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1期刊名：Journal of Hazardous Materials（危害性材料学报）危险材料杂志，半月刊，平均3.62个月的审稿周期，影响因子4.173，MedSci指数29.771杂志简介：The Journal of Hazardous Materials publishes full length research papers, reviews, project reports, case studies and short communications which improve our understanding of the hazards and risks certain materials pose to people and the environment or deal with ways of controlling the hazards and associated risks. To limit the scope the following areas are excluded: work place health & safety, drugs, and nuclear related topics. The Journal is published in two parts: Part A: Risk Assessment and Management Characterization of the harmful effects of hazardous materials Impact assessment methods and models - acute and chronic effects of hazardous chemical releases Approaches to risk assessment and management, including legislation Incident case histories and lessons for risk management Part B Environmental Technologies Pollution control processes Inherently safer and cleaner technologies Treatment and disposal of solid, liquid and gaseous hazardous wastes Remediation of contaminated soil and groundwater.危险材料杂志出版完整长度的研究论文、评论、项目报告、案例研究和简报，这些文章提高了我们对某些材料对人们和环境可能存在的危害和风险或者控制其危害和相关风险的处理方式的理解。为了限制范围，以下地区被排除在外:工作场所健康与安全、毒品、与核相关的话题。这种杂志在两部分发表。A部分：对有害物质危害性的风险评估和管理描述，影响评估的方法和模型危险化学品释放的急性和慢性影响，风险评估和管理的方法,包括立法事件案例的病史和借鉴风险管理。B部分：环境技术污染控制流程，本质上对固体、液体和气体危险废物污染的土壤和地下水修复要求更安全、更清洁的处理和处置技术。2 发表日期：20093 第一作者：Hui-LongWang（王慧龙）· 单    位  化学学院研究室  无机化学职    称  副教授博士生/硕士生导师学    历  博士电    话  E-mail  hlwang 4 文字内容（1）题目：Preparation and application of sustained release microcapsules of potassium ferrate(VI) for dinitro butyl phenol (DNBP) wastewater treatment（缓释高铁酸钾微胶囊在处理含地乐酚丁基苯酚的废水中的制备及应用的研究）地乐酚dinoseb 橙色固体，熔点3842。在水中的溶解度为100mg/L。大鼠急性经口LD5058mg/kg，对家兔急性经皮LD50为80200mg/kg，鲤鱼TLm(48h)0.10.3mg/L。制剂有乳油。触杀型除草剂。由苯酚与丁烯反应生成2-仲丁基苯酚，再经硝化而生成产品。可用于谷物地中防除一年生杂草，用量为2kg/ha。也可作马铃薯和豆科作物的催枯剂。 高铁酸钾纯品为暗紫色有光泽粉末。198以下干燥空气中稳定。极易溶于水而成浅紫红色溶液，静置后会分解放出氧气，并沉淀出水合三氧化二铁（即氧化铁）。溶液的碱性随分解而增大，在强碱性溶液中相当稳定，是极好的氧化剂。具有高效的消毒作用。比高锰酸钾具有更强的氧化性。 （2）关键词：2-sec-Butyl-4,6-dinitrophenol（2-仲丁基-4,6-二硝基苯酚；地乐酚）Potassium ferrate(VI)（高铁酸价） Microcapsule（微胶囊）Oxidative degradation（氧化降解） Wastewater treatment（废水处理）（3）摘要：The encapsulated potassium ferrate(VI) (K2FeO4) samples were successfully prepared by phase separation method in organic solvents. The ethyl cellulose and paraffin were selected for the microcapsule wall materials (WM). The as prepared microcapsules were characterized by X-ray diffraction (XRD) and Fourier transform infrared spectroscopy (FT-IR). The stability can be enhanced greatly when ferrate(VI) was encapsulated in the microcapsules with a mass ratio of Fe(VI):WM in the range of 1:11:3 for the same conserved time in air compared for pure K2FeO4. The sustained release behavior of the microcapsules with different Fe(VI):WM mass ratios in 8.0M KOH solution was also investigated. The results indicated that the Fe(VI) release was reduced with increase of Fe(VI):WM mass ratios from 1:1 to 1:3. The release kinetics of the microcapsules is found to obey RitgerPeppas equation. The prepared Fe(VI) microcapsules has been used for the removal of a typical alkyl dinitro phenol compound, 2-sec-butyl-4,6-dinitrophenol (DNBP), from aqueous solution. The effect of pH, microcapsule concentration and reaction time was studied thoroughly. The optimal pH for DNBP degradation was 6.5, and at this pH and a microcapsule concentration of 1.2 g/L, approximately 93% of the DNBP was degraded after 80 min. The encapsulated ferrate(VI) samples were found to be very effective in the decolorization and COD reduction of real wastewater from DNBP manufacturing. Thus, this study showed the feasible and potential use of encapsulated Fe(VI) samples in degradation of various toxic organic contaminants and industrial effluents.在有机溶剂中通过相分离法，可以成功的制备出封装的高铁酸钾(VI)(K2FeO4)样品。其中，乙基纤维素和石蜡被选为微胶囊壁材料（WM），作为制备的微胶囊通过x射线衍射(XRD)和傅立叶变换红外光谱(红外光谱)进行表征。与纯高铁酸价相比，在空气中保存相同的时间，以铁(VI): 微胶囊壁材料（WM）的质量比在1:1 -1:3的范围制备的封装的高铁酸钾，能够大大提高其稳定性。也调查了在8.0摩尔的KOH溶液中，以不同的铁(VI):WM质量比率下缓释微胶囊的行为。结果表明，随着铁(VI):WM质量比从1:1到1:3的增加，铁(VI)的释放反而减少。微胶囊的释放动力学被发现服从Ritger-Peppas方程。制备好的铁(VI)微胶囊已被用于从水溶液中移除一种典型的烷基酚化合物地乐酚（2-仲丁基-4,6-二硝基苯酚）。本文对pH值的影响,微胶囊浓度和反应时间进行了彻底研究。对于DNBP降解的最优PH值是6.5，在这个PH条件且微胶囊浓度为1.2 g / L时，大约80分钟后DNBP可被降解93%。封装的高铁酸盐(VI)样品被发现对去除生产DNBP产生的实际废水的脱色和COD的减少是非常有效的。因此，本研究表明封装的高铁酸盐(VI)在降解各种有毒有机污染物和工业废水方面的可行性和应用潜力。（4） 前言Alkyl dinitro phenols are widely acknowledged to be a group of toxic refractory chemicals, which can be detrimental to human health and the environment. 2-sec-butyl-4,6-dinitrophenol (DNBP) is a typical example of this class of toxic compounds. It is manufactured in high quantities, most being used as polymerization inhibitor for vinyl aromatics in petrochemical industry and as a herbicide in agriculture 1,2. DNBP is introduced into surface water from its manufacturing and application processes. DNBP has some undesirable side effects, such as toxicity and carcinogenity, and its uses and the maximum concentration level in water were restricted by the US Environmental Protection Agency (EPA) 35. Thus the degradation of DNBP and its removal from the environment are of great public concern. The more complex environmental problems are that DNBP is resistant to microbial degradations and can be hardly destroyed in conventional wastewater treatment, so there is a continuing interest in the application of more efficient water treatment chemical reagents to degrade DNBP and achieve higher water quality. 烷基酚类化合物被广泛公认为是一组有毒难治理的化学品,这些物质可能对人类健康和环境产生危害。地乐酚（DNBP)是这类的有毒化合物的一个典型的例子。它被大量的生产，大部分被用作石化行业对乙烯基芳烃的聚合抑制剂和农业中的除草剂，在其生产和使用的过程中被引入到地表水。地乐酚具有一些不好的副作用，,如毒性和致癌性，同时美国环境保护署(EPA)对它在水中的使用和最大浓度水平都有受限。因此，将地乐酚从环境中降解和去除已引起公众的极大关注。更复杂的环境问题是地乐酚耐微生物降解，并且在传统废水处理中几乎不能被分解破坏，所以本文对寻找更有效的水处理化学试剂降解地乐酚的应用和获得更高质量的水有着持续的兴趣。It has been well documented that potassium ferrate, K2FeO4, is receiving considerable attention at present as an efficient wastewater treatment chemical reagent owing to the high redox potential of the ferrate(VI) ion from 2.2 to 0.7V in acidic and basic solutions, respectively, and associated coagulation effect arising from the reduced Fe(III) species for metals and non-metals from solution . As well as the high oxidation capacity and coagulation effect, the ferrate(VI) also possesses the disinfection function . More importantly, ferrate(VI) is also an environmental friendly treatment chemical, which will not produce any harmful by-products in the treatment process. Such unique properties make the ferrate(VI) to be an environmental friendly and dual function chemical reagent and could combine the pre-disinfection/oxidation with coagulation into one unit . Due to such unique properties, many researches have been carried out in the use of potassium ferrate(VI) for degrading various synthetic and natural organic pollutants . However, the problems with the stability of the concentrated ferrate chemicals have hindered the implementation of ferrate(VI) technology in the full-scale treatment of wastewater. Currently, there is a need for further studies concerned with increasing the stability and reactivity of ferrate(VI) with contaminants of concern.众所周知,高铁酸钾（K2FeO4）作为一种高效的废水处理化学试剂，目前正受到相当多的关注,这是由于高铁酸盐(VI)离子具有较高的氧化还原电位，在酸性和碱性溶液中它的电极电势分别为2.2 V和0.7 V,同时由于溶液中的金属和非金属导致铁(III)减少，进而产生混凝效应。高铁酸盐(VI)不但具有较高的氧化能力和凝聚效应,它还具有消毒功能。更重要的是,高铁酸盐(VI)也是一种环境友好的化学处理试剂, 在处理过程中它不会产生任何有害的副产品。这种独特的性质使高铁酸盐(VI)成为一种环境友好和双功能化学试剂，并且能将预消毒/氧化与凝固结合成一个单元。由于这种独特的性质, 已经开展了许多关于高铁酸钾(VI)被用来降解各种合成和天然有机污染物的研究。然而，纯高铁酸盐化学物质的稳定性这一问题已成为阻碍高铁酸盐(VI)技术在全面的废水治理中实现。目前,有必要进一步研究有关增加稳定性和与高铁酸盐(VI)相关的污染物的反应性。 Presently, microencapsulation is very useful for modifying chemical properties of a core material. Microcapsules are minute heterogeneous containers and generally consist of a core material enclosed within a wall material. Microcapsules are widely used to control a core materials release characteristics and to improve its stability by protecting it from environmental stimuli . Although the performance of encapsulated potassium ferrate(VI) for oxidative remediation of trichloroethylene contaminated groundwater has been investigated recently , no comparative study results have been reported to address the preparation of encapsulated potassium ferrate(VI) using various methods and the performance of the encapsulated ferrate(VI) in the degradation of different organic pollutants, which is one of the objectives of this paper. In the present study, microcapsules of potassium ferrate(VI) were successfully synthesized by phase separation method in cyclohexane which was chosen as an organic solvent. The characteristics of the prepared microcapsules of potassium ferrate(VI) were analyzed by X-ray diffraction (XRD) and Fourier transform infrared spectroscopy (FT-IR). Specifically, this paper aims to investigate the performance of encapsulated potassium ferrate(VI) for aqueous degradation of 2-sec-butyl-4,6-dinitrophenol, which was chosen as a typical alkyl dinitro phenol organic pollutant.目前,微型胶囊对于改变一种核心材料的化学性质是非常有用的。微胶囊是微小的由不同成分形成的容器，并且通常由一种封闭在壁材料中的核心材料构成。微胶囊被广泛用于控制核心材料的释放特性,通过保护它免受环境的刺激来提高其稳定性。尽管最近已经调查了密封的高铁酸钾(VI)对被三氯乙烯污染的地下水的氧化修复的性能，但从未报道过对比的研究结果，从而解释使用各种方法制备密封的高铁酸钾(VI)的优劣及在降解不同的有机污染物过程中密封的高铁酸钾(VI)性能的好坏，这是本文的目标之一。在目前的研究中,用环己烷作为有机溶剂，通过相分离的方法已成功合成高铁酸钾(VI)微胶囊。所制备的高铁酸钾(VI)微胶囊的特点通过x射线衍射(XRD)和傅立叶变换红外光谱(FT-IR)进行了分析。具体来说, 本文旨在研究密封的高铁酸钾(VI)微胶囊水解2-仲丁基-4,6-二硝基苯酚（地乐酚）过程中的性能研究，这种地乐酚被选为一个典型的烷基地乐酚酚有机污染物。（5）Materials and methods（材料和方法）5.1 Chemicals（化学药品）The core material K2FeO4 (purity >98.5%) was prepared with a high yield (>80%) by the modified wet oxidation method via reacting ferric nitrate with hypochlorite in strongly basic media and then isolation from the saturated KOH solution 18. The wall materials (abbr. as WM) used were ethyl cellulose and paraffin (from Sinopharm Chemicals). DNBP was used as an alkyl dinitro phenol pollutant and obtained from Retell Fine Chemical Co., Ltd. (Tianjin, China).A stock solution of DNBP(1.7×104 M)was prepared by dissolving DNBP in deionized water. All other chemicals and reagents used were of analytical reagent (AR) grade and purchased from Kermel Chemical reagent Co. Ltd. (Tianjin, China) unless otherwise indicated.核心材料K2FeO4(纯度> 98.5%)的制备：采用改进的湿法氧化法，通过硝酸铁和次氯酸盐在强碱性媒介中反应，然后从饱和KOH溶液中分离出来，从而可制得高产率(> 80%)的K2FeO4。所用的壁材料成分为乙基纤维素和石蜡(来源于国药控股化学品公司)。DNBP作为一种烷基地乐酚的污染物被使用，来源于瑞泰精细化工有限公司(天津,中国)。DNBP储备溶液(1.7×104 M)的制备：在去离子水中溶解DNBP。除非另有说明，否则所有其他使用的化学物质和试剂都是分析纯试剂(AR)等级，且购买于科密欧化学试剂有限公司(天津,中国)。5.2. Experimental procedures（实验步骤）5.2.1. Preparation of Fe(VI) microcapsules（ 铁(VI) 微胶囊的制备）Microcapsules of potassium ferrate(VI) were prepared by a phase separation method in an organic solvent. The synthesis method was as follows: To a cyclohexane solution (50 mL) was added the wall materials ethyl cellulose (0.5 g) and paraffin (2.5 g) slowly. After complete addition, the mixture was stirred at 800rpm for 15min and heated to 60 C until the wall materials were dissolved completely. Then, the various amounts of core material K2FeO4 were slowly introduced to keep the mass ratios of Fe(VI):WM from 1:1 to 1:3, and the solution was sonicated and refluxed for 30min. After cooling to room temperature, the supernatant liquid was poured off and the final product was collected, washed twice with cyclohexane, dried in vacuo and stored in a vacuum desiccator prior to further use.在一种有机溶剂中，通过相分离法来制备高铁酸钾铁(VI) 微胶囊。合成方法如下: 将壁材料乙基纤维素(0.5克)和石蜡(2.5 g)缓慢加到环己烷溶液(50 mL)中，添加完成后, 在800 rpm（转/分钟）的转速下将混合持续搅拌15分钟，并加热到60C，直到壁材料完全溶解。然后，核心材料K2FeO4以不同的量慢慢加入到前面配的溶液中，要保持铁(VI):WM的质量比从1:1至1:3，再把溶液超声提取（sonicated and refluxed）三十分钟，冷却到室温后,上清液倒出来, 收集最终产品,。用环己烷洗两次,在真空条件下干燥并存储在一个真空干燥器中已被将来使用。5.2.2. Characterization of the microcapsules（微胶囊的表征）The X-ray diffraction patterns of the prepared microcapsule samples were obtained on a Shimadzu XRD-6000 diffractometer using Cu K radiation (40 kV, 30mA) with a scan rate of 0.06° s1. FT-IR studies were carried out in the 5004000cm1 frequency range in the transmission mode (Avatar 360, Thermo Nicolet Co., America).在日本岛津公司XRD- 6000衍射仪中获得了所制备的微胶囊的X射线衍射模式，该衍射仪采用铜钾辐射(40 kV, 30mA)且扫描速率为0.06°s1。在5004000cm1频率范围进行了傅立叶变换红外光谱在传输模式方面的研究（Avatar 360，热电尼高力公司，美国）。5.2.3. Stability of the microcapsules（微胶囊的稳定性）An accurate of the prepared microcapsules, equivalent to 0.5 g of K2FeO4 and 0.5 g of pure K2FeO4 were kept in air at 25 C for 30 days to evaluate for their stability. At different time intervals, the microcapsule samples were taken, accurately weighed and washed with 50mL of cyclohexane at 60 C for 20 min to remove the wall materials completely. The decomposition of Fe(VI) was monitored by determining the content of Fe(VI) at different time intervals. The degree of decomposition (D%) can be calculated by the following【（ W0 Wt）/W0 】× 100% (1)where W0 and Wt are the Fe(VI) content at time t = 0 and t, respectively. 所制备微胶囊的稳定性的一种准确的描述，相当于0.5克普通K2FeO4和0.5克纯K2FeO4在25C条件下保存在空气中30天后来评价其稳定性。在不同的时间间隔, 采集微胶囊样品,准确称重后，用50毫升的环己烷在60C温度下清洗20分钟以完全除去壁材料。通过测定在不同的时间间隔Fe(VI)的含量来检测高铁酸盐(VI)的分解量。分解度(D%)能通过以下式子计算：D% = × 100% (1)W0 和Wt分别表示在时间t = 0和t时铁(VI)的含量。5.2.4. Encapsulated Fe(VI) release test（封装的Fe(VI)的释放试验）The release of encapsulated potassium ferrate(VI) was carried out using 200mL of 8M KOH solution as dissolution medium at 25 C. An accurate weight of the microcapsules, equivalent to 50mg of potassium ferrate(VI) was added in dissolution medium while the solution was agitated for 40min. The sample solution was withdrawn at predetermined interval to analyze the Fe(VI) concentration by spectroscopy method. An equal volume of the same dissolution medium was added to maintain a constant volume. The Fe(VI) release amounts were plotted as the cumulative amount and percentage content in the dissolution medium against the release time.在25C条件下，使用200毫升8mol/L的KOH溶液作为溶剂，将胶囊状高铁酸钾(VI)进行释放。一粒精确重量的微胶囊，相当于添加50毫克的高铁酸钾(VI)至溶剂中，同时搅动溶液40分钟。为了采用光谱法分析Fe(VI)的浓度，需要在预先确定的时间间隔取出样品溶液。同体积的同种溶剂被添加到取出的样品溶液中以维持一个恒定的体积。最后以累积数量和百分比含量对释放时间作铁(VI)的释放量的坐标图。5.2.5. Degradation of DNBP（DNBP的降解）Oxidative reaction between encapsulated Fe(VI) samples and DNBP was carried out using 100mL conical borosilicate glass reactors in which DNBP solution was agitated with magnetic stirrers when an accurate weight of the microcapsules was added. The reactors were mechanically stirred for selected time periods. For analysis, sodium sulfite was added to the sample immediately at selected intervals to stop any further reaction. The samples were then filtered and the filtrate was centrifuged at 6000rpm for 10min before analysis. All the experiments were carried out at room temperature (25±1 C).Oxidative reaction time, solution pH and encapsulated Fe(VI) concentration were investigated for their effect on the oxidation performance in terms of DNBP removal, defined as removal (%) = (C0 C)/C0 ×100, where C0 and C are the concentration of DNBP at t = 0 and t, respectively.使用100毫升锥形硼硅酸盐玻璃瓶作为反应容器，在里面加DNBP溶液，用磁力搅拌器不断搅拌的同时，向