CN114870870A - 协同处理MO和Cr(Ⅵ)污染的磁性环境净化材料及其制备方法 - Google Patents
协同处理MO和Cr(Ⅵ)污染的磁性环境净化材料及其制备方法 Download PDFInfo
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Abstract
本发明提供了一种协同处理MO和Cr(Ⅵ)污染的磁性环境净化材料及其制备方法，属于环境净化材料领域。本发明的磁性环境净化材料由白铁矿/黄铁矿/四氧化三铁三相复合构成，具有通过光催化和氧化还原作用协同处理MO和Cr(Ⅵ)污染的能力，同时具备磁回收性。该材料的合成方法是以硫酸亚铁、硫脲和硫粉为原料，在160‑200℃的水热条件下得到白铁矿/黄铁矿相的二硫化亚铁，然后通过可控氧化在表面形成四氧化三铁，得到白铁矿/黄铁矿/四氧化三铁磁性复合环境净化材料。相比于传统光催化材料，该材料可以同时降解有机污染物与Cr(Ⅵ)，具有制备方法简单、成本低、使用回收方便等优点，在复杂污染污水净化领域有良好应用前景。
Description
技术领域
本发明提供了一种协同处理MO和Cr(Ⅵ)污染的磁性环境净化材料及其制备方法，该材料属于有机物光催化及重金属Cr(Ⅵ)复合降解领域。
背景技术
随着工业的不断发展，环境污染问题越来越受到重视。如何利用绿色节能的方式解决环境污染问题成为近年来的产品开发热点。有机污染物如染料、抗生素和农药等大量排入环境中，是环境污染中的一大问题；此外工业发展所带来的重金属污染问题也日益严重。有机污染物中代表性物质是甲基橙MO，主要来源于印染行业，会破坏生态环境且最终通过食物链聚集最终在人体内大量堆积；重金属污染的典型代表是Cr(Ⅵ)，主要来源于电镀和印染行业，Cr(Ⅵ)具有高毒性、高流动性、致癌性和畸变性，产生了极大的污染问题。而在实际生产过程中，污水往往含有有机物和重金属等多种污染物，复合污染水相中体系复杂，所需的治理手段和成本都大大增加，因此找到一种材料可以同时进行有机物和Cr(Ⅵ)的降解是非常有必要的。
对于有机物和重金属共存污水的治理方法，目前只有少部分的研究，比如专利CN105110448A利用零价铁还原Cr(Ⅵ)和活化过硫酸盐降解有机物，但是所使用的材料存在制备过程复杂、降解过程中材料消耗大以及成本较高等缺点。专利CN106830168B用多种基团表面修饰的石墨烯/碳纳米管用于有机物和重金属的吸附，该方法所用的材料成本较高。专利CN110282698A用硅藻土颗粒制备纤维膜用于去除重金属和有机物，但材料对污染物的去除效果较差，只能用于处理低浓度的废水。近年报道了传统半导体对有机物和Cr(Ⅵ)的共同降解，但是这些材料的制备条件要求较高，材料成本较大，且对有机物和Cr(Ⅵ)的协同降解速率都较低([1]李靖，曹译文，戴朝展，等.低温固相合成CaTiO3纳米粉及其光催化处理水中Cr(Ⅵ)和硝基苯陶瓷学报，2018，39(01):53-58.[2]王后锦，吴晓婧，王亚玲，等.二氧化钛纳米管阵列光电催化同时降解苯酚和Cr(Ⅵ)催化学报，2011，32(04):637-642.[3]魏凯，李可心，曾振兴，等.在Cr(Ⅵ)和4-氯酚复合污染系统中多孔石墨相氮化碳的协同光催化效应催化学报，2017，38(11):1804-1811.)，且使用非磁性粉末治理污水，存在材料难以回收再利用的缺点。因此，当前急需开发可以高效降解有机物和Cr(Ⅵ)且具有回收性的材料。
二硫化亚铁具有黄铁矿与白铁矿两种晶型，由于白铁矿型二硫化亚铁的较小的禁带宽度和低反应活性，目前尚无白铁矿型二硫化亚铁应用于环境净化的报道。目前已有相关研究对黄铁矿在环境净化方向上进行了探索，如专利CN201911392377.5研究了二硫化亚铁和碳化氮的复合材料在基于芬顿效应的光催化应用；如专利CN99109634.7研究了天然黄铁矿对Cr(Ⅵ)的降解；如专利CN201510460447.1研究了天然黄铁矿对孔雀石绿和Cr(Ⅵ)降解的协同作用。而上述发明专利中存在以下不足：(1)芬顿效应需要大量消耗过氧化氢导致成本过高；(2)天然矿物受制于比表面积过小、结晶度不高和杂质过多等缺陷，导致材料的光催化或Cr(Ⅵ)降解率过低或者反应速度过慢；(3)粉末材料在液相中没有回收性导致治理成本过高。
二硫化亚铁成分中含有的Fe2+和S22-都能够还原Cr(Ⅵ)，由于Fe离子的价态变化和体系中的电子交换作用可以在水相中产生H2O2和多种自由基，可以利用光催化和化学催化实现多种有机物的降解。本发明通过控制复合比例和表面氧化得到了白铁矿/黄铁矿/四氧化三铁复合材料。该材料通过白铁矿/黄铁矿复合形成异质结半导体，提高了材料在光照下产生载流子的分离效率；进一步的，几相复合的形式增加了其表面缺陷，使表面上的吸附态Fe离子量大，能够快速和溶液中的溶解氧、Cr(Ⅵ)以及光生载流子快速反应，强化了材料协同降解MO和Cr(Ⅵ)污染的能力；此外存在的四氧化三铁还使得材料具备了磁回收性，可以低成本、高效低处理MO和Cr(Ⅵ)混合污染。
发明内容
为了实现工业污水中有机污染物和重金属的共同降解，本发明提供了一种通过协同效应处理MO和Cr(Ⅵ)污染的磁性复合环境净化材料及制备方法。
为实现上述目的，本发明采用以下技术方案：
步骤1，称取0.025mol的硫酸亚铁置于40ml乙醇溶液中，搅拌30分钟后加入0.1mol的硫脲与0.01～0.04mol的硫粉，在常温下搅拌5-30分钟，得到混合悬液。
步骤2，将步骤1的混合悬液移入100ml溶剂热反应釜中，在160～200℃高温条件下溶剂热反应24～72小时，取出冷却至室温，固液分离，100ml乙醇清洗3次，100ml超纯水清洗3次，在50-60℃温度烘干6小时，研磨至小于200目。
步骤3，将通过步骤2获得的样品在湿度30-40％的烘箱中80～100℃表面氧化8～10小时，获得成品。本发明有如下的优点和有益效果在于：该材料无光照情况下2分钟之内能够使50mg/L的Cr(Ⅵ)降解99.4％；在有Cr(Ⅵ)存在时，该材料在紫外光照1.5小时后对20mg/L甲基橙的降解率能达到70.5％。相比于传统半导体仅对有机物有光催化作用，该材料可以快速降解Cr(Ⅵ)，可以在有机污染物与Cr(Ⅵ)共存污染液中发挥更好的环境净化功效，具有制备方法简单、磁性可回收、环境净化效率高等优点。
附图说明：
图1是本发明制备的铁基硫氧复合半导体材料的XRD谱图。
图2是本发明制备的铁基硫氧复合半导体材料的SEM图。
图3和图4是本发明制备的铁基硫氧复合半导体材料在紫外光照下对甲基橙MO和Cr(Ⅵ)的降解率图。
图5是本发明制备的铁基硫氧复合半导体材料在水相中环形磁铁聚集的照片。
具体实施方式：
下面结合附实施例对本发明做进一步说明。
实施例1
一种通过协同效应处理MO和Cr(Ⅵ)污染的磁性复合环境净化材料及制备方法。称取0.025mol的硫酸亚铁置于40ml乙醇中，加入0.1mol的硫脲与0.01mol硫粉，在常温下搅拌10分钟；将配置好的混合悬液移入100ml溶剂热反应釜中，在200℃温度条件下溶剂热24小时后将样品取出，然后用乙醇和去离子水清洗3次后，在50℃温度下烘干6小时后经研磨，最后将样品在100℃温度，30％湿度下氧化4小时得到样品。
实施例2
一种通过协同效应处理MO和Cr(Ⅵ)污染的磁性复合环境净化材料及制备方法。称取0.025mol的硫酸亚铁置于40ml乙醇中，加入0.4mol的硫脲与0.01mol硫粉，在常温下搅拌20分钟；将配置好的混合悬液移入100ml溶剂热反应釜中，在180℃温度条件下溶剂热72小时后将样品取出，然后用乙醇和去离子水清洗3次后，在50℃温度下烘干6小时后经研磨，最后将样品在90℃温度，35％湿度下氧化6小时得到样品。
实施例3
一种通过协同效应处理MO和Cr(Ⅵ)污染的磁性复合环境净化材料及制备方法。称取0.025mol的硫酸亚铁置于40ml乙醇中，加入0.2mol的硫脲与0.01mol硫粉，在常温下搅拌30分钟；将配置好的混合悬液移入100ml溶剂热反应釜中，在160℃温度条件下溶剂热72小时后将样品取出，然后用乙醇和去离子水清洗3次后，在60℃温度下烘干6小时后经研磨，最后将样品在80℃温度，40％湿度下氧化8小时得到样品。
实施例4
一种通过协同效应处理MO和Cr(Ⅵ)污染的磁性复合环境净化材料及制备方法。称取0.025mol的硫酸亚铁置于40ml乙醇中，加入0.1mol的硫脲与0.03mol硫粉，在常温下搅拌30分钟；将配置好的混合悬液移入100ml溶剂热反应釜中，在180℃温度条件下溶剂热72小时后将样品取出，然后用乙醇和去离子水清洗3次后，在60℃温度下烘干6小时后经研磨，最后将样品在100℃温度，40％湿度下氧化10小时得到样品。
以实施例4为例，图1为所得到的样品的XRD谱图，可以看出所得样品的XRD谱图与黄铁矿PDF#42-1340、白铁矿PDF#74-1051和四氧化三铁#PDF79-0416匹配较好，说明该方法制备出了白铁矿/黄铁矿/四氧化三铁复合半导体材料；图2为所得样品的SEM图，所制备的样品为球状和颗粒状，可以看出两者结合紧密，说明制备出的原位复合材料结合较好。
图3为该材料在单一和共存污染液中对Cr(Ⅵ)的降解率，实验证明在2分钟之内该材料能够使50mg/L的Cr(Ⅵ)降解99.4％；图4为该材料在单一和共存污染液中对甲基橙MO的降解率，在有Cr(Ⅵ)体系中，材料对20mg/L甲基橙MO的降解率能达到70.5％。该材料可以快速降解Cr(Ⅵ)，可以在有机污染物与Cr(Ⅵ)共存污染液中发挥更好的环境净化功效。
图5为材料在水相中的磁性聚集照片(外部磁场为环形和方形，左图为环形，右图为方形)，材料在不同形状的磁场作用下会以一定形状聚集在一起，证明了材料具有磁可回收性。
以上所述仅为本发明的实施例，并非因此限制本发明的专利范围，凡是利用本发明说明书及附图内容等效变换，或直接或间接运用在其他相关的技术领域，均同理包括在本发明的专利保护范围内。
Claims (3)
1.本发明提供了一种协同处理MO和Cr(Ⅵ)污染的磁性环境净化材料，该材料的特征为：由白铁矿/黄铁矿/四氧化三铁三相复合构成，复合结构基体是球形的白铁矿/黄铁矿相二硫化亚铁，表面是颗粒状四氧化三铁。
2.根据权利要求1中所述的协同处理MO和Cr(Ⅵ)污染的磁性环境净化材料，该材料具有在水环境中协同进行光催化降解甲基橙(MO)及快速降解Cr(Ⅵ)的功能，且具有可回收磁性。
3.根据权利要求1中所述的协同处理MO和Cr(Ⅵ)污染的磁性环境净化材料的制备方法，其特征在于，包括以下步骤：
步骤1，称取0.025mol的硫酸亚铁置于40ml乙醇溶液中，搅拌30分钟后加入0.1mol的硫脲与0.01～0.04mol的硫粉，在常温下搅拌5-30分钟，得到混合悬液。
步骤2，将步骤1的混合悬液移入100ml溶剂热反应釜中，在160～200℃高温条件下溶剂热反应24～72小时，取出冷却至室温，固液分离，100ml乙醇清洗3次，100ml超纯水清洗3次，在50-60℃温度烘干6小时，研磨至小于200目。
步骤3，将通过步骤2获得的样品在湿度30-40％的烘箱中80～100℃表面氧化8～10小时，获得成品。
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