纳米钛酸锶钡粉体吸附富集-火焰原子吸收光谱法测定水样中锰离子

提出了纳米钛酸锶钡粉体吸附富集,火焰原子吸收光谱法测定水中痕量锰的含量。在pH 6的氨性缓冲介质中,采用纳米钛酸锶钡(0.02 g)对水样(10 mL)中的锰离子振荡吸附15 min。优化条件下吸附容量达5.4 mg.g-1。方法检出限(3s/k)为2.1μg.L-1。用0.15 mg.L-1锰(Ⅱ)标准溶液连续测定6次,求得其相对标准偏差(n=6)为3.4%。用于河水和地下水中痕量锰的测定,用标准加入法测得方法的回收率在93.5%~99.7%之间。     

手控注射式钛酸锶钡多孔球富集器分离富集-火焰原子吸收法测定水中铅和镉

以D311树脂为模板,采用溶胶-凝胶法制备了纳米钛酸锶钡多孔球,用X射线衍射仪(XRD)、扫描电子显微镜(SEM)和傅立叶变换红外光谱仪(FTIR)进行了表征.考察了Pd2+和Cd2+的吸附和解脱条件.将微球装柱,制成注射式富集器,研究了此富集器对水中痕量Pd2+和Cd2+的富集性能.结果表明: 此法合成的多孔球,由钙钛矿结构的纳米钛酸锶钡组成,晶体平均粒径为21 nm,球体表面布满了不规则的纳米孔洞.当pH 4～7时,此多孔球对水中的Pd2+和Cd2+具有很强的吸附能力,静态吸附容量分别为61.9和14.8 mg/g.由多孔球装柱制成的手控注射式富集器,可成功实现对水中Pd2+和Cd2+的同时吸附.用2 mol/L HNO3洗脱后,火焰原子吸收测定.建立了手控注射式纳米钛酸锶钡富集器分离富集、FAAS法测定水中痕量Pd2+和Cd2+的新方法.此方法对Pd2+和Cd2+的检出限分别为0.099和0.0034 μg/L.用于水样中痕量Pd2+和Cd2+的富集和原子吸收测定,回收率分别为97.8%～106.5%和93.0%～100.7%.     

基于秸秆模板法制备多孔纳米钛酸锶钡及其对重金属的吸附性能

以高粱秸秆为模板,采用溶胶-凝胶法制备了纳米钛酸锶钡多孔吸附剂(SPBST),以X射线衍射(XRD)、扫描电子显微镜(SEM)和傅立叶变换红外光谱(FTIR)进行表征.考察了该多孔吸附剂对水中重金属铅、镉和锌的吸附富集性能,探讨了煅烧温度对吸附剂形貌和吸附性能的影响.并以镉离子为例,系统地研究了吸附热力学和动力学.结果表明,各煅烧温度下合成的多孔材料均由钙钛矿结构的纳米钛酸锶钡组成,晶体粒径均不大于20nm,多孔吸附剂对水中铅、镉和锌均有较强的吸附能力,吸附性能与材料的煅烧合成温度和介质的pH值以及吸附时间有关.煅烧温度过高,纳米钛酸锶钡晶体团聚严重,吸附能力降低;温度过低,材料松散易碎,不利于重复使用,750℃煅烧6h合成的材料性能最好.当介质的pH值为5～8时,吸附70min,对铅、镉和锌的静态吸附容量分别为191.51,19.00和19.97mg?g―1.其吸附行为符合Freundlich吸附等温模型和HO准二级动力学方程式,吸附过程焓变(?H)为35.905kJ?mol-1,各温度下的自由能变(?G)均小于零,熵变(?S)均为正值,吸附过程的活化能(Ea)为62.430kJ?mol-1.该吸附过程是自发的吸热物理过程.被吸附的金属离子均可用1mol?L-1的硝酸完全洗脱回收.对铅、镉和锌的富集因子均超过200.将其应用于水中痕量铅、镉和锌的吸附富集和原子吸收测定,回收率分别为90.3%～103.4%,91.5%～103.2%和94.35%～101.1%.     

双硫腙包覆钛酸锶钡粉体对水中铅的吸附行为

用草酸化学共沉淀法合成了钛酸锶钡(BST)粉体, 以双硫腙为表面修饰剂, 采用静态浸渍法对钛酸锶钡粉体进行表面包覆修饰, 制备出新型固态粉体吸附剂. 利用X射线衍射(XRD)、扫描电镜(SEM)和傅立叶变换红外光谱(FTIR)进行了表征. 研究了该吸附剂对水中铅的吸附行为. 结果表明: 双硫腙通过与钛酸锶钡表面羟基形成氢键作用包覆于该粉体上; 当吸附介质pH值大于4时, 该吸附剂对水中的铅有较强的吸附能力; 室温下, 5 min内吸附达到平衡. 其吸附行为符合Langmuir吸附等温模型和HO准二级动力学方程式, 吸附焓变(ΔH)为19.42 kJ•mol^－1, 活化能(E_a)为22.187 kJ•mol^－1, 该吸附过程是吸热的物理过程. 吸附在双硫腙包覆钛酸锶钡粉体上的铅, 可用1 mol•L^－1的硝酸溶液进行洗脱. 建立了吸附富集、火焰原子吸收法测定水中铅的新方法, 应用于地表水和自来水中铅的测定, 取得了令人满意的结果.     

纳米二氧化钛对痕量铅的吸附性能研究

提出了纳米TiO2分离富集, 火焰原子吸收光谱法测定水样中痕量铅的新方法.考察了铅在纳米TiO2上的吸附动力学、最佳酸度和吸附容量.实验结果表明：在最佳实验条件下,纳米TiO2能定量、快速地吸附水中的痕量Pb^2＋,其静态吸附容量为17.90 mg/g.吸附在纳米TiO2上的Pb^2＋可用0.1 mol/L HNO3＋0.1 mol/L CH3COOH完全洗脱.对Pb2＋的检出限为2.57 ng/mL, 相对标准偏差为2.5% （n=11, ρ=0.10 μg/mL）,加标回收率在94.5%～102.5%之间.可用于实际水样中铅的测定.     

纳米SiO_2分离富集-火焰原子吸收法测定水中痕量银

研究了纳米SiO_2分离富集-火焰原子吸收法测定水中痕量银的新方法.考察了溶液pH、吸附时间、洗脱条件和干扰离子等因素对Ag~+分离富集的影响,确定了纳米SiO_2对Ag~+吸附的最佳条件.结果表明:在pH 4.1时,纳米SiO_2能定量吸附银,吸附在纳米SiO_2上的Ag~+可用0.5 mol/L HCl+0.5 mol/L硫脲定量洗脱.该法对银的检出限为0.77 ng/mL(3σ,n=11);线性范围为0.005～1.5μg/mL,对0.5μg/mL的Ag~+标液进行7次测定,RSD为3.6%,回收率在94.0%～101.5%之间;方法可用于环境水样中痕量银的测定.     

纳米硅羟基磷灰石分离富集-火焰原子吸收法测定水样中痕量铅

提出了纳米硅羟基磷灰石(Si-HAP)分离富集,火焰原子吸收光谱法(FAAS)测定水样中痕量铅的新方法。考察了铅在纳米Si-HAP上的吸附动力学、最佳酸度和吸附容量。实验结果表明:在最佳实验条件下,纳米Si-HAP能定量、快速地吸附水中的痕量Pb2+,其静态吸附容量24.33 mg/g;吸附在纳米Si-HAP上的Pb2+可用0.01mol/L EDTA-Ca完全洗脱。本法对Pb2+的检出限为1.33 ng/mL,相对标准偏差为4.0%(n=11,c=1μg/mL),加标回收率在94.9%~102.0%之间。方法用于实际水样中铅的测定,结果满意。     

纳米钛酸钙粉体的制备及其对水中铅和镉的吸附行为

采用柠檬酸络合溶胶-凝胶法制备了纳米钛酸钙粉体. 以X射线衍射(XRD)、透射电子显微镜(TEM)和傅立叶变换红外光谱(FTIR)对其进行了表征. 考察了该纳米粉体对水中重金属铅和镉的吸附性能, 并以镉离子为例, 系统地研究了吸附热力学和动力学. 结果表明, 该法合成的钛酸钙为钙钛矿结构的纳米粉体, 粒径大小受灼烧温度的影响, 灼烧温度越高, 粉体平均粒径越大, 600 ℃灼烧2 h条件下, 粉体的平均粒径最小, 约为20 nm. 当介质的pH值为4～8时, 钛酸钙对水中的铅和镉具有很强的吸附能力. 其对镉离子的吸附行为符合Langmuir 吸附等温模型和HO准二级动力学方程式, 吸附过程焓变(ΔH)为39.312 kJ•mol－1, 各温度下的自由能变(ΔG)均小于零, 熵变(ΔS)均为正值, 吸附过程的活化能(Ea)为20.359 kJ•mol－1. 该吸附过程是自发的吸热物理过程. 被吸附的铅和镉均可用1 mol•L－1的硝酸完全洗脱回收. 对铅和镉的富集因子均超过200. 将其应用于水中痕量铅和镉的吸附富集和测定, 回收率分别为96.3%～107.2%和93.5%～104.0%, 与石墨炉原子吸收光谱法测定结果一致.     

分子印迹功能介孔材料富集-火焰原子吸收光谱法测定溶液中痕量铅

以2-巯基苯骈噻唑为修饰剂,铅离子为印迹离子成功制备分子印迹功能介孔材料,并用扫描电镜(SEM)、傅里叶红外光谱对材料进行了结构表征。铅离子分子印迹功能介孔材料能很好地将Pb(II)与性质相近的二价重金属离子Cu(II),Cd(II)和Hg(II)分离,具有非常好的吸附选择性,且静态吸附容量0.64 mmol/g。利用该材料制备的分离富集柱可以很好地富集溶液中痕量铅离子,且仅用2 mL 0.5 mol/L EDTA以0.4 mL/min流速即可完全洗脱,富集倍数高达250倍。样品预富集后的火焰原子吸收光度法线性范围为0.5～1.2×104μg/L,r=0.999 2,检出限(3σ,n=11)为0.04μg/L。利用功能介孔材料分离富集水样中痕量铅离子,用火焰原子吸收法测定含量,相对标准偏差(RSD)小于等于3%(n=6),回收率在98.2%～99.1%之间。     

二苯卡巴腙键合硅胶固定相的制备及对重金属离子的选择性分离富集研究

制备了二苯卡巴腙键合硅胶,研究了此键合硅胶的性质及对常见重金属离子的分离富集行为,发现对水中痕量Hg(Ⅱ)有好的选择性富集效果,通过实验对富集条件进行了选择。研究结果表明:对Hg(Ⅱ)的最大富集率可达100%,最大吸附量为1.84×10-3mmol g。该键合硅胶对于水中痕量Hg(Ⅱ)的富集分离与测定具有较高的灵敏度和较好的富集作用,富集倍率为540。可在Cd(Ⅱ)、Ni(Ⅱ)、Co(Ⅱ)、Mn(Ⅱ)等多种金属离子存在下对Hg(Ⅱ)进行选择性富集。     

Nanometer titanium dioxide immobilized on silica gel as sorbent for preconcentration of metal ions prior to their determination by inductively coupled plasma atomic emission spectrometry

Nanometer titanium dioxide immobilized on silica gel (immobilized nanometer TiO₂) was prepared by sol-gel method and characterized by using X-ray diffraction (XRD) and scanning electron microscope (SEM). The adsorptive potential of immobilized nanometer TiO₂ for the preconcentration of trace Cd, Cr, Cu and Mn was assessed in this work. The metal ions studied can be quantitative retained at a pH range of 8-9, and 0.5 mol L⁻¹ HNO₃ was sufficient for complete elution. The adsorption capacity of immobilized nanometer TiO₂ for Cd, Cr, Cu and Mn was found to be 2.93, 2.11, 6.69 and 2.47 mg g⁻¹, respectively. A new method using a microcolumn packed with immobilized nanometer TiO₂ as sorbent has been developed for the preconcentration of trace amounts of Cd, Cr, Cu and Mn prior to their determination by inductively coupled plasma atomic emission spectrometry (ICP-AES). The method has been successfully applied for the determination of trace elements in some environmental samples with satisfactory results.     

Determination of gold by nanometer titanium dioxide immobilized on silica gel packed microcolumn and flame atomic absorption spectrometry in geological and water samples

A new method has been developed for the determination of gold based on separation and preconcentration with a microcolumn packed with nanometer TiO₂ immobilized on silica gel (immobilized nanometer TiO₂) prior to its determination by flame atomic absorption spectrometry. The optimum experimental parameters for preconcentration of gold, such as pH of the sample, sample flow rate and volume, eluent and interfering ions, have been investigated. Gold could be quantitatively retained by immobilized nanometer TiO₂ in the pH range of 8-10, then eluted completely with 0.1 mol L⁻¹ HNO₃. The detection limit of this method for Au was 0.21 ng mL⁻¹ with an enrichment factor of 50, and the relative standard deviation (R.S.D.) was 1.8% at the 100 ng mL⁻¹ Au level. The method has been applied for the determination of trace amounts of Au in geological and water samples with satisfactory results.     

Speciation of chromium by selective separation and preconcentration of Cr(III) on an immobilized nanometer titanium dioxide microcolumn

Nanometer titanium dioxide immobilized on silica gel (immobilized nanometer-scale TiO2 particles) was prepared by a sol-gel method and characterized by X-ray diffraction and scanning electron microscopy. The adsorptive behavior of Cr(III) and Cr(VI) on immobilized nanometer TiO2 was assessed. Cr(III) was selectively sorbed on immobilized nanometer TiO2 in the pH range of 7-9, while Cr(VI) was found to remain in solution. A sensitive and selective method has been developed for the speciation of chromium in water samples using an immobilized nanometer TiO2 microcolumn and inductively coupled plasma atomic emission spectrometry. Under optimized conditions (pH 7.0, flow rate 2.0 mL/min), Cr(III) was retained on the column, then eluted with 0.5 mol/L HNO3 and determined by ICP-AES. Total chromium was determined after the reduction of Cr(VI) to Cr(III) by ascorbic acid. The adsorption capacity of immobilized nanometer TiO2 for Cr(III) was found to be 7.04 mg/g. The detection limit for Cr(III) was 0.22 ng/mL and the RSD was 3.5% (n = 11, c = 100 ng/ mL) with an enrichment factor of 50. The proposed method has been applied to the speciation of chromium in water samples with satisfactory results.     

离子色谱法测定石英微粉水萃取液中的Cl-

建立了离子色谱法测定石英微粉水萃取液中Cl^-的方法。比对试验证明，该方法的精密度和准确度与经典方法无显著性差异，而且简便、快捷，检测时间从4h缩短到15min。     

气相二氧化硅为载体固定金纳米和酪氨酸酶的研究及应用

采用硅烷试剂对气相二氧化硅表面进行活化,并以此为载体固定N-乙酰基-L-半胱氨酸修饰的金纳米(NAC-金纳米)和酪氨酸酶,最后得到的复合物作为荧光探针,建立测定邻苯二酚的固体荧光猝灭分析方法。考察了各种实验条件对酪氨酸酶和NAC-金纳米固定到气相二氧化硅表面的影响,并对其进行优化。用荧光光谱仪对NAC-金纳米-酪氨酸酶-气相二氧化硅的固体荧光进行研究并加以应用。实验结果表明,随着通入不同浓度的邻苯二酚溶液,固体粉末的荧光被有效猝灭,基于此建立了测定邻苯二酚的固体荧光法。该方法的检出限为1.0×10-7mol/L,线性范围为5.0×10-7～4.0×10-4mol/L。     

Indicator Tubes and Indicator Powders for Determining Fluoride and Chloride Ions

Noncovalent immobilization of Arsenazo I, Alizarin Red, Xylenol Orange, and diphenylcarbazone by incorporation into silicic acid xerogels and modification of silica gels was studied, and procedures for determining fluoride and chloride ions by solid-phase spectrophotometry and test methods were developed. Reactions of immobilized reagents with aluminum(III), zirconium(IV), and mercury(II) were studied. The possibility of using immobilized reagent–metal ion–halide ion systems for the determination of halide ions was assessed. Indicator powders were proposed for determining 0.5–10 mg/L fluoride ions and 1–30 mg/L chloride ions, and indicator tubes were developed for determining 20–200 mg/L chloride ions. The determination of fluoride and chloride ions is based on exchange complexation reactions proceeding in the systems immobilized Xylenol Orange–zirconium(IV) and immobilized diphenylcarbazone–mercury(II), respectively. Performance characteristics of the developed procedures were estimated. The procedures were verified by determining halide ions in Narzan mineral water.     

Sol-Gel Derived Barium-Strontium Titanate Films

Sol-gel techniques for the preparation of barium-strontium titanate (BST) films are discussed. The evolution of film microstructure during heat treatment, and the dielectric properties of BST films prepared from alkoxide solutions and from alkoxide solutions modified by 2-ethylhexanoic acid were studied. It is shown that the extent of the modification of the precursors by 2-ethylhexanoic acid changes the precursor molecular complexity governing the microstructure of the films and their electrical properties.     

Possibilities of Production of New Reference Material – Preparation of Gaseous Standard Mixtures Using Thermal Decomposition of Immobilized Compounds – the Effect of Selected Parameters on the Amount of Released Analyte

The paper presents the results of research on a novel type of matrix-free reference materials for volatile organic compounds based upon thermal decomposition of appropriate immobilized compounds. The effect of parameters such as the kind of support (silica gel, porous glass, glass fiber) and the method of chemical modification of the support surface on the amount of chloromethane released as the analyte has been investigated. It was demonstrated that the amount of chloromethane released during thermal decomposition of immobilized compounds formed on the surface of silica gel and porous glass was larger when trimethylamine rather than N-morpholine was used for the preparation of immobilized compound. Reproducibility of the chemical modification procedure using silica gel and the stability of support with the immobilized compound were also examined. The full uncertainty budget of determination of liberated amount of chloromethane has been calculated.