CN112774623A - 硅基负载型硫化纳米零价铁复合材料的制备方法及应用 - Google Patents

硅基负载型硫化纳米零价铁复合材料的制备方法及应用 Download PDF

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CN112774623A
CN112774623A CN202011624833.7A CN202011624833A CN112774623A CN 112774623 A CN112774623 A CN 112774623A CN 202011624833 A CN202011624833 A CN 202011624833A CN 112774623 A CN112774623 A CN 112774623A
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李辉
相明辉
司若凡
黄渊
王文兵
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Abstract

本发明公开了一种硅基负载型硫化纳米零价铁复合材料的制备方法及应用。该复合材料以表面起皱二氧化硅纳米球为载体，单分散的硫化纳米零价铁颗粒均匀分散在树突状纤维孔道中，整体形貌呈球形且高度分散，对溴代有机污染物四溴双酚A有更好的反应性和在石英砂柱中的运输性。本发明制备的硅基负载型硫化纳米零价铁复合材料的工艺简单、原料廉价易得、绿色环保。本发明制备的硅基负载型硫化纳米零价铁复合材料可用于土壤地下水中的卤代有机污染物的原位修复，可操作性强，修复效果明显。

Description

硅基负载型硫化纳米零价铁复合材料的制备方法及应用
技术领域
本发明涉及土壤修复材料制备领域，尤其涉及一种硅基负载型硫化纳米零价铁复合材料的制备及应用。
背景技术
四溴双酚A(TBBPA)是全球生产和使用最广泛的溴化阻燃剂(BFR)之一，它使工业产品，例如塑料，橡胶，纺织品和纤维，具有良好的阻燃性和自熄性。TBBPA不可避免地释放到环境中，由于其亲脂性，持久性和远距离迁移性，已在空气，土壤，水，沉积物和生物中被检测出。TBBPA在动物中具有内分泌破坏能力，神经毒性，肾毒性和肝毒性，并且可以刺激人体细胞的氧化应激，炎症和免疫抑制，暴露于人体的TBBPA污染环境对健康的潜在风险已引起广泛关注。因此，必须开发有效的技术从受污染的环境介质中去除TBBPA。
硫化纳米零价铁(S-NZVI)具有比纳米零价铁颗粒更好的电子转移效率和反应活性，现已成为土壤地下水卤代有机污染修复中的研究热点。然而，S-NZVI在范德华力，高表面能和固有的磁相互作用下仍趋于聚集，这将导致土壤孔隙堵塞，影响其在多孔介质中的流动性，所以限制了其在实际环境修复工程中的应用。为了提高其稳定性和分散性，可以将S-NZVI负载在易于合成，结构可调，化学稳定性强的多孔硅基载体上，但是大多数硅铁复合材料的形状不规则，不能有效利用载体的比表面积，这不利于修复材料在土壤中的运输和去除地下水污染。
发明内容
本发明的目的是提供一种硅基负载型硫化纳米零价铁复合材料的制备及应用，以表面起皱二氧化硅纳米球为载体，将硫化纳米零价铁分散在树突状纤维孔道中，从而克服硫化纳米零价铁易团聚的缺陷，同时提高吸附和还原反应能力，更高效的穿透土壤含水层以去除地下水中的四溴双酚A。
为实现上述发明目的，本发明提供了种硅基负载型硫化纳米零价铁复合材料的制备方法，其特征在于，具体包括以下步骤：
步骤1、将0.068g三乙醇胺溶于25mL水中，80-100℃搅拌0.5h，再加入0.380g十六烷基三甲基溴化铵和0.167-0.251g水杨酸钠，搅拌1h形成混合溶液，其中十六烷基三甲基溴化铵为结构导向剂；
步骤2、向上述混合溶液中加入2-4mL正硅酸四乙酯充分反应1-2h后，在7000rpm下离心5min后收集白色固体产物；
步骤3、将上述白色固体产物在60℃下用酸性乙醇萃取3次去除十六烷基三甲基溴化铵，再用无水乙醇洗涤3次，60℃烘箱干燥12h后获得表面起皱二氧化硅纳米球；其中，盐酸和乙醇的体积比为2:98；
步骤4、将0.05-0.3g表面起皱二氧化硅纳米球和0.483g六水合三氯化铁溶解在60mL超纯水和30mL无水乙醇的混合溶液中，超声2h并机械搅拌30min；
步骤5、在通入氮气保护下用蠕动泵向上述溶液中滴加20mL含有0.350g硼氢化钠和0.008-0.047g连二亚硫酸钠的溶液，继续搅拌30min；
步骤6、在5000rpm下离心5min后收集黑色产物，经无水乙醇洗涤后在60℃真空干燥箱中干燥2h后得到最终产物硅基负载型硫化纳米零价铁复合材料。
进一步地，十六烷基三甲基溴化铵和水杨酸钠的摩尔比为1-1.5，复合材料的硅铁质量比为0.5-3。
本发明还提供了一种用于验证硅基负载型硫化纳米零价铁复合材料去除四溴双酚A的方法，其特征在于，
步骤1、将0.1g表面起皱二氧化硅纳米球、0.1g硫化纳米零价铁和0.2g硅基负载型硫化纳米零价铁复合材料投加到含100mL 10-40mg/L四溴双酚A地下水溶液的摇瓶中，调节溶液pH至6.5±0.3，在30℃250rpm的振荡箱中遮光反应8h，在设定时间点下取部分水样用高效液相色谱仪检测四溴双酚A浓度。
步骤2、将100mL 1g/L硫化纳米零价铁或硅基负载型硫化纳米零价铁复合材料悬浮液泵入装有石英砂(20-10目)的树脂柱(直径25mm，高170mm，孔隙率0.41)中，收集每分钟流出物，用HCl酸化6小时后通过邻菲罗啉法测定总铁浓度。
进一步地，石英砂为20-10目，石英砂的树脂柱为直径25mm，高170mm，孔隙率0.41。
本发明的有益效果在于：
(1)本发明所制备的表面起皱二氧化硅纳米球具有孔径由内向外逐渐增大的中心-径向孔结构，可通过改变十六烷基三甲基溴化铵和水杨酸钠的摩尔比调节表面起皱二氧化硅纳米球的大小。
(2)本发明所制备的硅基负载型硫化纳米零价铁复合材料可轻易调节硅铁质量比和硫铁摩尔比以获得最佳的反应活性。
(3)本发明所制备的硅基负载型硫化纳米零价铁复合材料改善了硫化纳米零价铁的聚集提高了分散性，强化了对污染物的吸附作用并暴露出更多的活性位点，在去除四溴双酚A污染的地下水中展现出高效的反应性，表面电荷的改变使其在土壤多孔介质中有着更强的运输性。
(4)本发明结合了表面起皱二氧化硅纳米球和硫化纳米零价铁的优点合成了硅基负载型硫化纳米零价铁复合材料，提高了硫化纳米零价铁在修复环境中的分散性、反应性和运输性，证明了该复合材料在实际污染场地修复中的应用潜力。
附图内容
图1为本发明制备的不同材料的透射电镜图；
图2为本发明制备的硅基负载型硫化纳米零价铁复合材料去除土壤地下水中四溴双酚A的降解效果图；
图3为本发明制备的硅基负载型硫化纳米零价铁复合材料在石英砂柱中的穿透曲线图。
具体实施方式
以下将结合附图1-3对实施例的技术方案进行详细说明。
实施例1：
该实施例提供了一种硅基负载型硫化纳米零价铁复合材料的制备方法，具体包括以下步骤：
步骤1、将0.068g三乙醇胺溶于25mL水中，80℃搅拌0.5h，再加入0.380g十六烷基三甲基溴化铵和0.251g水杨酸钠，搅拌1h形成混合溶液，其中十六烷基三甲基溴化铵为结构导向剂；
步骤2、向上述混合溶液中加入4mL正硅酸四乙酯充分反应2h后，在7000rpm下离心5min后收集白色固体产物；
步骤3、将上述白色固体产物在60℃下用酸性乙醇(盐酸和乙醇的体积比为2:98)萃取3次去除十六烷基三甲基溴化铵，再用无水乙醇洗涤3次，60℃烘箱干燥12h后获得表面起皱二氧化硅纳米球；
步骤4、将0.1g表面起皱二氧化硅纳米球和0.483g六水合三氯化铁溶解在60mL超纯水和30mL无水乙醇的混合溶液中，超声2h并机械搅拌30min；
步骤5、在通入氮气保护下用蠕动泵向上述溶液中滴加20mL含有0.350g硼氢化钠和0.031g连二亚硫酸钠的溶液，继续搅拌30min；
步骤6、在5000rpm下离心5min后收集黑色产物，经无水乙醇洗涤后在60℃真空干燥箱中干燥2h后得到最终产物硅基负载型硫化纳米零价铁复合材料。
硫化纳米零价铁的制备除了不需加入表面起皱二氧化硅纳米球，其他与硅基负载型硫化纳米零价铁复合材料制备步骤一致。
用此方法制备的复合材料特性如下：
如图1所示，为本发明制备的不同材料的透射电镜图。硫化纳米零价铁是表面粗糙具有圆形核和片状壳形的球形颗粒，并严重聚集成粒径较大的链状结构(图1a)。表面起皱二氧化硅纳米球的孔结构是放射状的，并且孔径沿着颗粒的中心朝向表面逐渐增大(图1b)。硅基负载型硫化纳米零价铁复合材料显示球形和分散的硫化纳米零价铁颗粒(尺寸接近50nm)均匀地分散在纤维状中心-径向孔道中，分散性得到有效提升(图1c)。
实施例2：
该实施例提供了一种硅基负载型硫化纳米零价铁复合材料的制备及其降解土壤地下水中四溴双酚A的方法，具体包括以下步骤：
步骤1、将0.068g三乙醇胺溶于25mL水中，90℃搅拌0.5h，再加入0.380g十六烷基三甲基溴化铵和0.167g水杨酸钠，搅拌1h形成混合溶液，其中十六烷基三甲基溴化铵为结构导向剂；
步骤2、向上述混合溶液中加入3mL正硅酸四乙酯充分反应1h后，在7000rpm下离心5min后收集白色固体产物；
步骤3、将上述白色固体产物在60℃下用酸性乙醇(盐酸和乙醇的体积比为2:98)萃取3次去除十六烷基三甲基溴化铵，再用无水乙醇洗涤3次，60℃烘箱干燥12h后获得表面起皱二氧化硅纳米球；
步骤4、将0.05g表面起皱二氧化硅纳米球和0.483g六水合三氯化铁溶解在60mL超纯水和30mL无水乙醇的混合溶液中，超声2h并机械搅拌30min；
步骤5、在通入氮气保护下用蠕动泵向上述溶液中滴加20mL含有0.350g硼氢化钠和0.031g连二亚硫酸钠的溶液，继续搅拌30min；
步骤6、在5000rpm下离心5min后收集黑色产物，经无水乙醇洗涤后在60℃真空干燥箱中干燥2h后得到最终产物硅基负载型硫化纳米零价铁复合材料。
硫化纳米零价铁的制备除了不需加入表面起皱二氧化硅纳米球，其他与硅基负载型硫化纳米零价铁复合材料制备步骤一致。
步骤7、将0.1g表面起皱二氧化硅纳米球、0.1g硫化纳米零价铁和0.2g硅基负载型硫化纳米零价铁复合材料投加到含100mL 10mg/L四溴双酚A地下水溶液的摇瓶中，调节溶液pH至6.5，在30℃250rpm的振荡箱中遮光反应8h，在设定时间点下取部分水样用高效液相色谱仪检测四溴双酚A浓度。
如图2所示，为本发明制备的硅基负载型硫化纳米零价铁复合材料去除土壤地下水中四溴双酚A的降解效果图。反应8h后，硅基负载型硫化纳米零价铁复合材料显示了对土壤地下水中四溴双酚A降解的最佳效率(91.4％)，显著高于仅依靠还原能力的硫化纳米零价铁(66.3％)和仅依靠吸附能力的表面起皱二氧化硅纳米球(9.5％)。结果表明硅基负载型硫化纳米零价铁复合材料中的吸附和还原有着明显的协同作用，有效提高了对四溴双酚A的降解效果。
实施例3：
该实施例提供了一种硅基负载型硫化纳米零价铁复合材料在石英砂柱中的运输方法，具体包括以下步骤：
将100mL 1g/L硫化纳米零价铁或硅基负载型硫化纳米零价铁复合材料悬浮液泵入装有石英砂(20-10目)的树脂柱(直径25mm，高170mm，孔隙率0.41)中，收集每分钟流出物，用HCl酸化6小时后通过邻菲罗啉法测定总铁浓度。
如图3所示，为本发明制备的硅基负载型硫化纳米零价铁复合材料在石英砂柱中的穿透曲线图。约70.5％的硅基负载型硫化纳米零价铁复合材料成功穿透石英砂柱到达底部，相反，只有不到1％的硫化纳米零价铁随出水流出。表明带负电的硅基负载型硫化纳米零价铁复合材料可增强与带负电荷的石英砂之间的静电排斥力，从而更有效地穿透土壤含水层运输至受污染的区域开展修复。
本领域技术人员应该理解，上述实施例仅仅是对本发明的示意性实现方式的解释，并非对本发明包含范围的限定。实施例中的细节并不构成对本发明范围的限制，在不背离本发明的精神和范围的情况下，任何基于本发明技术方案的等效变换、简单替换等显而易见的改变，均落在本发明保护范围之内。

Claims (4)

1.一种硅基负载型硫化纳米零价铁复合材料的制备方法，其特征在于，具体包括以下步骤：
步骤1、将0.068g三乙醇胺溶于25mL水中，80-100℃搅拌0.5h，再加入0.380g十六烷基三甲基溴化铵和0.167-0.251g水杨酸钠，搅拌1h形成混合溶液，其中十六烷基三甲基溴化铵为结构导向剂；
步骤2、向上述混合溶液中加入2-4mL正硅酸四乙酯充分反应1-2h后，在7000rpm下离心5min后收集白色固体产物；
步骤3、将上述白色固体产物在60℃下用酸性乙醇萃取3次去除十六烷基三甲基溴化铵，再用无水乙醇洗涤3次，60℃烘箱干燥12h后获得表面起皱二氧化硅纳米球；其中，盐酸和乙醇的体积比为2:98；
步骤4、将0.05-0.3g表面起皱二氧化硅纳米球和0.483g六水合三氯化铁溶解在60mL超纯水和30mL无水乙醇的混合溶液中，超声2h并机械搅拌30min；
步骤5、在通入氮气保护下用蠕动泵向上述溶液中滴加20mL含有0.350g硼氢化钠和0.008-0.047g连二亚硫酸钠的溶液，继续搅拌30min；
步骤6、在5000rpm下离心5min后收集黑色产物，经无水乙醇洗涤后在60℃真空干燥箱中干燥2h后得到最终产物硅基负载型硫化纳米零价铁复合材料。
2.根据权利要求1所述的硅基负载型硫化纳米零价铁复合材料的制备方法，其特征在于：十六烷基三甲基溴化铵和水杨酸钠的摩尔比为1-1.5，复合材料的硅铁质量比为0.5-3。
3.一种用于验证硅基负载型硫化纳米零价铁复合材料去除四溴双酚A的方法，其特征在于，
步骤1、将0.1g表面起皱二氧化硅纳米球、0.1g硫化纳米零价铁和0.2g硅基负载型硫化纳米零价铁复合材料投加到含100mL10-40mg/L四溴双酚A地下水溶液的摇瓶中，调节溶液pH至6.5±0.3，在30℃250rpm的振荡箱中遮光反应8h，在设定时间点下取部分水样用高效液相色谱仪检测四溴双酚A浓度。
步骤2、将100mL 1g/L硫化纳米零价铁或硅基负载型硫化纳米零价铁复合材料悬浮液泵入装有石英砂的树脂柱中，收集每分钟流出物，用HCl酸化6小时后通过邻菲罗啉法测定总铁浓度。
4.根据权利要求3所述的用于验证硅基负载型硫化纳米零价铁复合材料去除四溴双酚A的方法，其特征在于：石英砂为20-10目，石英砂的树脂柱为直径25mm，高170mm，孔隙率0.41。
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