CN112742340A - 一种s-zvi磁性环境修复材料及其制备方法和用途 - Google Patents
一种s-zvi磁性环境修复材料及其制备方法和用途 Download PDFInfo
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Abstract
本发明公开了一种S‑ZVI磁性环境修复材料及其制备方法和用途，用还原剂（硼氢化钠、硼氢化钾）还原三价铁离子为零价铁，进而加入硫源（如硫代硫酸钠）使零价铁表面形成一层硫铁化物，制得S‑ZVI材料。用硫源改性后，S‑ZVI材料克服了零价铁易团聚和易钝化的问题，提高了零价铁的电子传递速率和反应活性。本发明制备方法制备的环境修复材料成本低，制备方法简便且对环境的负面影响小，同时该方法制备的材料对重金属铬的去除效果有优势且该材料稳定性好，便于回收利用。
Description
技术领域
本发明属于环境修复材料技术领域，具体涉及一种S-ZVI磁性环境修复材料及其制备方法和用途。
背景技术
铬（Cr）被广泛应用于冶金、颜料以及制革等行业，其常见价态为三价铬（Cr（III））和六价铬（Cr（VI））。由于Cr（VI）活性高且具有强氧化性，对环境和人类健康造成了极大的危害，因此Cr（VI）的还原固定研究具有重要意义。
零价铁（ZVI）作为一种还原剂，具有很强的电子贡献能力以及高反应活性，已被广泛用于各种环境污染物的去除，但由于ZVI的高表面能及磁特性导致其容易发生团聚沉降，降低了ZVI反应能力；此外ZVI还易与水发生钝化反应，使其在反应过程中的活性逐渐降低，电子传递能力减弱，限制了ZVI的应用范围。
与ZVI相比，硫化亚铁（FeS）具有疏水性、较大的比表面积和较强的电子传递能力，对污染物的去除效果相对持久，但去除能力较弱，且自身没有磁性，不利于回收。
发明内容
目的：为解决现有技术的不足，本发明提供一种S-ZVI磁性环境修复材料及其制备方法和用途，其作为环境修复材料用于环境中Cr（VI）的去除。相比于其他硫化材料，该复合材料具有较好的磁性、较大的比表面积及优异的电化学性能，有利于高效去除污染物，解决了Fe0易钝化失活以及铁硫化物难于回收的缺点，具有广泛的应用前景。
将ZVI与FeS复合制备S-ZVI，FeS本身的疏水性可以降低ZVI与水反应造成的钝化损失，使S-ZVI复合材料能与水中的Cr（VI）充分接触；FeS的还原性可协同提高ZVI的电子传递能力，进而提高了复合材料对Cr（VI）的去除性能，同时也具备较好磁响应性。
硫化零价铁（S-ZVI）常用的合成方法是在湿法合成零价铁的过程中加入硫源（硫代硫酸钠、硫化钠、连二亚硫酸钠等），硫化物腐蚀零价铁表层并在表面形成一层 FeSx壳。根据合成过程中硫源的添加顺序可分为前置合成法和后置合成法。前置合成法是指将硫源和硼氢化物混合在一起还原溶液中的铁源形成ZVI和FeSx混合物；后置合成法是指用硼氢化钠把铁源还原为零价铁后加入硫源最终合成FeSx包裹的ZVI。目前S-ZVI的制备大多采用常规液相前置还原法，硫源多采用硫化钠或连二亚硫酸钠。但硫化钠有较强的吸湿性使合成的材料不易储存，连二亚硫酸钠在合成过程中会过多地消耗零价铁，导致改性后的材料反应性降低，因此，选择一种稳定有效的硫源能极大提高硫化零价铁的应用价值。
实现本发明目的的技术解决方案是：
一种S-ZVI磁性材料的制备方法，包括：
步骤（1）、取一定量铁盐溶液于容器中，并通Ar2气体，赶走铁盐溶液中的溶解氧；
步骤（2）、在Ar2保护和超声的条件下，将还原剂滴入步骤（1）制得的铁盐溶液中，滴加完毕后继续超声反应，得含有ZVI的混合液；
步骤（3）、在Ar2保护和超声的条件下，向步骤（2）所得混合液中滴入一定量的硫源硫代硫酸钠，滴加完毕后继续超声反应，得到S-ZVI混合液；
步骤（4）、利用磁铁分离出步骤（3）所得产物，经乙醇与去离子水混合液洗涤后真空干燥，得到S-ZVI磁性材料。
在一些实施例中，步骤（1）中，所述铁盐采用三价铁盐；优选的，铁盐采用硝酸铁、氯化铁、硝酸铁水合物、氯化铁水合物中的一种或几种；
更优选的，采用铁盐FeCl3·6H2O，FeCl3·6H2O溶液浓度为0.1 mol·L-1。
在一些实施例中，步骤（2）中，所述还原剂采用硼氢化钠、硼氢化钾中的一种或几种；
还原剂加入的量为还原剂中硼氢根与铁盐溶液中铁离子的摩尔比为3~5，优选为3。
在一些实施例中，步骤（2）中，加入的硫源为硫代硫酸钠、硫化钠、连二亚硫酸钠中的一种或几种；
硫源加入的量为硫源中硫元素与铁盐溶液中铁元素的摩尔比为0.02~2，优选为0.2。
进一步优选的，硫源为硫代硫酸钠，加入的硫代硫酸钠与铁盐中铁离子的摩尔比为0.01~1，优选为0.1。
在一些实施例中，步骤（3），中，所述硫源为浓度为0.1 mol·L-1的Na2S2O3溶液。
步骤（2）中、还原剂滴加完毕后继续超声反应30min以上，制得ZVI；
步骤（3）中、硫源滴加完毕后继续超声反应30min以上，得到S-ZVI，
本发明提供的一种S-ZVI磁性环境修复材料，由上述的方法制备得到。
本发明所述的S-ZVI磁性环境修复材料作为去除水体污染物的环境修复材料的应用。
进一步的，所述应用为用于水体中Cr（VI）污染物的去除。
在一些实施例中，所述的应用，将所述S-ZVI磁性环境修复材料投加到水体中，经振荡、吸附即可；优选的，S-ZVI磁性材料的投加量为0.2~2.0g/L，更优选为1.0g/L。,
有益效果：本发明提供的一种S-ZVI磁性环境修复材料及其制备方法和用途，原材料易于获取、成本低，制备方法简便且对环境的负面影响小，同时该方法制备的材料对重金属铬的去除效果有优势且该材料稳定性好，便于回收利用。此外，该复合材料具有较好的电化学特性，相比于ZVI，本发明所得S-ZVI磁性材料电子传递能力更强，有利于深入研究对重金属污染物的去除机理，更高效的去除污染物，也有利于尝试改性材料以优化其性能。具有以下优点：
（1）本发明的材料采用一步法制备，工艺简单，且硫代硫酸钠廉价易得，生产成本低，有利于规模化制备。
（2）采用硫铁化物修饰零价铁，是基于硫铁化物的比表面积大且具有较好的电化学性能，既能保护零价铁，减少其钝化，又能促进零价铁的电子传递。
（3）本发明的复合材料S-ZVI，具有较好的还原性，不仅能提高对Cr（VI）的吸附量，还能将大部分的Cr（VI）还原为Cr（III），因此复合材料可以将铬从水环境中转移到了材料的表面，大大的降低了铬的生物毒性。
（4）本发明对材料的优化改性探究取得初步成功，有利于后续的深入研究。
（5）本发明合成的环境修复材料具有较高的饱和磁化强度，能够快速的实现固液分离，防止二次污染。
附图说明
图1是本发明实施例1的扫描电镜图；
图2是本发明实施例2的扫描电镜图；
图3是本发明实施例3的HRTEM Mapping图；
图4是本发明实施例4的磁滞回线图；
图5是本发明实施例5的Zeta电位图；
图6是本发明实施例6的Tafel腐蚀曲线图；
图7是本发明实施例7的不同pH值条件下材料对Cr（VI）的吸附效果图；
图8是本发明实施例7的吸附材料表面铬的解析图。
具体实施方式
下面结合实施例对本发明作进一步描述。以下实施例只是用于更加清楚地说明本发明的性能，而不能仅局限于下面的实施例。
根据ZVI具有优异的磁性能，在其合成的过程中掺杂硫元素，制备出了易于回收的环境修复材料，用于水体环境中的Cr（VI）的去除。
制备的环境修复功能材料用于处理Cr（VI）的实施方法，主要包括：材料对Cr（VI）的吸附实验以及解析实验、进行环境修复材料的电化学性能测试、表征测试。
实施例1
取25 mL 0.1 M FeCl3·6H2O于250 mL锥形瓶中，持续通Ar2 20 min，赶走溶液中的溶解氧，在Ar2保护和超声的条件下，滴加25 ml 0.3 M NaBH4溶液，滴加完毕后继续超声反应30 min。利用磁铁分离出所得产物，经乙醇与去离子水混合液（体积比2:1）洗涤后，60℃真空干燥12 h，得到ZVI固体材料。其扫描电镜图如图1所示，ZVI呈链状结构，团聚在一起。
实例2
取25 mL 0.1 M FeCl3·6H2O于250 mL锥形瓶中，持续通Ar2 20 min，赶走溶液中的溶解氧，在Ar2保护和超声的条件下，滴加25 ml 0.3 M NaBH4溶液，滴加完毕后继续超声反应30 min；然后在Ar2保护和超声的条件下，在上述溶液中滴加2.5 ml 0.1 M Na2S2O3溶液，滴加完毕后继续超声反应30 min。利用磁铁分离出所得产物，经乙醇与去离子水混合液（体积比2:1）洗涤后，60℃真空干燥12 h，得到S-ZVI固体材料。其扫描电镜图如图2所示，S-ZVI呈片状结构。
实例3
将制备的S-ZVI，进行元素能谱分析表征，表征结果如图3所示。颗粒含有Fe、S、O元素，其中Fe元素为主要成分，说明硫掺杂使S-ZVI颗粒内部或表面形成了FeSx，这与XRD零价铁衍射峰强度减弱的结果一致。由此证实，S-ZVI制备是成功的。。
实例4
将制备的ZVI和S-ZVI进行了饱和磁化强度测试。其磁滞回线如图4所示，ZVI以及S-ZVI饱和磁化强度分别为48.94，38.63emu/g，都可以实现固液分离，为实际应用提供可能。
实例5
将制备的ZVI和S-ZVI在室温的条件下进行了Zeta电位的测试。如图5所示，ZVI和S-ZVI的等电点分别为5.5和6.9，复合材料的等电点高于ZVI，有利于S-ZVI对Cr（VI）进行静电吸附从而进行高效去除。
实例6
Tafel腐蚀曲线测定：4mg ZVI和S-ZVI分散在1mL分散剂中（由50 μL0.5%(wt)Nafion和950μL无水乙醇溶液组成），超声10min，移取40uL悬浮液滴在玻碳电极上，室温风干后进行测试。使用电化学工作站在三电极体系中进行测定。三电极体系由玻碳工作电极，银-氯化银参比电极和铂片对电极组成，进行Tafel腐蚀曲线测定。在-1.2-0V电位范围测试，扫描速率为0.01V/S。该测试在100mg/L Cr（VI）溶液中进行。
Tafel腐蚀曲线可以定性分析材料的电子传递速率，材料的腐蚀电位越低其电子传递速率越快。Tafel曲线如图6所示， ZVI的腐蚀电位低于S-ZVI，表明S-ZVI在Cr（VI）还原过程中有更快的电子传递速率。
实例7
取0.01g的ZVI，S-ZVI分别加入到10ml，浓度为100 ml/L的Cr（VI）溶液中，通过使用1.0M HCl和1.0MNaOH调节Cr（VI）初始溶液的pH的值，研究在3、4、5、6、7、9 pH值下，吸附剂对Cr（VI）的去除效果。150rpm/min振荡24h，吸附结果如图7所示。在不同的pH值条件下，S-ZVI对Cr（VI）的吸附效果都优于ZVI。在pH值为3的条件按下，S-ZVI对Cr（VI）的吸附量最高为29.97mg/g。在pH值为3的条件下进行的Cr（VI）吸附实验结束后，磁性分离吸附剂和溶液，随后在离心管中加入10mL1.5molHCl溶液对材料进行解吸实验，室温振荡12h。HCl作为Cr（III）的解吸液，用来确定材料表面Cr（III）的还原量。如图8所示，ZVI和S-ZVI将吸附在材料表面的Cr（VI）还原为Cr（III）的量分别为9.18、24.87mg/g，Cr（III）的含量分别占Cr总量的83%、82.9%。Cr（VI）大部分被还原为Cr（III），说明材料都有较好的还原性质，能够有效降低铬的生物毒性。
以上已以较佳实施例公开了本发明，然其并非用以限制本发明，凡采用等同替换或者等效变换方式所获得的技术方案，均落在本发明的保护范围之内。
Claims (10)
1.一种S-ZVI磁性材料的制备方法，其特征在于，包括：
步骤（1）、取一定量铁盐溶液于容器中，并通Ar2气体，赶走铁盐溶液中的溶解氧；
步骤（2）、在Ar2保护和超声的条件下，将还原剂滴入步骤（1）制得的铁盐溶液中，滴加完毕后继续超声反应，得含有ZVI的混合液；
步骤（3）、在Ar2保护和超声的条件下，向步骤（2）所得混合液中滴入一定量的硫源硫代硫酸钠，滴加完毕后继续超声反应，得到S-ZVI混合液；
步骤（4）、利用磁铁分离出步骤（3）所得产物，经乙醇与去离子水混合液洗涤后真空干燥，得到S-ZVI磁性材料。
2.根据权利要求1所述的S-ZVI磁性材料的制备方法，其特征在于，步骤（1）中，所述铁盐采用三价铁盐；优选的，铁盐采用硝酸铁、氯化铁、硝酸铁水合物、氯化铁水合物中的一种或几种；
更优选的，采用铁盐FeCl3·6H2O，FeCl3·6H2O溶液浓度为0.1 mol·L-1。
3.根据权利要求1所述的S-ZVI磁性材料的制备方法，其特征在于，步骤（2）中，所述还原剂采用硼氢化钠、硼氢化钾中的一种或几种；
还原剂加入的量为还原剂中硼氢根与铁盐溶液中铁离子的摩尔比为3~5，优选为3。
4.根据权利要求1所述的S-ZVI磁性材料的制备方法，其特征在于，步骤（2）中，加入的硫源为硫代硫酸钠、硫化钠、连二亚硫酸钠中的一种或几种；
硫源加入的量为硫源中硫元素与铁盐溶液中铁元素的摩尔比为0.02~2，优选为0.2。
5.根据权利要求4所述的S-ZVI磁性材料的制备方法，其特征在于，优选的硫源为硫代硫酸钠，加入的硫代硫酸钠与铁盐中铁离子的摩尔比为0.01~1，优选为0.1。
6.根据权利要求1所述的S-ZVI磁性材料的制备方法，其特征在于，步骤（3），中，所述硫源采用浓度为0.1 mol·L-1的Na2S2O3溶液。
7.一种S-ZVI磁性材料，其特征在于，由权利要求1-6任一项所述的方法制备得到。
8.权利要求7所述的S-ZVI磁性材料作为去除水体污染物的环境修复材料的应用。
9.根据权利要求8所述的应用，其特征在于，所述应用为用于水体中Cr(Ⅵ)污染物的去除。
10.根据权利要求9所述的应用，其特征在于，将所述S-ZVI磁性材料投加到水体中，经振荡、吸附即可；
优选的，S-ZVI磁性材料的投加量为0.2~2.0g/L，更优选为1.0g/L。
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| CN116371383A (zh) * | 2023-05-30 | 2023-07-04 | 北京科净源科技股份有限公司 | 一种强化除磷复合填料、其制备方法及应用 |
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