卟啉敏化的钛酸盐纳米管的可见光催化活性

制备了四碘化5,10,15,20-四(对-N,N,N三甲基苯胺基)卟啉敏化的钛酸盐纳米管(TAPPI-TNTs),并利用甲基橙(MO)作为模型污染物考察了其可见光催化活性。结果表明,TAPPI-TNTs是一个高效的可见光催化剂,在其催化作用下,可见光照射1 h后,甲基橙的降解率为89%。与此相反,纯钛酸盐纳米管并不具有可见光催化活性。此外,TAPPI-TNTs的稳定性较高,可以多次循环使用,在第五次循环中,甲基橙的降解率仍可达到50%以上。这可能是由于带正电荷的卟啉与带负电荷的钛酸盐纳米管之间存在着较强的静电吸引作用,卟啉紧密地吸附在钛酸盐纳米管上,导致卟啉的光激发电子易于向钛酸盐纳米管转移,从而使钛酸盐纳米管得到了有效敏化。     

多壁碳纳米管-钛酸盐纳米管复合纳米材料的制备及其生物电化学性能

以TiO2纳米颗粒为前体,采用碱性水热法制备出钛酸盐纳米管(TNTs)与多壁碳纳米管(MWCNTs)的复合纳米材料(MWCNT-TNT);借助透射电子显微镜、傅立叶变换红外光谱仪和X射线衍射仪分析了纳米材料的结构、组成和形貌.将辣根过氧化酶,室温离子液体,Nafion和复合纳米材料共同修饰在电极表面组成酶电极,利用循环伏安法研究了该酶电极的电化学性能.结果表明,TiO2纳米颗粒完全转化为钛酸盐纳米管并且很好的与MWCNTs结合在一起;复合材料修饰酶电极的循环伏安行为明显优于TNTs修饰酶电极,表明引入MWCNTs可改善钛酸盐纳米材料的导电性以及电化学性能.     

聚3-甲基噻吩及聚3-己基噻吩修饰钛酸盐纳米管的光电化学性能研究

采用水热法制备了钛酸盐纳米管, 并将钛酸盐纳米管制备成纳米结构电极进行光电化学研究. 钛酸盐纳米管产生阳极光电流, 具有n-型半导体特性. 结果表明, 聚3-甲基噻吩[poly(3-methylthiophene), PMeT]、聚3-己基噻吩[poly(3-hexylthiophene), P3HT]修饰钛酸盐纳米管后产生的光电流均较纯钛酸盐纳米管的光电流高, 且使产生光电流的波长向长波区移动. 钛酸盐纳米管/PMeT、钛酸盐纳米管/P3HT的光电转换效率分别达11.40%, 0.91%(未校正光子损失). 钛酸盐纳米管/PMeT的光电转换效率较钛酸盐纳米管/P3HT的光电转换效率高10.5%. 钛酸盐纳米管/PMeT、钛酸盐纳米管/P3HT中存在p-n异质结, 在一定条件下p-n异质结的存在有利于光生电子/空穴的分离.     

Ag/AgNO3修饰钛酸盐纳米管薄膜的制备及性能

采用水热法合成了钛酸盐纳米管薄膜,通过光催化还原反应将Ag/AgNO3纳米粒子负载其上,制得Ag/AgNO3修饰钛酸盐纳米管薄膜,并对其形貌、结构和化学组成进行了表征.Ag/AgNO3修饰后钛酸盐纳米管薄膜的性能发生了明显变化,不仅展示出光致变色的性能,而且光催化活性得到显著提高,此外,纳米管表面产生出的活泼自由基协同具有强氧化能力的Ag+能有效抑制或杀灭细菌,使薄膜具有优异的抗菌性能.     

钛酸盐纳米管的制备及光电性能研究

采用水热法制备了钛酸盐纳米管, 并用TEM、XRD、XPS对其进行了表征. 纳米管管径在5~30 nm之间, 管长约为0.1~1 μm, 具有不同于锐钛矿型的钛酸盐结构, 分子组成可能是Na4－xHxTi2O5. 将钛酸盐纳米管制备成纳米管结构电极, 并进行了光电化学研究. 钛酸盐纳米管产生阳极光电流, 具有n型半导体特性.     

纳米羟基磷灰石纳米管的一种简便制备方法及其对溶液中重金属离子的吸附

采用简便的方法合成了20~40 nm长、56 m^2·g^-1的比表面积的羟基磷灰石纳米管(HAP)。然后用制备的HAP纳米管在水溶液中同时吸附Pb^2+、Cd^2+、Cu^2+、Co^2+、Ni^2+、Zn^2+和Hg^2+,其具有高的吸附能力,并能实现快速去除。此外,制备的HAP纳米管对7种重金属离子的脱附率均小于1%,表现出较强的稳定性。实验数据采用Langmuir等温线模型和Freundlich等温线模型进行分析。2个方程的应用结果表明,吸附平衡最适合Langmuir模型,单层饱和吸附能力为958.28 mg·g^-1,具有较好的吸附性能。通过能量色散X射线光谱(EDS)和X射线衍射(XRD)图进一步研究了吸附机理,结果表明,当溶液中Pb^2+离子数量足够时,吸附机理为Pb取代了HAP中的Ca,形成了更稳定的Pb5(PO4)3(OH)。上述实验研究预测了利用HAP纳米管处理含铅废水在环境污染治理中的可行性。     

钛酸盐纳米管薄膜的合成、结构与性质

在水热条件下, 控制反应温度和氢氧化钠的浓度, 分别采用去离子水和盐酸进行洗涤处理, 在钛金属基底表面合成出含钠元素和不含钠元素的两种钛酸盐纳米管薄膜(TiNTW和TiNTA), 并利用X射线衍射分析、扫描电子显微镜、透射电子显微镜和能量色散X射线光谱等对其结构、组成和性质进行了表征. 结果表明, TiNTW和TiNTA均由宽约8 nm、长约1 μm的纳米管组成, 但TiNTA表现出较好的光催化活性和储氢性能, 而热稳定性弱于TiNTW, 二者在性质上的显著区别归因于2种钛酸盐纳米管薄膜的晶体结构和元素组成的不同.     

纳米羟基磷灰石纳米管的一种简便制备方法及其对溶液中重金属离子的吸附（英文）

采用简便的方法合成了20～40 nm长、56 m~2·g~(-1)的比表面积的羟基磷灰石纳米管(HAP)。然后用制备的HAP纳米管在水溶液中同时吸附Pb~(2+)、Cd~(2+)、Cu~(2+)、Co~(2+)、Ni~(2+)、Zn~(2+)和Hg~(2+),其具有高的吸附能力,并能实现快速去除。此外,制备的HAP纳米管对7种重金属离子的脱附率均小于1%,表现出较强的稳定性。实验数据采用Langmuir等温线模型和Freundlich等温线模型进行分析。2个方程的应用结果表明,吸附平衡最适合Langmuir模型,单层饱和吸附能力为958.28 mg·g~(-1),具有较好的吸附性能。通过能量色散X射线光谱(EDS)和X射线衍射(XRD)图进一步研究了吸附机理,结果表明,当溶液中Pb~(2+)离子数量足够时,吸附机理为Pb取代了HAP中的Ca,形成了更稳定的Pb_5(PO_4)_3(OH)。上述实验研究预测了利用HAP纳米管处理含铅废水在环境污染治理中的可行性。     

钛金属表面结构可控多层钛酸盐纳米管薄膜的制备和结构稳定性

在水热条件下, 通过控制反应温度和氢氧化钠的浓度, 在钛金属表面得到结构可控的多层钛酸盐纳米管薄膜. 根据扫描电子显微镜和高倍透射电子显微镜的观测结果, 认为钛金属表面多层钛酸盐纳米管薄膜的形成经历以下4个阶段: (1) 钛金属的水合和碱性钛酸盐水凝胶的生成; (2) 碱性钛酸盐水凝胶分解并形成层状Na₂Ti₃O₇; (3) 层状Na₂Ti₃O₇的生长; (4) 层状Na₂Ti₃O₇的劈裂和多层卷曲成轴形成纳米管. 研究了薄膜形成后机械处理对薄膜形貌和结构稳定性的影响, 并利用超声的方法实现了多层膜的层分离.     

规则结构钛酸盐自组装聚集体的制备

在水热条件下, 采用不同的钛源, 通过控制溶液碱度和冷却温度等反应条件, 利用无模板自组装技术, 在钛酸盐薄膜表面及溶液相中制备了鸟巢状和绒球状钛酸盐纳米带自组装聚集体以及海胆状钛酸盐纳米管自组装聚集体. 通过引入碳酸钠模板, 制备出形貌新颖的钛酸钠-碳酸钠香蒲状自组装聚集体复合材料. 初步研究了纳米自组装聚集体的形成机理, 认为其形成经历了一维纳米结构(纳米带或纳米管)的生长和一维纳米结构的自组装2个过程.     

聚羟基丁酸酯/碳纳米管复合纳米纤维膜的制备及其对重金属离子吸附分离性能的研究

以聚羟基丁酸酯和碳纳米管为原料,采用三氯甲烷/二甲基甲酰胺混合溶液为溶剂,利用静电纺丝技术制备了聚羟基丁酸酯/碳纳米管复合纳米纤维膜.研究了碳纳米管的含量对纳米纤维膜形貌和力学性能的影响,探讨了复合纳米纤维膜对重金属Cu(II)、Cd(II)和Pb(II)的吸附特性.实验结果表明:加入1 wt%碳纳米管能够将纳米纤维的平均直径从(728±146)nm降低至(468±89)nm,纳米纤维膜的比表面积从27.24 m~2/g提高至43.45 m~2/g;碳纳米管的复合能够有效增强聚羟基丁酸酯纳米纤维,当碳纳米管含量1 wt%为最佳,拉伸强度可达5.85 MPa,较纯聚羟基丁酸酯纳米纤维提升了115%.复合纳米纤维膜对重金属离子具有良好的吸附特性,其对Cu(II)、Cd(II)和Pb(II)的最佳吸附pH值为5,此时最大吸附容量分别为91.04、171.05和197.03mg/g,平衡吸附时间分别约为50、60和60 min,吸附率分别为1.79、2.83和3.28 mg/g/min;热力学和动力学分析表明,复合纳米纤维膜对重金属Cu(II)、Cd(II)和Pb(II)的吸附行为更符合Freundlich模型,吸附过程更符合Pseudo-second order模型;循环使用实验表明,重复使用5次后,其吸附容量可保持在初始值的87%以上,具有较好的使用寿命.     

Carbon nanotubes modified with 5,7-dinitro-8-quinolinol as potentially applicable tool for efficient removal of industrial wastewater pollutants

The environmental pollution due to the industrial wastewater of four different areas in the Gulf of Suez, Red Sea, Egypt, was studied. Adsorption capacities toward the concerned heavy metal ions Cu(II), Zn(II), Fe(II), and Pb(II) by multiwalled carbon nanotubes (MWCNTs) and modified-MWCNTs with 5,7-dinitro-8-quinolinol were investigated. MWCNTs as well as the modified-MWCNTs were characterized using Fourier transform infrared (FTIR), Scanning electron microscopy (SEM) and Transmission electron microscopy (TEM). Adsorption of the studied divalent metal ions was measured by atomic absorption spectrometry (AAS). The effects of solution conditions such as pH, shaking time, metal ion concentration, ionic strength and adsorbent dosage on the adsorption process were also examined. The obtained results showed that removals of the heavy metal ions under consideration by MWCNTs are obviously dependent on the experimental conditions. The maximum adsorption capacities as calculated applying Langmuir equation to single ion adsorption isotherms were found to be 142.8 mg/g for Cu(II), 250 mg/g for Zn(II), 111.1 mg/g for Fe(II), and 200 mg/g for Pb(II) using MWCNTs; meanwhile, the modified-MWCNTs exhibited higher values of the respective maximum adsorption capacities as 333.3 mg/g for Cu(II), 500 mg/g for Zn(II), 200 mg/g for Fe(II), and 333.3 mg/g for Pb(II). Kinetic studies were also performed and the experimental data followed a pseudo-second order model of the adsorption process. The obtained results suggest that the tested adsorption systems of MWCNTs and modified-MWCNTs have suitable affinity toward the metal ion under consideration. Both systems could act as potentially applicable tool in environmental protection.     

Preparation and characterization of porous calcium titanate-based coated glass fiber filter material and its application in determination of lead and cadmium ion concentrations in water

Glass fiber filter coated with a porous block adsorption agent of calcium titanate (GPCTO) was prepared by the citric acid sol-gel method, and characterized by X-ray diffraction, scanning electron microscopy, and FTIR spectrophotometry. Its Pb2+ and Cd2+ adsorption properties from water were studied. Adsorption and elution were investigated under different conditions, as were the thermodynamics and kinetics of adsorption, using Cd ion as representative. Calcium titanate may react with glass fiber, forming Si-O-Ti and B-O-Ti bonds and becoming a composite adsorbent. The Pb and Cd ions were quantitatively retained at pH 4-9; their adsorption capacities by the GPCTO were 199.72 and 19.68 mg/g, respectively. The isothermal data were described by the Langmuir equation. The dynamic data followed the pseudo-second-order kinetic model well. The enthalpy change (AH) of the adsorption process was 37.160 kJ/mol. At various temperatures, Gibbs free energy changes (delta G) were negative, and entropy changes (delta S) were positive. The activation energy (Ea) was 38.127 kJ/mol for the adsorption. Cd ion adsorption by the GPCTO was endothermic and spontaneous. The adsorbed Pb and Cd ions were completely recovered by elution with 2 M HNO3. The Pb+ and Cd2+ concentration factors were up to 200. The method has been applied to the preconcentration for flame atomic absorption spectrometric determinations of trace Pb and Cd ions in water samples. The recoveries were 95.2 to 102.4% for Pb and 92.2 to 98.0% for Cd.     

羧甲基二硫代氨基甲酸酯功能化聚氯乙烯树脂的合成及对Ag~+的吸附与选择性能

以聚氯乙烯为大分子骨架,经三乙烯四胺胺化,再与二硫化碳和乙醇钠反应,得到的二硫代氨基羧酸盐改性聚氯乙烯树脂(PV-NS)进一步与氯乙酸钠反应,合成了一种同时舍N,S,O的羧甲基二硫代氨基甲酸酯改性聚氯乙烯树脂(PV-NSO).合成树脂的功能基结构经红外和元素分析确认.对合成树脂的吸附性能研究表明,合成树脂对Ag+、Hg2+、Au<'3+>、Pb2+离子的吸附容量在实验条件下分别达2.058mmol/g、1.514mmol/g,1.125mmol/g和0.415mmol/g,而对Cu2+、Cd2+、Zn2+、Ni2+、Mg2+等离子的吸附容量很小,甚至不吸附.树脂的选择性吸附表明,树脂对Ag+的吸附选择性较好,在有Hg2+、Pb2+、Cd2+、Zn2+、Cu2+或Mg2+共存时,树脂对Ag+的选择性吸附系数分别达4.74、17.33,12.98、∞、7.60和74.14.合成树脂在极性溶剂中的溶胀性能均比在非极性溶剂中好.     

Facile Synthesis,Crystal Structure,and Adsorption Property of Small Titanate Nanowires

Small titanate nanowires with NaTi_2O_4(OH) formulation were directly synthesized via the hydrothermal reaction of amorphous titanate particles with concentrated Na OH solution.The average width of these nanowires is smaller than 20 nm,and the surface area is higher than 200 m~2/g.Compared with the larger nanowires obtained by the hydrothermal treatment of crystalline titania in alkaline solution,these small nanowires exhibit larger adsorption capacities and faster adsorption rate in the removal of both heavy metal ions and dyes.     

Preparation of amidoxime-modified polyacrylonitrile (PAN-oxime) nanofibers and their applications to metal ions adsorption

Polyacrylonitrile (PAN) nanofibers were applied to metal adsorption. PAN nanofibers (prepared by an electrospinning technique) were chemically modified with amidoxime groups, which are suitable for metal adsorption due to their high adsorption affinity for metal ions. The adsorption of the amidoxime-modified PAN (PAN-oxime) (25% conversion) nanofibers followed Langmuir isotherm. The saturation adsorption capacities for Cu(II) and Pb(II) of 52.70 and 263.45 mg/g (0.83 and 1.27 mmol/g), respectively, indicating that the monolayer adsorption occurred on the nanofiber mats. In addition, over 90% of metals were recovered from the metal-loaded PAN-oxime nanofibers in a 1 mol/L HNO₃ solution after 1 h.     

过渡金属离子置换钛酸(盐)纳米管的合成和表征

以掺杂(Mn、Cr、Cu)的锐钛矿相二氧化钛纳米粉体为前驱体, 采用水热法合成了过渡金属离子置换的钛酸(盐)纳米管, 并用扫描电镜(SEM)、透射电镜(TEM)、能谱元素分析(EDX)、粉末X射线衍射(XRD)、 荧光发射光谱(PL)和拉曼光谱(Raman)对产物进行了表征. 结果表明, 过渡金属离子置换的钛酸(盐)纳米管荧光发射强度随金属离子的置换都有不同程度的降低, 一般认为低电子空穴对复合率意味着高光量子效率. 期望置换后的钛酸(盐)纳米管有可能在催化领域得到应用.     

Adsorptive accumulation of Cd(II), Co(II), Cu(II), Pb(II), and Ni(II) from water on montmorillonite: influence of acid activation

The present work investigates the influence of acid activation of montmorillonite on adsorption of Cd(II), Co(II), Cu(II), Ni(II), and Pb(II) from aqueous medium and comparison of the adsorption capacities with those on parent montmorillonite. The clay-metal interactions were studied under different conditions of pH, concentration of metal ions, amount of clay, interaction time, and temperature. The interactions were dependent on pH and the uptake was controlled by the amount of clay and the initial concentration of the metal ions. The adsorption capacity of acid-activated montmorillonite increases for all the metal ions. The interactions were adsorptive in nature and relatively fast and the rate processes more akin to the second-order kinetics. The adsorption data fitted both Langmuir and Freundlich isotherms, indicating that strong forces were responsible for the interactions at energetically nonuniform sites. The Langmuir monolayer capacity of the acid-activated montmorillonite is more than that of the parent montmorillonite (Cd(II): 32.7 and 33.2 mg/g; Co(II): 28.6 and 29.7 mg/g; Cu(II): 31.8 and 32.3 mg/g; Pb(II): 33.0 and 34.0 mg/g; and Ni(II): 28.4 and 29.5 mg/g for montmorillonite and acid-activated montmorillonite, respectively). The thermodynamics of the rate processes showed the adsorption of Co(II), Pb(II), and Ni(II) to be exothermic, accompanied by decreases in entropy and Gibbs free energy, while the adsorption of Cd(II) and Cu(II) was endothermic, with an increase in entropy and an appreciable decrease in Gibbs free energy. The results have established the potential use for montmorillonite and its acid-activated form as adsorbents for Cd(II), Co(II), Cu(II), Ni(II), and Pb(II) ions from aqueous media.     

Investigation of Metal Ion Removal Selectivity Properties of the Modified Polyacrylamide Hydrogels Prepared by Transamidation and Hofmann Reactions

Modified crosslinked polyacrylamides having different functional groups prepared by transamidation reaction in aqueous and non‐aqueous medium and by Hofmann reaction were used as chelating agents for removal of Cu(II), Cd(II) and Pb(II) ions from aqueous solutions at different pH values. Under non‐competitive conditions, polymers adsorbed different amounts of metal ions, depending on their functional groups and swelling abilities. The metal ion adsorption capacities of polymers changed between 0.11–1.71 mmol/g polymer. Under competitive conditions, while the polymers having mainly secondary amine groups were highly selective for Cu(II) ions (99.4%), those having mainly secondary amide and carboxylate groups have shown high selectivity towards Pb(II) ions (99.5%). The selectivity towards Cu(II) ion decreased and Pb(II) ion selectivity increased by the decrease of the pH of the solutions. The high initial adsorption rate (<10 min) suggests that the adsorption occurs mainly on the polymer surface. A regeneration procedure by treatment with dilute HCl solution showed that the modified polymers could be used several times without loss of their adsorption capacities.     

两种有机物改性膨润土对Cu2+和Zn2+的吸附-解吸研究

选用天然有机物料(猪粪降解液)和有机化学试剂[十六烷基三甲基溴化胺(HDTMA)]对钠基膨润土进行表面改性,比较了膨润土对两类有机物的吸附特性,以及两种有机物改性膨润土对Cu2+、Zn2+吸附-解吸性能的差异。结果表明,膨润土对HDTMA和猪粪降解液是优惠吸附,且前者最大吸附量为382.4mg/g,是后者的4.19倍。HDTMA改性膨润土对Cu2+、Zn2+的最大吸附量均大于猪粪降解液改性膨润土,前者分别为后者的1.12倍(Cu2+)和1.09倍(Zn2+),且两种吸附剂对Cu2+的最大吸附量和吸附速率均大于Zn2+。Zn2+在两种改性膨润土上的解吸率均高于Cu2+,且Cu2+、Zn2+在猪粪改性膨润土上的解吸率均要高于在HDTMA改性膨润土的。两种有机物改性的钠基膨润土对重金属离子具有良好的吸附性能,可以用于含重金属废水的处理和重金属污染土壤的钝化修复,而猪粪降解液改性膨润土是环境友好的重金属钝化剂。