From Synthetic Approaches to Functional Material App

学号：2012420011

北京化工大学 博士研究生学位论文开题报告

论 文 题 目 ： Polyoxometalates Intercalated Layered Double Hydroxides: From Synthetic Approaches to Functional Material Applications

学 院 名 称：理学院 专

业：化

学

研究生姓名： Solomon Omwoma （ 所 罗 门 ） 导 师 姓 名 ： Yu -Fei Song （ 宋 宇 飞 ） 开 题 日 期 ： 2013.10.27

考核 成绩 审核 小组 成员 以及 职称

姓

名

职

称

1.课题名称及项目来源 课题名称：Polyoxometalates Intercalated Layered Double Hydroxides: From Synthetic Approaches to Functional Material Applications 项目来源： 摘要：多酸因其诱人的特性和巨大的潜力，满足着当今社会中涉及环境、材料、能源、健康 和信息技术等行业的需求。发展多酸基功能材料对于多酸的高效利用和面对各种挑战是非常 重要的。近年来，将多酸插进水滑石层板之间已被证明是一种发展多酸基多功能材料行之有 效的方法。本课题的主要工作是总结近期制备多酸插层水滑石的最新进展和他们的应用，合 成一类新的多酸插层水滑石复合材料并用于去除废水中有害元素如 Cr(VI), Pb, Cd, F and Cl 等。 Keywords: 多酸 水滑石 功能材料 废水 Cr(VI), Pb, Cd, F,

Cl

Abstract: Polyoxometalates (POMs) exhibit attractive properties and great potential to meet with contemporary society demands regarding environment, materials, energy, health and information technologies etc. The development of POMs-based advanced functional materials is of significance in order to effectively utilize POMs and to match various challenges. In recent years, the intercalation of POMs anions into layered double hydroxides (LDHs) has been a versatile and important approach for the development of POMs-based multifunctional materials. This work intends to summarize the latest progress on the preparation of POMs intercalated LDHs (denoted as POMs/LDHs) and their material application. Thereafter, new POMs/LDHs nanocomposite materials will be synthesised and used to decontaminate wastewater from harmful chemical pollutants such as Cr(VI), Pb, Cd, F and Cl.

Keywords: Polyoxometalate, Layered double hydroxide, Functional materials, wastewater, Cr(VI), Pb, Cd, F, Cl

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Contents

1. Introduction ............................................................................................................... 3 1.1 Objectives ................................................................................................................ 4 2.0 Literature review...................................................................................................... 5 2.1 Synthesis of Fe3O4@SiO2@LEuH@PW10 Nanomaterial for the Chemisorption of Hexavalent Chromium Anions from Aqueous Media

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2.2 Synthesis of Sorbent Materials from in situ Polymerization of Na2WO4 on Layered Rare Earth Hydroxides Nanosheets ............................................................................... 6 3.1 Chemical materials and characterization

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3.1.1 Chemical materials: ..................................................................................... 8 3.1.2 Characterization:.......................................................................................... 8 3.2 Preparation of Fe3O4@SiO2@LEuH nanoparticles: 9 3.3 Preparation of Fe3O4@SiO2@LEuH@PW10 nanoparticles:

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3.4 Adsorption experiments: 10 3.5 Kinetic studies:

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3.5.1 Determination of adsorption rate and equilibrium: ................................... 10 3.5.2 Adsorption Isotherms: ............................................................................... 10 3.5.3

Preparation

of

LEuH-[H2W12O40].nH2O

nanocomposite

(in

polymerization): .......................................................................................... 11 Budget .......................................................................................................................... 12 References................................................................................................................... 13

2

situ

1. Introduction Polyoxometalates (POMs) are a class of discrete anionic metal oxides of groups 5 and 6 and POMs exhibit attractive properties such as thermal and oxidative stability, remarkable electronic and magnetic properties, and Brønsted acidity etc, which result in intriguing applications ranging from medicine, catalysis to material science. We have witnessed the significant progresses during past decades that have been summarized in different books, reviews and thematic journal issues [1-10], including books by Pope in 1984 and Müller in 2004 [1, 2], a review by Pope and Müller in 1991 [3], the thematic POM issues in Chemical Reviews and in Chemical Society Reviews [4, 5], and several contributions from Coordination Chemistry Reviews [6-10]. POMs are most well-known as catalysts and have been widely applied in industry [11-14]. The development of highly efficient, easily recovered and reusable POMs-based heterogeneous catalysts has long been and will continue to be the focus for the practical application of POMs. As a result, two strategies [15-19], namely “solidification” and “immobilization” of catalytically active POMs, have been adopted in the development of POMs-based molecular heterogeneous catalysts. One way for the immobilization of POMs is the intercalation of POMs into LDHs layers, which results in the formation of a number of interesting nanocomposites with unique properties. The first scientific publication of the POMs/LDHs nanocomposites was reported by Pinnavaia in 1988 [20]. It should be mentioned that an interesting POM/LDH composite material was reported to be able to apply in exhaust gas and hydrocarbon conversion in a US patent [21] in 1984. The POMs/LDHs nanocomposites are a class of very important and versatile materials. Previously, Wang et al. (1997) [22], Pinnavaia et al. (1998) [23], Rives & Ulibarri (1999) [24], Hu and Li (2004) [15], and Rives et al (2010) [16] reviewed this type of materials from different perspective, and most of them mainly focused on the introduction of the preparation methods, characterization and some application in catalytic reactions. The first section of the thesis intents to summarize the recent advances on polyoxometalates intercalated layered double hydroxides: From synthetic approaches to functional material applications. A brief introduction of the classical synthetic approaches (ion exchange, reconstitution, and co-precipitation) of the POMs/LDHs nanocomposites will be made and a summary of some other synthetic pathways that have been employed in engineering the POMs/LDHs composite materials in recent years will be discussed. The important applications of the POMs/LDHs nanocomposites in material science will also be highlighted before advancing on some newer applications. In the second part of the thesis, new nanocomposite materials will be synthesised based on POMs/LDHs and used to solve various environmental related problems.

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1.1 Objectives 1. To summarize the recent advances on polyoxometalates intercalated layered double hydroxides: From synthetic approaches to functional material applications.

2. To synthesize Fe3O4@SiO2@LEuH@PW10 nanomaterial for the chemisorption of hexavalent chromium anions from aqueous media. 3. To synthesize sorbent materials from in situ polymerization of Na2WO4 on layered rare earth hydroxides nanosheets.

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2.0 Literature review

2.1 Synthesis of Fe3O4@SiO2@LEuH@PW10 Nanomaterial for the Chemisorption of Hexavalent Chromium Anions from Aqueous Media Chromium is released into the environment from various natural and industrial sources. As a result, its presence in various environmental compartments is inevitable [25-28].

In general, chromium

exists as trivalent or hexavalent species, depending on the prevailing redox conditions [29]. The trivalent form (Cr(III)) adsorbs or precipitates as a solid (oxy)-hydroxide phase [Cr(OH)]2+ over the pH range of most natural waters [30]. In contrast, the hexavalent form (Cr(VI)) exists as oxy-acids in the pH range of most surface waters, where the primary hydrolyzed forms are chromic acid, hydrogen chromate ion, chromate ion and dichromate ion [29, 31-33]. The maximum set standard level for total chromium in drinking water is 0.1 ppm and Cr(VI) is 0.05 ppm [34]. Indeed, the set limit is high and as a result, it is being reconsidered for revision based on the emerging toxicological effects of Cr(VI) [35]. Trivalent chromium is an essential micro-nutrient to plants and animals metabolism whereas Cr(VI) is carcinogenic, highly toxic to animals and plants at levels above 0.1 ppm, and it causes allergic dermatitis [36,37]. To date, the most adopted technology of Cr(VI) removal from waste water involves its reduction to the trivalent form at pH 2 and subsequent precipitation of Cr(OH)3 by increasing pH to 9~10 using lime [38,39]. The disadvantages of such technology lie in the fact that 1) the reduction process produces large amounts of sludge. For example, 32 Kg of sludge can be generated in order to remove 1 kg of Cr(VI) [40]. 2) the use of lime to precipitate the trivalent chromium makes the process complicated and more expensive. Under such circumstances, a number of adsorbents such as activated carbon, ligno-cellulose, hydrotalcite and mesoporous zirconium titanium oxides etc have been utilized for adsorption of the chromium species [29,31,32,38,41,42]. Nevertheless, similar problems of adsorbent disposal and cost implications still dominate. In addition, most Cr(VI) adsorbents reported so far use permanent physisorption mechanisms that do not allow reusability of adsorbents nor recovery of the Cr(VI) anions. In terms of bacteria, fungi, algae and different plants as adsorbents, they do show good adsorption capability in laboratory [38]. The scale-up experiments by the application of these biological adsorbents into water treatments is not successful due to their relatively poor natural

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abundance [38]. Therefore, removal of Cr(VI) from waste water still represents a great challenge in waste water treatment technology. Recently, Bajpe et al reported that slow addition of H3PW12O40 to an aqueous solution of K2CrO4 at room temperature (PH = 6.6±0.2) led to formation of the final pro duct K14[P2W20O72]•24H2O (denoted as P2W20) [43]. It was proposed that a Cr(VI)-stabilized [PW10O36(CrO4)2]9- intermediate was formed, which played a significant role for the formation of the P 2W20 cluster. In other words, without the addition of K2CrO4 in the reaction mixture, the final product could not be obtained. Moreover, the Cr(VI)-stabilized species of [PW10O36(CrO4)2]9- could dissociate upon the increase of the temperature above 40oC. Unfortunately, this intermediate was not isolated. However, the proposed intermediate shows the capability of Cr(VI) anions to chemically bond with PW10 anions. Therefore, a better understanding of the mechanism of reaction herein can be very beneficial for Cr(VI) removal from aqueous solutions provided that the [PW10O36]7- (denoted as PW10) [44] cluster is heterogenized. In this contribution, we intent to isolate the above mentioned intermediate by electrostatically immobilizing [PW10O36]7- anions onto the surface of Fe3O4@SiO2@LEuH, in which the core magnetite iron nanoparticles coated with silica [45,46] will be electrostatically interacted with the layered rare earth hydroxide nanosheets of Eu2(OH)5CO3•H2O (LEuH) [47-49]. The resulting nanocomposite material of Fe3O4@SiO2@LEuH@PW10, will be used in chemisorptions experiments of hexavalent chromium from different aqueous solutions. Note that layered rare-earth hydroxides (LRHs) are typical anion-exchangeable lamellar

compounds, and they are structurally similar to LDHs and consist of positively charged rare-earth hydroxide layers with exchangeable, charge-balancing anions in the interlayer space [31]. 2.2 Synthesis of Sorbent Materials from in situ Polymerization of Na2WO4 on Layered Rare Earth Hydroxides Nanosheets Harmful chemical wastes generation by industries are unavoidable due to high demand of useful products, like steel, needed by growing economies. The harmful chemical wastes, most frequently generated in negligible amounts, accumulate in environmental systems leading to severe life threatening problems in both aquatic and non-aquatic life. It is 6

important for the industries to isolate these harmful chemicals from wastes before the later can be discarded into the environment. Failure to observe this green chemistry technology may cost the industries great financial loses like the case of Chisso Corporation in Japan associated with minamata mercury poisoning [32]. Toxic metals such as cadmium, lead, and hexavalent chromium are ubiquitous, have no beneficial role in human homeostasis, and contribute to non-communicable chronic diseases. Their existence in wastewater, even at trace levels, is detrimental to environmental systems [33]. In contrast, halides are of benefit and/or do not affect human homeostasis at low concentrations: below 1ppm, 5ppm and 6ppm for fluoride, chloride and bromide respectively [34-36]. Heavy metals and halide concentration in wastewater from industries using these chemicals will be higher than recommended levels. Hence the need to remove them before wastewater is discharged to environmental systems. Economically, wastewater treatment plants use cheap and effective treatment technologies. Unfortunately, efficient removal of cationic and anionic harmful waste chemicals such us heavy metals and halides require very expensive processes like ionic exchangers. Under such circumstances, some industries ignore the chemicals while others opt to use adsorbent materials. Most sorbent materials reported to date use physosorption mechanisms that are associated with long contact time, low sorption of the adsorbent and generation of large amounts of secondary wastes [37, 38]. Moreover, these secondary wastes are more toxic and difficult to dispose. Polyoxometalates (POMs), a class of discrete anionic metal oxides, exhibit attractive properties which result in intriguing applications ranging from medicine, catalysis to material science [39-41]. Layered rare-earth hydroxides (LRHs), anion-exchangeable lamellar compounds similar in structure to layered double hydroxides, consist of positively charged rare-earth hydroxide layers with exchangeable charge-balancing anions in the interlayer space [42]

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Intercalation of POMs into LRHs has resulted into versatile materials such as heterogeneous catalysts and adsorbents [39-42] In this work, in situ polymerization of Na2WO4.2H2O on delaminated europium containing LRHs nanosheets Eu2(OH)5Cl•H2O, (refered to as LEuH), at pH 4 under nitrogen environment will be used to produce Eu2(OH)5[H2W12O40].nH2O heterogenized porus material. The resultant material will be used in adsorption experiments of cationic chemicals in aqueous media followed by their anionic counterparts.

3. Experimental Section 3.1 Chemical materials and characterization 3.1.1 Chemical materials: Analytically pure K2CrO4, KOH, NaOH, Na2WO4, CH3COONa, H2WO3, Eu2O3, FeCl3, H3PO4, HCl, H2SO4, CsOH, CrCl3, PbCl3, CdCl3,, NaF, KBr, Lacmoid ethanol, methanol, ammonium solution, ethylene glycol, tetraethyl orthosilicate and 1,5-diphenylcarbazide will be purchased fromAlfa Asear and used without further purification. The synthesis of the decatungstophosphate anion ([α-PW10O36]7-) [43] referred to PW10, Eu-containing layered europium hydroxide (Eu2(OH)5Cl•nH2O) nano-sheets [46]

referred to as LEuH and silicon coated magnetic iron

nanoparticles (denoted as Fe3O4@SiO2 nanospheres) [44,45] will be synthesized and characterized according to literature methods.

3.1.2 Characterization: Powder X-ray diffraction (XRD) patterns will be recorded on a Rigaku XRD-6000 diffractometer under the following conditions: 40 kV, 30 mA, Cu-Ka radiation (λ = 0.154 nm), scan step of 0.01° and scan range between 3° and 80°. Fourier transform infrared (FT-IR) spectra will be recorded on a Bruker Vector 22 infrared spectrometer, using the KBr pellet method. Scanning electron microscopy (SEM) images and energy dispersive X-ray spectroscopy (EDX) analytical data will be obtained using a Zeiss Supra 55 SEM equipped with an EDX detector. Transmission electron microscopy (TEM) micrographs will be recorded using a Hitachi H-800 instrument. Inductively coupled plasma-atomic emission spectroscopy (ICP-AES) analysis will be performed using a

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Shimadzu ICPS-7500 spectrometer after a weighed amount is dissolved in HCl solution. The fluorescence emission spectra will be recorded with a Hitachi F-7000 fluorospectrometer with a Xe lamp as the excitation source. The UV absorption measurements will be performed with a TU-1901 UV/Vis spectrophotometer with 1 nm optical resolution over the range of 190–900 nm. The specific surface area determination and pore volume and size analysis will be performed by Brunauer−Emmett−Teller (BET) and Barrett−Joyner−Halenda (BJH) methods, respectively, by use of a Quantachrome Autosorb-1C-VP analyzer. Prior to the measurements, the samples will be degassed at 100 °C for 6 h. The OH content will be obtained by neutralization back-titration after the sample have been dissolved in 0.1N standard H2SO4. Thermo gravimetric analysis will be carried out on a locally-produced HCT-2 thermal analysis system in flowing N2 with a heating rate of 10 oC min-1.

3.2 Preparation of Fe3O4@SiO2@LEuH nanoparticles: Fe3O4@SiO2 (0.1g) will be dispersed in deionized water under sonication. LEuH nano-sheets will be prepared by ultra-sonicating freshly prepared LEuH (0.2g) in aqueous media for 10 min to delaminate the positively charged nano-sheets, followed by centrifugation at 2000 rpm to remove un-delaminated material. The resultant delaminated nano-sheets of LEuH (0.05 g) will be added dropwise to the above prepared Fe3O4@SiO2. The mixture will be stirred at room temperature (RT) for 12 hours, separated by a magnet, washed several times with deionized water and this procedure repeated for 5 times to get the Fe3O4@SiO2@LEuH material that will be dried in vacuum at 40°C for 12 hours.

3.3 Preparation of Fe3O4@SiO2@LEuH@PW10 nanoparticles: A wet fresh sample of Fe3O4@SiO2@LEuH (0.11 g) will be dispersed in deionized water (50 ml) under sonication for 10 min. The sonicated Fe3O4@SiO2@LEuH will be transferred into a beaker and Cs7[PW10O36] (5 g), prepared by dispersion in deionized water (40 ml) under sonication for 10 min, will be added drop wise as the contents are stirred at RT overnight. The desired Fe3O4@SiO2@LEuH@PW10 material will be washed for several times with deionized water before being dried at 40oC for 12 hours.

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3.4 Adsorption experiments: The resultant nano-particles, Fe3O4@SiO2@LEuH and Fe3O4@SiO2@LEuH@PW10, will be used to remove Cr(VI) anions from deionized water, laboratory tap water and municipal waste water. For deionized water and tap water, a known concentration of Cr(VI) anions will be introduced into the water sample and the nanoparticles (0.4 g) added. Then, the test solution will be kept stirring for 1 hour. The nanoparticles will be separated by a magnet and the water tested for Cr(VI) using EPA method 218.7 [47]. For the municipal waste water, a known concentration of Cr(VI) will be introduced into the sampled water in Teflon bottles and left to acclimatize to the sample collection ambient environment. After two days, the waste water will be filtered, treated with the nanoparticles as indicated above and the concentration of Cr(VI) determined using EPA method 218.7. The separated nanoparticles after the experiments will be heated at 40°C in a small amount of aqueous solution for 30 minutes to yield a concentrated chromate anion solution and the adsorbent reused for ten times. The chromate anions will be recovered by adding stoichiometric amounts of KOH solution to the solution to yield potassium chromate powder after solvent evaporation.

3.5 Kinetic studies: 3.5.1 Determination of adsorption rate and equilibrium: Ten samples of deionized water (100 ppm) solutions will be treated with 0.2 g of Fe3O4@SiO2@LEuH@PW10 nanoparticles for 0, 10, 20, 30, 40, 50, 60, 80, 100 and 150 minutes. After each experiment, the magnetic nanoparticles will be separated and the deionized water tested for Cr(VI) concentration.

3.5.2 Adsorption Isotherms: Fe3O4@SiO2@LEuH@PW10 nanoparticles (0.2 g) will be stirred with 50 ml solutions having different concentrations (1, 5, 10, 20, 50, 100, 200, 300, 400, 500, and 1000 ppm) for 1 h to insure equilibrium. The magnetic nanoparticles will be separated and the resulting aqueous solutions tested for Cr(VI) concentration. The amount of Cr(VI) up taken per gram of the nanoparticles (q) will be determined according to Equation 1, in which Co is the initial Cr(VI) concentration, C is the concentration of the equilibrated final solution, V is the volume of the aqueous phase, and m is the mass of the nano-particles in the system.

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q

(C0  C )V m

Equation  1

The optimized reaction temperature and pH for the nanoparticles with Cr(VI) anions will be determined by reacting the Fe3O4@SiO2@LEuH@PW10 nanoparticles (0.2 g) with 50 ml of Cr(VI) solution (00ppm) at different temperatures and pH. The pH will be adjusted by 0.1 N HCl or diluted by NaOH solutions respectively.

3.5.3 Preparation of LEuH-[H2W12O40].nH2O nanocomposite (in situ polymerization): LEuH nanosheets will be prepared by ultrasonicating fresh wet LEuH material (0.2 g) in aqueous media for 10 minutes to delaminate the positively charged nanosheets followed by centrifugation at 2000 rpm to remove undelaminated material. The resultant delaminated nano-sheets of LEuH (0.05 g) will be dispersed in decarbonated deionized water (75 ml) under vigorous stirring at 70 oC, in nitrogen environment. The pH of the nanosheets will slowly be adjusted to 4 using 1N HCl. Na2WO4.2H2O (6.6 mM) dissolved in 150 ml of decarbonated deionized water will be added slowly with stirring and maintaining the pH at 4. The mixture will be stirred at 70 oC for 3 hours, put in a beaker and left undisturbed for 12 hours. The resultant white solid will be separated and washed several times with decarbonated deionized water and dried in vacuum at 40°C for 12 hours. In contrast, ion exchange method will also be used to prepare LEuH-[H2W12O40].nH2O nanomaterial by replacing Na2WO4.2H2O with (NH4)6[H2W12O40].nH2O in the above procedure and reducing reaction time to 3 hours. The resultant nanocomposites will be used in adsorption experiments similar to the ones outlined above with the test ions ranging from Pb, Cd, Cr, Cl and F

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Time Schedule

Literature

Laboratory

Survey

trials

Synthesis and characterization

Waste water

of

decontamination

Fe3O4@SiO2@LEuH@PW10

experiments

Time/Activity

Term 1 Yr 1 Term 2 Yr1 Term 1 Yr2 Term 2 Yr2 Term 1 Yr3

Thesis and paper writing

Term 2 Yr3

Thesis Evaluation

NB: Term 1 Yr 1 = 2012-09-01 to 2013-02-01; Term 2 Yr 3 = 2015-03-01 to 2013-07-01

Budget Items

Cost (元)

Information retrieval, copying costs…………2,000 Chemicals………………………………..….20,000 Miscellaneous expenses ……………….……..2,000 Workshops, seminars and conferences………10,000 Total Cost …………………………………… 34000

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审核小组意见：

审核小组组长签字： 年

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研究生根据审核小组意见对开题报告的改进措施：

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备注：

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