CN111908513A - 一种用于染料吸附的介晶铁氧化物材料及其制备方法 - Google Patents
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Abstract
本发明公开了一种用于染料吸附的介晶铁氧化物材料及其制备方法，属于染料吸附材料领域，一种用于染料吸附的介晶铁氧化物材料的制备方法，包括以下步骤：步骤一：将一定浓度的EDTA与Fe2+溶液均匀混合，20‑30℃下陈化一天，得到γ‑FeOOH或α‑FeOOH前驱体；步骤二：将步骤一得到的前驱体离心洗涤至少一次后冷冻干燥；步骤三：在一定温度下通氩气或空气加热处理，通过高温作用下前驱体脱水得到介晶磁铁矿（Fe3O4）和磁赤铁矿（γ‑Fe2O3）矿相，本方案涉及了应用生物矿化技术可控制备介晶磁性铁氧化物过程及介晶磁性铁氧化物复合碳材料的新材料制备，所获得的新材料具有易分离、廉价、高效吸附阴阳离子型染料污染物等特点。
Description
技术领域
本发明涉及染料吸附材料领域，更具体地说，涉及一种用于染料吸附的介晶铁氧化物材料及其制备方法。
背景技术
染料废水的产生是纺织、造纸、印刷、食品、化妆品等行业使用的结果。据估，每年生产的染料中有2％的染料在生产经营过程中随污水排放。染料废水具有有机物含量高、有毒、难处理等特点，可导致多种疾病，如癌症、贫血、呼吸系统疾病等。因此，治理染料废水具有重要的环境意义。目前，处理染料的方法包括电化学法、光催化法、生物氧化法和吸附法等。其中，吸附法因具备操作廉价、简单、高效等特点是目前研究较多且较实用的方法。不同的吸附剂如活性炭、天然材料、生物吸附剂、高分子材料、纳米多孔结构、纳米纤维和碳基材料等都进行了研究。其中，高比表面积和高孔隙率的材料被认为是当前最具有实际应用前景的染料吸附材料。不过，现阶段所用的材料因比表面积较小、孔隙率低、吸附剂吸附容量低、成本高、吸附剂难分离等问题难以满足实际工程应用的要求。因此急需开发廉价、易分离、高吸附容量的材料。
生物矿化是合成无机晶体的受控过程。先前的研究发现自然界中的铁氧化菌和锰氧化菌在温和条件下可液相生成高比表面的铁锰氧化物，其氧化状态、晶相和形态均受自然条件控制。至此之后，金属氧化物的生物矿化过程在生物学、晶体生长及其应用等方面引起了人们的极大兴趣。例如，先前的研究表明铁氧化物可以在趋磁细菌的细胞内和细胞外矿化。当存在Fe2+和Fe3+情况下，趋磁细菌可促进铁氧化物形成。通过基因组和蛋白质组分析，目前已确定与铁氧化物形成有关的生物分子。研究人员认为微生物产生的生物多聚物在铁物种的吸附和铁氧化物的成核方面起重要作用。
发明内容
1.要解决的技术问题
针对现有技术中存在的问题，本发明的第一目的在于提供一种用于染料吸附的介晶铁氧化物材料的制备方法，它采用乙二胺四乙酸二钠(EDTA)作为配体螯合剂，通过改变合成条件(pH、温度、EDTA浓度等)，制备了系列介晶磁性铁氧化物；
第二目的在于提供一种用于染料吸附的介晶铁氧化物材料，它利用上述方法制成，具有易分离、高孔隙率、高吸附容量、高比表面积等特点，一方面可作为吸附剂高效吸附阴阳离子型染料，另一方面又可作为理想的载体进一步负载比表面积更大、孔隙率更高的材料实现染料的高效吸附。
2.技术方案
为解决上述问题，本发明采用如下的技术方案。
一种用于染料吸附的介晶铁氧化物材料的制备方法，包括以下步骤：
步骤一：将一定浓度的EDTA与Fe2+溶液均匀混合，20-30℃下陈化一天，得到γ-FeOOH或α-FeOOH前驱体；
步骤二：将步骤一得到的前驱体离心洗涤至少一次后冷冻干燥；
步骤三：在一定温度下通氩气或空气加热处理，通过高温作用下前驱体脱水得到介晶磁铁矿(Fe3O4)和磁赤铁矿(γ-Fe2O3)矿相。
进一步的，步骤一所述EDTA的浓度为0.01-0.1mol/L。
进一步的，所述陈化温度为20-30℃。
进一步的，步骤三所述加热处理的温度范围为300-600℃，加热时间为1-30min。
进一步的，采用如权利要求1所述的一种用于染料吸附的介晶铁氧化物材料的制备方法制成的系列介晶磁性铁氧化物。
进一步的，一种用于染料吸附的介晶铁氧化物材料在去除阴阳离子型染料上的应用，所述阴阳离子型染料可以为刚果红、日落黄、胭脂红、结晶紫、亚甲基蓝、苯胺紫、孔雀石绿等。
进一步的，一种用于染料吸附的介晶铁氧化物材料作为载体的应用。
3.有益效果
相比于现有技术，本发明的优点在于：
一、本方案利用EDTA代替胞外聚合物，模拟生物矿化过程，以生物矿化的思路来制备材料，且制得的材料比表面大、易分离、孔隙率高。
二、本方案制备的材料具有大比表面和大量活性位点，可实现阴阳离子染料的高效吸附。
三、本方案吸附后的材料可通过磁棒进行回收，环境污染风险较低。
四、利用本方案制备的介晶材料还可以作为有效的载体。
附图说明
图1为本发明的介晶磁性铁氧化物合成过程示意图；
图2为本发明的介晶γ-Fe2O3的XRD谱图；
图3为本发明的介晶γ-Fe2O3的TEM图(左)和HRTEM图(右)；
图4为本发明的介晶γ-Fe2O3的N2吸附脱附等温线；
图5为本发明的介晶γ-Fe2O3的N2吸附脱附相应的孔径分布图；
图6为本发明的介晶γ-Fe2O3和γ-Fe2O3@C的亚甲基蓝等温吸附曲线；
图7为本发明的吸附后的γ-Fe2O3@C材料磁棒分离图片。
具体实施方式
下面将结合本发明实施例中的附图；对本发明实施例中的技术方案进行清楚、完整地描述；显然；所描述的实施例仅仅是本发明一部分实施例；而不是全部的实施例，基于本发明中的实施例；本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例；都属于本发明保护的范围。
合成实施例1：
请参阅图1，500ml烧杯中加入0.1mol/L Fe2+溶液,然后向烧杯内加入0.132g乙二胺四乙酸二钠，搅拌混合均匀，pH＝5，25℃条件下陈化一天，得到γ-FeOOH前驱体；前驱体离心洗涤3次后冷冻干燥；400℃下通2min空气加热处理，通过高温作用下前驱体脱水得到γ-Fe2O3矿相。
合成试试例2：
请参阅图1，500ml烧杯中加入0.1mol/L Fe2+溶液,然后向烧杯内加入0.0132g乙二胺四乙酸二钠，搅拌混合均匀，pH＝5，30℃条件下陈化一天，得到γ-FeOOH前驱体；前驱体离心洗涤3次后冷冻干燥；400℃下通10min空气加热处理，通过高温作用下前驱体脱水得到γ-Fe2O3矿相。
合成实施例3：
请参阅图1，500ml烧杯中加入0.1Fe2+溶液,然后向烧杯内加入0.066g乙二胺四乙酸二钠，搅拌混合均匀，pH＝10，25℃条件下陈化一天，得到α-FeOOH前驱体；前驱体离心洗涤2次后冷冻干燥；400℃下通氩气加热处理，通过高温作用下前驱体脱水得到Fe3O4矿相。
合成实施例4：
请参阅图1，500ml烧杯中加入0.1Fe2+溶液,然后向烧杯内加入0.066g乙二胺四乙酸二钠，搅拌混合均匀，pH＝10，20℃条件下陈化一天，得到α-FeOOH前驱体；前驱体离心洗涤2次后冷冻干燥；600℃下通氩气加热处理，通过高温作用下前驱体脱水得到Fe3O4矿相。
验证实施例：
请参阅图2，以γ-Fe2O3的表征为例：X射线衍射(XRD)谱图显示，所得的矿相具有γ-Fe2O3的特征峰，与标准磁赤铁矿JCPDS卡片No.25-1402相符。
请参阅图3，透射电子显微镜(TEM)图显示所制备的材料由尺寸小于5纳米的纳米晶体组成(图3左)，结构较为疏散，符合介晶材料特点。高分辨透射电子显微镜图(HRTEM；图3右)观察到了明显的晶格条纹，其晶面间距与γ-Fe2O3可很好的吻合，再次证明了所得的物相为磁赤铁矿。
请参阅图4-5，γ-Fe2O3的N2吸附-脱附等温线(图4)展示出典型的IV型吸附特征，且存在明显的H3型回滞环，说明γ-Fe2O3具有大量介孔结构。此结构通过Barrett-Joyner-Halenda(BJH)孔径分布得到进一步证实，结果显示γ-Fe2O3孔径分布主要在2～50nm范围内(参阅图5)。γ-Fe2O3的表面积经BET法估算为273m2/g，远高于传统合成的γ-Fe2O3(约50m2/g)，突出了EDTA参与合成的优势。上述结果证明了高比表面的介晶磁赤铁矿材料的成功合成。
阴阳离子型染料去除的应用实施例：
请参阅图6，将上述制备的材料用于阴阳离子型染料的去除。以吸附亚甲基蓝染料为例，等温吸附结果显示磁赤铁矿对亚甲基蓝染料的吸附量高达127.9mg/g。材料具备高吸附容量的直接原因是所制备的介晶材料具备高比表面积及发达的孔隙结构，这提升了材料表面的吸附位点。
载体实施例：
利用合成的介晶磁赤铁矿作为有效载体，将目前已报道的部分具有较优性能的碳基材料负载于介晶磁赤铁矿表面。这一方面可利用磁赤铁矿易分离性解决碳基材料难分离的特点，另一方面可进一步提升材料的吸附性能。
以负载生物炭为例，具体的制备方法如下：
称取20g过10目筛子的干燥芦苇粉末置于坩埚中，盖上盖子600℃炭化处理6h；冷却至室温后取出，制得的炭化产物用200ml1mol/L的HCl溶液处理12h后，置于烘箱70-80℃烘干得到生物炭。进一步的将生物炭与介晶磁赤铁矿均匀混合，老化12h后通过磁棒分离，200℃干燥后得到生物炭负载介晶磁赤铁矿材料(γ-Fe2O3@C)。得到的材料相比磁赤铁矿具备更高的比表面积(1402m2/g)。等温吸附曲线数据与Langmuir模型有较好拟合，模型相关系数高于Freundlich模型，说明亚甲基蓝染料在吸附剂上的吸附以单层吸附为主。亚甲基蓝染料吸附容量显示γ-Fe2O3@C的饱和吸附容量为429mg/g(见图6)，远高于相关文献报道的甲基蓝吸附容量(表1)。
请参阅图7，吸附后亚甲基蓝的材料可通过磁棒进行回收，满足了制备材料易分离的需求。
表1本方案的材料与其他材料亚甲基蓝吸附容量
以上所述；仅为本发明较佳的具体实施方式；但本发明的保护范围并不局限于此；任何熟悉本技术领域的技术人员在本发明揭露的技术范围内；根据本发明的技术方案及其改进构思加以等同替换或改变；都应涵盖在本发明的保护范围内。
Claims (7)
1.一种用于染料吸附的介晶铁氧化物材料的制备方法，其特征在于：包括以下步骤：
步骤一：将一定浓度的EDTA与Fe2+溶液均匀混合，20-30℃下陈化一天，得到γ-FeOOH或α-FeOOH前驱体；
步骤二：将步骤一得到的前驱体离心洗涤至少一次后冷冻干燥；
步骤三：在一定温度下通氩气或空气加热处理，通过高温作用下前驱体脱水得到介晶磁铁矿（Fe3O4）和磁赤铁矿（γ-Fe2O3）矿相。
2.根据权利要求1所述的一种用于染料吸附的介晶铁氧化物材料的制备方法，其特征在于：步骤一所述EDTA的浓度为0.01-0.1 mol/L。
3.根据权利要求1所述的一种用于染料吸附的介晶铁氧化物材料的制备方法，其特征在于：所述陈化温度为20-30℃。
4.根据权利要求1所述的一种用于染料吸附的介晶铁氧化物材料的制备方法，其特征在于：步骤三所述加热处理的温度范围为300-600℃，加热时间为1-30 min。
5.采用如权利要求1所述的一种用于染料吸附的介晶铁氧化物材料的制备方法制成的系列介晶磁性铁氧化物。
6.根据权利要求6所述的一种用于染料吸附的介晶铁氧化物材料在去除阴阳离子型染料上的应用。
7.根据权利要求6所述的一种用于染料吸附的介晶铁氧化物材料作为载体的应用。
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