CN112452327B - 一种铁基双层介孔硅-碳微球纳米复合材料及其制备方法和应用 - Google Patents
一种铁基双层介孔硅-碳微球纳米复合材料及其制备方法和应用 Download PDFInfo
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Abstract
本发明提供一种铁基介孔硅‑碳微球纳米复合材料及其制备方法和应用,本发明提供的铁基介孔硅‑碳微球纳米复合材料,通过在介孔碳硅小球堆积的微球中引入纳米零价铁,大幅提升了对水体中重金属的去除性能。铁基介孔硅‑碳微球纳米复合材料对重金属的去除过程主要通过吸附、还原、沉淀等多种途径实现。其中,有序介孔结构显著增强了对重金属的吸附性能,而纳米零价铁的原位合成则成功引入了多个反应活性位点。本发明可用于对水体中铬(Ⅵ)、镉(Ⅱ)等多种重金属的去除,具有去除能力强、可再生循环等优点。
Description
技术领域
本发明属于污水处理技术领域,具体涉及一种铁基双层介孔硅-碳微球纳米复合材料及其制备方法和应用。
背景技术
随着工业化的发展和农业的规模化,人类一直面临严峻的水环境问题。到2025年,世界上约三分之二的人口将面对严重缺水的状况,保障水环境安全是20世纪面临的重大挑战之一。作为主要的水体污染物类型之一,重金属在水环境中的积累会对水生生态系统造成严重危害,它们不仅不能在自然条件下降解,而且可以通过食物链在人体内富集,从而威胁人体健康甚至生命安全。这些重金属不论以何种状态、以何种水平存在,对生物和环境都具有明显的毒性。世界卫生组织(WHO)规定了可接受的最大污染水平,将水源中的重金属浓度限制为零或仅允许阈值,其中镉(Cd)和铬(Cr)的最大污染水平分别为3ppb和100ppb。水体中重金属离子的污染正严重影响我国社会和经济的发展,对其研究、去除刻不容缓。
发明内容
本发明针对上述缺陷,提供一种将纳米零价铁负载至制备得到的介孔硅-碳微球纳米复合材料,形成铁基介孔硅-碳微孔复合材料,并应用所述铁基介孔硅-碳微孔复合材料去除水体中重金属离子的应用,该纳米复合改性材料对重金属具有较好的去除效果。
本发明提供如下技术方案:一种铁基双层介孔硅-碳微球纳米复合材料的制备方法,包括如下步骤:
(1)、在室温下,将4g的聚环氧乙烷-聚环氧丙烷-聚环氧乙烷三嵌段共聚物非离子表面活性剂P123溶解在质量分数浓度为16%、体积为150mL的盐酸水溶液中,形成非离子表面活性剂P123盐酸水溶液,然后依次将3g的1,3,5-三甲苯、8g的正硅酸四乙酯逐滴加入到所述非离子表面活性剂P123盐酸水溶液中,并在35℃下持续搅拌2h;
(2)、将所述步骤(1)得到的混合液倒入水热反应釜,置于烘箱内进行水热反应,然后过滤、洗涤、干燥;然后将所得样品用质量分数为1.5%的硫酸进行预碳化处理,得到预碳化后的材料;
(3)、将所述步骤(2)得到的预碳化后材料在氮气气氛下加热至600℃,获得外硅层、内碳层均由介孔硅-碳小球堆积而成的双层介孔硅-碳微球纳米复合材料;
(4)、将所述步骤(3)得到的0.4g的双层介孔硅-碳微球纳米复合材料中均匀分散在10mL无水乙醇中,将Fe(NO3)3·9H2O完全溶解于2mL无水乙醇中,混合上述两种溶液,在室温下连续搅拌直到乙醇溶剂蒸发;
(5)、将所述步骤(4)得到的混合物放入敞口玻璃管中,将所述敞口玻璃管置于装有10mL质量分数为14%的氨水溶液的Teflon瓶中,避免样品与氨水溶液直接接触;将所述Teflon瓶密封并在60℃下水热反应3h,之后用去离子水和乙醇洗涤以除去生成的NH4NO3,最后在100℃下干燥过夜;
(6)、将所述步骤(5)得到的物质在还原气氛中进行热还原,使纳米零价铁在双层介孔硅-碳微球纳米复合材料的孔道内和孔壁上原位生成,最终得到所述铁基双层介孔硅-碳微球纳米复合材料。
进一步地,所述的步骤(2)中水热反应的条件为,35℃下水热24h,100℃下水热36h。
进一步地,所述的步骤(2)中预碳化处理条件为先室温放置2h,再在160℃下干燥12h。
进一步地,所述的步骤(4)中加入Fe(NO3)3·9H2O的质量为0.2g~0.4g。
进一步地,所述的步骤(5)中的还原气氛为氢气,还原温度为400℃。
本发明还提供上述制备方法制备得到的铁基双层介孔硅-碳微球纳米复合材料,所述铁基介孔硅-碳微球的孔体积为1.38cm3/g,比表面积为491m2/g,微孔表面积为65m2/g,所述铁基介孔硅-碳微球的孔径为2nm~50nm。
本发明还提供上述铁基双层介孔硅-碳微球纳米复合材料在重金属去除中的应用,所述重金属离子为Cr6+或Cd2+中的一种或两种。
本发明的有益效果为:
1、纳米零价铁(nZVI)能够有效地去除和固定多种重金属离子。作为一种具有优异性能的材料,nZVI可去除水中多种污染物质。负载型nZVI以多孔材料为载体,有效地将nZVI分散开,减少nZVI单独应用于污水处理时易团聚和易氧化等缺点,避免了它在环境修复领域中的应用颗粒团聚现象的发生,进而增强污染物去除能力。
2、与现有技术的其他载体材料相比,有序介孔材料具有比表面积高、孔体积大、孔道均一性好、孔道排布有序等特殊结构,作为纳米零价铁(nZVI)的载体主要有以下优势:1)高比表面积有利于纳米颗粒的分散与固定;2)高度有序的介孔结构能够将纳米颗粒精准限域并抑制其氧化;3)互穿的孔道促进了分子的扩散和运输。因此,有序介孔材料是包含nZVI在内的各种催化剂和纳米颗粒的极佳载体。
3、本发明提供的制备方法得到铁基双层介孔硅-碳微球有序介孔材料具有均匀的孔径(2nm~50nm)、规则的介孔结构、以及较大的表面积和孔体积等独特的优势,因而是一种有前途的载体材料,可用于负载纳米零价铁。
4、本申请提供的铁基双层介孔硅-碳微球纳米复合材料,具有由纳米小球紧密堆积而成的微球形态,呈现外硅层、内碳层的独特结构。
5、本申请提供的铁基双层介孔硅-碳微球纳米复合材料不仅能够精确地连接、分散和固定纳米零价铁颗粒,抑制其氧化,而且能够有效地促进重金属离子的扩散与运输。因此,本发明制备的铁基双层介孔硅-碳微球纳米复合材料对重金属具有较好的去除效果。
附图说明
在下文中将基于实施例并参考附图来对本发明进行更详细的描述。其中:
图1为本发明实施例1中提供的预碳化后的材料的扫描电镜图(SEM);
图2为本发明实施例1中提供的外硅层、内碳层的介孔硅-碳小球堆积而成的双层介孔硅-碳微球纳米复合材料的扫描电镜图(SEM);
图3为本发明实施例1中提供的铁基双层介孔硅-碳纳米复合材料的扫描电镜图(SEM);
图4为本发明实施例1中提供的铁基双层介孔硅-碳纳米复合材料的X射线能谱图(EDS);
图5为本发明实施例1中提供的HF酸刻蚀后的铁基双层介孔硅-碳纳米复合材料的透射电镜图(TEM);
图6为本发明实施例2中提供的铁基双层介孔硅-碳纳米复合材料的X射线能谱图(EDS)。
具体实施例方式
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。
实施例1
本实施例提供的一种铁基介孔硅-碳微球纳米复合材料,包括以下步骤:
(1)、首先,在室温下,将4g的聚环氧乙烷-聚环氧丙烷-聚环氧乙烷三嵌段共聚物非离子表面活性剂P123溶解在150mL的质量分数浓度为16%的盐酸水溶液中,然后,依次将3g的1,3,5-三甲苯(TMB)、8g的正硅酸四乙酯(TEOS)逐滴加入到上述溶液中,并在35℃下持续搅拌2h;
(2)、将所述步骤(1)得到的混合液倒入水热反应釜,置于烘箱内35℃下水热24h,100℃下水热36h,然后过滤、洗涤、干燥。将所得样品用质量分数为1.5%的硫酸进行预碳化处理,即先室温放置2h,再在160℃下干燥12h,得到预碳化后的材料,扫描电镜图如图1所示;
(3)、将所述步骤(2)得到的样品在氮气下加热至600℃,获得外硅层、内碳层均由介孔硅-碳小球堆积而成的双层介孔硅-碳微球纳米复合材料,扫描电镜图如图2所示;
(4)、将所述步骤(3)得到的0.4g双层介孔硅-碳微球纳米复合材料中均匀分散在10mL无水乙醇中,将0.2g Fe(NO3)3·9H2O完全溶解于2mL无水乙醇中,混合上述两种溶液,在室温下连续搅拌直到乙醇溶剂蒸发;
(5)、将所述步骤(4)得到的样品放入敞口玻璃管中,将所述敞口玻璃管置于装有10mL氨水溶液(质量分数为14%)的Teflon瓶中,避免样品与氨水溶液直接接触。将所述Teflon瓶密封并在60℃下水热反应3h,之后用去离子水和乙醇洗涤以除去生成的NH4NO3,最后在100℃下干燥过夜;
(6)、将所述步骤(5)得到的物质在400℃的氢气气氛中进行热还原,使纳米零价铁在双层介孔硅-碳微球纳米复合材料的孔道内和孔壁上原位生成,最终得到铁基双层介孔硅-碳微球纳米复合材料,其材料表征结果如图3-6所示。
图3为最终得到的铁基双层介孔硅-碳微球纳米复合材料的扫描电镜图(SEM),从图中可以看出,纳米零价铁颗粒均匀地嵌在孔壁上和孔道中,颗粒大小约为2nm左右,没有明显地铁颗粒团聚。说明通过氨气原位熏蒸的方法,可以很好地控制铁在双层介孔硅-碳微球纳米复合材料中的原位固定和转化,有效地减少团聚现象的发生。图4为最终得到的铁基双层介孔硅-碳微球纳米复合材料的X射线能谱图(EDS),表明所述材料中铁元素的含量为3.92%。为了进一步证明所述复合材料外硅层、内碳层的双层结构,用HF酸对铁基双层介孔二氧化硅-碳微球纳米复合材料进行刻蚀,将二氧化硅和纳米零价铁颗粒溶出,刻蚀后的透射电镜图如图5所示,可见铁基仍保持着类似的介孔小球形貌,说明在介孔硅球的内部确实形成了碳层。
对实施例1中制备的铁基介孔硅-碳微球纳米复合材料进行水中重金属去除实验,以Cr6+、Cd2+为重金属离子代表,在一定体积、一定初始浓度的重金属模拟废水中加入一定量的复合材料。采用电感耦合等离子体发射光谱仪(ICP-OES)测量反应前后的重金属浓度。实验参数如下:
所述复合材料投加量为20mg;
所述重金属初始浓度为5~15mg/L,体积为20mL;
所述反应温度为常温25℃;
所述反应时间是100min,摇床速度为200rpm/min;
实施例1中制备的复合材料对Cr6+和Cd2+的去除效果如表1和表2所示。
表1实施例1中复合材料对Cr6+的去除效果
表2实施例1中复合材料对Cd2+的去除效果
实施例2
(1)、首先,在室温下,将4g的聚环氧乙烷-聚环氧丙烷-聚环氧乙烷三嵌段共聚物非离子表面活性剂P123溶解在150mL的质量分数浓度为16%的盐酸水溶液中,然后,依次将3g的1,3,5-三甲苯(TMB)、8g的正硅酸四乙酯(TEOS)逐滴加入到上述溶液中,并在35℃下持续搅拌2h;
(2)、将所述步骤(1)得到的混合液倒入水热反应釜,置于烘箱内35℃下水热24h,100℃下水热36h,然后过滤、洗涤、干燥。将所得样品用质量分数为1.5%的硫酸进行预碳化处理,即先室温放置2h,再在160℃下干燥12h,得到预碳化后的材料;
(3)、将所述步骤(2)得到的样品在氮气下加热至600℃,获得外硅层、内碳层均由介孔硅-碳小球堆积而成的双层介孔硅-碳微球纳米复合材料;
(4)、将所述步骤(3)得到的0.4g介孔硅-碳微球纳米复合材料中均匀分散在10mL无水乙醇中,将0.4g Fe(NO3)3·9H2O完全溶解于2mL无水乙醇中,混合上述两种溶液,在室温下连续搅拌直到乙醇溶剂蒸发;
(5)、将所述步骤(4)得到的样品放入敞口玻璃管中,将所述敞口玻璃管置于装有10mL氨水溶液(质量分数为14%)的Teflon瓶中,避免样品与氨水溶液直接接触;将所述Teflon瓶密封并在60℃下水热反应3h,之后用去离子水和乙醇洗涤以除去生成的NH4NO3,最后在100℃下干燥过夜;
(6)、将所述步骤(5)得到的物质在400℃的氢气气氛中进行热还原,使纳米零价铁在双层介孔硅-碳微球纳米复合材料的孔道内和孔壁上原位生成,最终得到铁基双层介孔硅-碳微球纳米复合材料,其X射线能谱图(EDS)如图6所示。
对实施例2中制备的铁基双层介孔硅-碳微球纳米复合材料进行水中重金属去除实验,以Cr6+、Cd2+为重金属离子代表,在一定体积、一定初始浓度的重金属模拟废水中加入一定量的复合材料。采用电感耦合等离子体发射光谱仪(ICP-OES)测量反应前后的重金属浓度。实验参数如下:
所述复合材料投加量为20mg;
所述重金属初始浓度为5~15mg/L,体积为20mL;
所述反应温度为常温25℃;
所述反应时间是100min,摇床速度为200rpm/min;
实施例2中制备的复合材料对Cr6+和Cd2+的去除效果如表3和表4所示。
表3实施例2中复合材料对Cr6+的去除效果
表4实施例2中复合材料对Cd2+的去除效果
以上各实施例仅用以说明本发明的技术方案,而非对其限制;尽管参照前述各实施例对本发明进行了详细的说明,本领域的普通技术人员应当理解:其依然可以对前述各实施例所记载的技术方案进行修改,或者对其中部分或者全部技术特征进行等同替换;而这些修改或者替换,并不使相应技术方案的本质脱离本发明各实施例技术方案的范围。
此外,本领域的技术人员能够理解,尽管在此的一些实施例包括其它实施例中所包括的某些特征而不是其它特征,但是不同实施例的特征的组合意味着处于本发明的范围之内并且形成不同的实施例。例如,在上面的权利要求书中,所要求保护的实施例的任意之一都可以以任意的组合方式来使用。公开于该背景技术部分的信息仅仅旨在加深对本发明的总体背景技术的理解,而不应当被视为承认或以任何形式暗示该信息构成已为本领域技术人员所公知的现有技术。
Claims (6)
1.一种铁基双层介孔硅-碳微球纳米复合材料的制备方法,其特征在于,包括如下步骤:
(1)、在室温下,将4g的聚环氧乙烷-聚环氧丙烷-聚环氧乙烷三嵌段共聚物非离子表面活性剂P123溶解在质量分数浓度为16%、体积为150mL的盐酸水溶液中,形成非离子表面活性剂P123盐酸水溶液,然后依次将3g的1,3,5-三甲苯、8g的正硅酸四乙酯逐滴加入到所述非离子表面活性剂P123盐酸水溶液中,并在35℃下持续搅拌2h;
(2)、将所述步骤(1)得到的混合液倒入水热反应釜,置于烘箱内进行水热反应,然后过滤、洗涤、干燥;然后将所得样品用质量分数为1.5%的硫酸进行预碳化处理,得到预碳化后的材料;所述的水热反应的条件为,先在35℃下水热24h,然后于100℃下水热36h;
(3)、将所述步骤(2)得到的预碳化后材料在氮气气氛下加热至600℃,获得外硅层、内碳层均由介孔硅-碳小球堆积而成的双层介孔硅-碳微球纳米复合材料;
(4)、将所述步骤(3)得到的0.4g的双层介孔硅-碳微球纳米复合材料中均匀分散在10mL无水乙醇中,将Fe(NO3)3·9H2O完全溶解于2mL无水乙醇中,混合两种溶液,在室温下连续搅拌直到乙醇溶剂蒸发;
(5)、将所述步骤(4)得到的混合物放入敞口玻璃管中,将所述敞口玻璃管置于装有10mL质量分数为14%的氨水溶液的Teflon瓶中,避免样品与氨水溶液直接接触;将所述Teflon瓶密封并在60℃下水热反应3h,之后用去离子水和乙醇洗涤以除去生成的NH4NO3,最后在100℃下干燥过夜;
(6)、将所述步骤(5)得到的物质在还原气氛中进行热还原,使纳米零价铁在双层介孔硅-碳微球纳米复合材料的孔道内和孔壁上原位生成,最终得到所述铁基双层介孔硅-碳微球纳米复合材料。
2.根据权利要求1所述的一种铁基双层介孔硅-碳微球纳米复合材料的制备方法,其特征在于,所述的步骤(2)中预碳化处理条件为先室温放置2h,再在160℃下干燥12h。
3.根据权利要求1所述的一种铁基双层介孔硅-碳微球纳米复合材料的制备方法,其特征在于,所述的步骤(4)中加入Fe(NO3)3·9H2O的质量为0.2g~0.4g。
4.根据权利要求1所述的一种铁基双层介孔硅-碳微球纳米复合材料的制备方法,其特征在于,所述的步骤(6)中的还原气氛为氢气,还原温度为400℃。
5.根据权利要求1~4任一所述的制备方法制备得到的铁基双层介孔硅-碳微球纳米复合材料,其特征在于,所述铁基介孔硅-碳微球的孔体积为1.38cm3/g,比表面积为491m2/g,微孔表面积为65m2/g,所述铁基介孔硅-碳微球的孔径为2nm~50nm。
6.根据权利要求5所述的一种铁基双层介孔硅-碳微球纳米复合材料在重金属去除中的应用,其特征在于,所述重金属离子为Cr6+或Cd2+中的一种或两种。
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