallinity

We prepared five samples of pure goethite and three samples of aluminous goethite with mole fractions of aluminium ranging from 0·05 to 0·20. One of the samples of pure goethite was repeatedly heated in an autoclave at 150°C. We studied the samples using transmission electron microscopy and XRD and we measured the surface area (BET), rate of dissolution of the samples in acid, the surface charge in four concentrations of sodium nitrate from pH 4–10, and the sorption of calcium and chloride from a dilute solution of calcium chloride. Surface areas ranged from 18 to 132 m² g^?1. The BET adsorption-desorption isotherms had hysteresis loops which increased as the surface area increased. These showed that there were pores present with diameters smaller than 2 nm and that the number of pores increased as the surface area increased. All samples of goethite showed typical X-ray diffraction patterns but with peak heights decreasing, and width increasing, as surface area increased. Mean coherence lengths, as determined by XRD line broadening, were smaller than those determined by transmission electron microscopy. This was because each crystal was composed of several domains, and the XRD data reflect the size of the domains. Heating one of the goethite samples in an autoclave caused most of the domains to coalesce and slightly decreased the surface area. As the surface area of the eight goethite samples increased, the mean coherence length in the direction of the a, b and c axes decreased. The better crystallized samples dissolved more slowly in acid and the dissolution curves were sigmoid because the acid was able to penetrate between the domains allowing access to a larger surface area and consequently accelerated dissolution. The points of zero charge increased with increasing surface area of the goethite. The charge carried by the goethite at pH values distant from the point of zero charge increased as the surface area increased. This may indicate movement of protons or hydroxyl ions into pores or other defects in the crystal. The effects of pH and of salt concentration on surface charge were closely described by the variable-charge/variable-potential model. This model also closely described adsorption of Ca²⁺ and Cl^? from calcium chloride solutions requiring only the allocation of constants for these ions. The substitution of aluminium for iron did not affect the charge properties of goethite.     

水溶性有机物与多环芳烃结合特征的红外光谱学研究

水溶性有机物（DOM）与多环芳烃（PAHs）之间的相互作用一直是尚未弄清的理论问题。对其正确阐释有利于更好地理解DOM对PAHs环境行为与生态效应的影响及科学地评估PAHs的环境风险，并对PAHs污染土壤的修复具有极其重要的意义。本研究以有机物料猪粪、污水污泥和带根茬水稻土作为DOM的提取材料，以菲（Phenanthrene，Phe）和芘（Pyrene，Pyr）为PAHs代表，采用红外光谱学技术研究DOM与PAHs的相互作用。红外图谱显示，供试DOM在4000—3000cm^-1、2969—2900cm^-1、1700-1375cm^-1、1300—1000cm^1和900-600cm^-1存在明显的吸收峰，这说明DOM中含有-OH或酚-OH、-NH、苯环、-C-O及-CH2等功能团。对比DOM与DOM—Phe／Pyr的图谱发现，DOM—Phe／Pyr在4000—3000cm^-1、1700—1375cm^-1和900—600cm^-1的吸收峰发生不同程度的朝长波方向飘移，表明NH-π和π-π作用参与了DOM与Phe及Pyr结合物的形成。     

Removal of Phosphate from Waste Waters by Adsorption

In this study, the adsorption of phosphate on gas concrete from aqueous solutions has been studied as functions of temperature, mixing rates and suspension pH. Over 99% of phosphate removal was found. The chemical composition of the gas concrete has been defined by X-ray analysis. Experimental data was fitted to the Langmuir equation in order to Langmuir coefficients. After calculating Langmuir coefficients, adsorption free energy (Δ G ⁰ _ads.) has been determined. In order to gather information about adsorption mechanism, electrophoretic mobilites of particles were measured at various pHs by using Zeta meter 3.0+. It has been found that the adsorption is driven by the interactions between the ionizations of CaO and Al₂O₃ and the formation of AlPO₄. According to the BET (N₂) measurements, the specific surface area of gas concrete was found as 22 m²g^-1. The surface area after adsorption has been found as 17 m²g^-1. The surface area covered by adsorbate has been found as 5.23 m²g^-1 by usinga_s = n^s _m. a_m. N_A. These two areas determined by BET and Langmuir model were close to each other (BET: 22 m²g^-1–17 m²g^-1).     

不同pH、电解质浓度条件下草酸对针铁矿吸附Cd(II)的影响及机制

用吸附平衡法研究了不同草酸浓度、体系pH对针铁矿 (G)吸附Cd2+的影响与机制以及电解质 (KNO3)浓度对针铁矿、草酸化针铁矿 (G+40 )吸附Cd2+的影响差别及原因。结果表明 ,低浓度草酸 (1mmolL-1 )促进Cd2+的吸附 ;高浓度草酸 (1mmolL-1/sup )抑制Cd2+的吸附。已吸附在针铁矿表面的草酸对Cd2+ 吸附的影响与液相中草酸的影响不同 ,这主要与草酸引起的针铁矿表面电荷性质的变化、草酸在固液两相间的分配、草酸与Cd2+的配合作用和竞争作用有关。电解质 (KNO3)浓度对针铁矿和草酸化针铁矿吸附Cd2+的影响明显不同 ,随KNO3 浓度的提高 ,针铁矿的Cd吸附率由 44.5%增至 95%以上 ,而草酸化针铁矿吸附率由 29%降至6.2% ,这主要决定于二者的电荷零点 (PZC)和体系pH变化的不同。     

7Be: 中国贵州Hongfeng湖流域表土季节性侵蚀的地球化学示踪剂

7Be penetrative depth in undisturbed surface soil is within 4mm.^7Be activity shows exponential decrease with soil depth,which is expressed as a diffusion process.7Be penetrative depth in undisturbed surface soil is apparently deeper in the fall (0.22-0.37g cm^-1) than in the spring (0.11-0.28g cm^-2) at the same site;Whereas,^7Be apparent activity at the top of surface soil is higher in the spring (0.3-2.2Bq g^-1)than in the fall (0.2-0.5Bqg^-1) at the same site,The 7Be inventory(189-544Bq m^-2)changes with both locations and seasons.Although the ^7Be flux to the earth‘s surface increases with amount of precipitation,its maximum inventory in the soil profiles decreases to 30%-40% after the rainy period.Calculated by the diffusion equation,the erosion and accumulation rates of soil particles are agreeable with the observation in situ,Which shows that the rates in fall are 1.5 times those in spring.The eroded soil particles almost all have been removed on the tablelands rathel than transported into the drainage system.This indicates that the soil erosion process in the karst region is only partial transportation within a short distance.     

磷和柠檬酸共存对高岭石和针铁矿吸附铅的影响

通过平衡吸附试验及矿物电动电位(Zeta电位)的变化分析,研究了磷(P)和柠檬酸(CA)共存对针铁矿和高岭石吸附铅的影响。结果表明:(1)针铁矿和高岭石对铅的吸附量随柠檬酸浓度的升高呈现"峰形"曲线变化,铅吸附量达到峰值的柠檬酸浓度均为0.5 mmol L~(-1),不同浓度磷存在下柠檬酸对矿物吸附Pb2+量有不同程度增加。(2)随着磷添加浓度的增加,两种矿物对铅吸附量均呈增加趋势,磷添加浓度分别为1 mmol L~(-1)和0.6 mmol L~(-1)时,针铁矿和高岭石吸附铅量达到平衡;当处理中添加不同浓度柠檬酸,两种矿物均表现为对铅的吸附量增加,且随着柠檬酸浓度增加促进铅吸附的作用增强,说明在磷及试验浓度柠檬酸存在下促进了矿物对铅的吸附。(3)高岭石体系中,加入磷或(和)柠檬酸后,Zeta电位-pH曲线向负值方向位移,降低程度大小顺序为1.0 mmol L~(-1) P+0.5mmol L~(-1) CA0.5 mmol L~(-1) CA1.0 mmol L~(-1) P,说明高岭石表面增加的负电荷也部分增加了其对铅的电性吸附;添加磷和柠檬酸处理针铁矿的Zeta电位显著降低,且随着体系pH的升高其Zeta电位没有明显变化,表明磷和柠檬酸均主要是通过吸附到针铁矿表面而增加对铅的专性吸附。