CN112473672A - 水合介孔二氧化硅包覆纳米铁钴双金属复合材料及其应用 - Google Patents
水合介孔二氧化硅包覆纳米铁钴双金属复合材料及其应用 Download PDFInfo
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Abstract
本发明公开了一种水合介孔二氧化硅包覆纳米铁钴双金属复合材料的制备方法。制备方法包括以下步骤:步骤1、在乙醇和水的混合溶液中加入0.496g七水合硫酸铁和0.502g七水合硫酸钴,机械搅拌直到固体颗粒溶解;步骤2、向混合溶液中以1.5ml/min的速度滴加NaBH4溶液,继续搅拌30min,获得纳米零价铁钴双金属悬浮液;步骤3、继续向溶液中添加氨水和十六烷基三甲基溴化铵,持续搅拌30min,往里面添加1ml正硅酸四乙酯,低速(300rpm)搅拌4h;步骤4、用磁铁将固体与液体分离,依次用去离子水和无水乙醇各洗涤三次,最后在干燥箱干燥12h。获得最终产物水合介孔二氧化硅包覆纳米铁钴双金属复合材料。通过水合介孔二氧化硅包覆纳米铁钴双金属作用克服了纳米铁钴双金属易团聚、易失活和Co离子浸出的问题,提高了纳米铁钴双金属的分散性和反应性。将本发明方法得到的水合介孔二氧化硅包覆纳米铁钴双金属复合材料与双氧水构成类Fenton体系,用于去除地下水中四溴双酚A。该方法对于四溴双酚A污染场地土壤地下水有很强的修复效果。
Description
技术领域
本发明属于地下水污染物的处理技术领域,具体涉及一种水合介孔二氧化硅包裹纳米铁钴双金属复合材料及其与双氧水的应用。
背景技术
四溴双酚A(TBBPA)属于溴化阻燃剂(BFR),在我们的生活中广泛应用。占BFRs市场份额的60%以上。TBBPA主要用作反应性阻燃剂应用在电路板、塑料和化工等中,全球市场需求非常大。由于TBBPA的应用及其广泛以及人类对其废物的不当处置,导致大量的TBBPA被释放到环境中。目前在各个环境介质中都检测到了TBBPA,比如土壤、空气、水环境以及动物和人体内。已成为一种普遍存在的污染物。有研究表明,TBBPA具有甲状腺激素活性,雌激素活性和致癌性,对环境中的生物产生巨大的危害。因此寻找出来有效降解TBBPA的材料具有重大意义。
目前国内外对于四溴双酚A的降解研究很多,常见的方法有物理吸附,生物降解和高级氧化技术(AOTs)(光催化,电催化,臭氧氧化和Fenton方法)等。由于物理吸附和生物降解的修复周期长,实际应用受到了限制。尽管有许多报道称光催化具有较高的氧化性能和较少的二次污染,但由于高能耗和高成本,其使用条件受到了限制。电催化可以通过一次电池的作用快速转移电子,从而提高降解效率。然而,这种方法要求苛刻的反应条件和对电极的高要求,这极大地限制了其使用条件的局限性。臭氧在降解过程中会产生一些惰性中间体,这会影响污染物的完全降解。Fenton法由于pH应用范围较窄也限制了其应用。这些降解方法单独使用都不是很好的去除四溴双酚A的方法。同时很多方法还仅限于实验室中,无法应用于实际污染场地修复中或者修复效果很差。
发明内容
针对上述问题,本发明的目的在于克服现有技术的不足,提供一种水合介孔二氧化硅包覆纳米铁钴双金属复合材料的制备方法及其应用,以水合介孔二氧化硅为壳,将纳米铁钴双金属包覆在介孔的二氧化硅里面,从而克服了纳米铁钴双金属团聚的缺点,其特有的介孔网络结构还防止了重金属离子的浸出,避免了二次污染。水合介孔二氧化硅包覆纳米铁钴双金属复合材料与双氧水构成的类Fenton体系,可以在较高的pH值下有效的去处环境中的四溴双酚A。
本发明技术方案如下
本发明的有益效果体现在:
(1)本发明所制备的水合介孔二氧化硅壳具有中空结构以及独有的介孔网络结构,水合介孔二氧化硅包覆纳米铁钴双金属复合材料中铁钴摩尔比可以调控。
(2)本发明所利用的硅源廉价可再生,并且具有及其简单的制备流程,成本低廉,可以大规模进行生产。
(3)本发明所制备的水合介孔二氧化硅包覆纳米铁钴双金属复合材料具有较大的比表面积,可以提供更多的暴露活性位点增大反应速率。
(4)本发明所制备的水合介孔二氧化硅包覆纳米铁钴双金属复合材料其独有的介孔网络结构防止了重金属离子的浸出,避免了二次污染。
(5)本发明所制备的水合介孔二氧化硅包覆纳米铁钴双金属复合材料,由于纳米铁钴双金属被水合二氧化硅所包裹,克服了纳米铁钴双金属易团聚易失活的缺点,提高了纳米铁钴双金属分散性和反应性。
(6)本发明所制备的水合介孔二氧化硅包覆纳米铁钴双金属复合材料和双氧水构成的类Fenton体系,能够在较大pH值下有效去处地下水中的四溴双酚A。
附图说明
图1是本发明制备的几种材料的透射电镜图(SEM)。
图2是本发明制备的几种材料的X射线衍射(XRD)图。
图3是本发明制备水合介孔二氧化硅包覆纳米铁钴双金属复合材料和双氧水构成的类Fenton体系去除水环境中四溴双酚A的效果图。
图4是本发明制备水合介孔二氧化硅包覆纳米铁钴双金属复合材料循环降解四溴双酚A后铁钴离子的浸出浓度。
具体实施方式
为使发明专利更好的展示目的性和优点性,下面将结合1-4附图对发明的具体实施例的进一步说明。
实施例1:
该实施例提供了一种水合介孔二氧化硅包覆纳米铁钴双金属复合材料的制备方法,具体包括以下步骤:
步骤1、将0.496g FeSO4·7H2O和0.502g CoSO4·7H2O溶解在95mL水和乙醇的混合溶液中,其中水和乙醇的体积比为(45-50):(50-45),搅拌使之完全溶解;
步骤2、称取0.05g-0.06gNaBH4溶解到50ml的去离子水中,置于三颈烧瓶中。将装NaBH4溶液的三颈烧瓶放入到超声仪中(功率显示50-70%)。有在氮气的保护下,向该溶液中以3mL/min的速度滴加步骤一的混合溶液,滴加完毕后。继续搅拌30-60min,溶液变成黑色或者深棕色,获得纳米铁钴双金属悬浮液;
步骤3、继续向三颈烧瓶中添加5mL NH3.H2O和0.6g十六烷基溴化铵,在600-800rmp的速度下搅拌30min后,加入1mL正硅酸四乙酯搅拌4-6小时;
步骤4、用磁铁把黑色固体和液体分离,依次用去离子水和无水乙醇洗涤,重复洗涤各三次后获得产物;
步骤5、将产物放入40-60℃真空干燥箱中干燥10-12h得到最终样品水合介孔二氧化硅包覆纳米铁钴双金属。
水合二氧化硅材料的制备:将水合介孔二氧化硅包覆纳米铁钴双金属复合材料放入到2mol/mL的盐酸溶液中刻蚀12-24h,在3000-4500rpm离心5min后,依次用去离子水和无水乙醇洗涤,重复洗涤各三次后获得产物,放入真空干燥箱干燥4-6h。
用此方法制备的复合材料特征如下:
如图1所示,为纳米零价铁钴双金属和水合介孔二氧化硅包覆的铁钴双金属的投射电镜图。
从图1(a)我们可以看出铁钴双金属团聚在一起呈链装的结构。
从图1(b)我们可以看出,纳米铁钴双金属被水合介孔二氧化硅覆盖后,复合材料均匀的分散,呈现核-壳结构。这一结果表明二氧化硅成功地将纳米铁钴双金属包覆在内部,减少了纳米铁钴双金属的团聚。
如图2所示,为水合介孔二氧化硅、纳米铁钴双金属和水合介孔二氧化硅包覆铁钴双金属复合材料的X射线衍射图。
水合介孔二氧化硅在23.15°由无定形水合二氧化硅引起的衍射峰;纳米铁钴双金属晶体结构的衍射峰为显示在2θ为46°处的单峰,这是因为铁与钴相互作用并形成了合金晶体。水合介孔二氧化硅包覆的铁钴双金属复合材料的衍射峰,分别对应于水合介孔二氧化硅和纳米铁钴双金属的特征峰,但是在23.15°处衍射峰的强度较低,可能是因为纳米铁钴双金属嵌入在水合介孔二氧化硅的内部。该结果进一步表明表明水合介孔二氧化硅包覆的铁钴双金属复合材料已成功合成。
实施案例2:
该实施例提供了实施例1所获得的水合介孔二氧化硅包覆的铁钴双金属复合材料对地下水中四溴双酚A去处的方法,具体包括以下几个步骤:
步骤1、取5个100mL的血清瓶,分别添加50ml四溴双酚A(10mg/L)溶液。再取出4个血清瓶添加20mmol/L的双氧水,仅留一个只含有50ml四溴双酚A(10mg/L)的血清瓶。将5个血清瓶中溶液都调到pH=7。
步骤2、称取实施例1中所获得的水合介孔二氧化硅包覆的铁钴双金属复合材料1g/mL(含0.25g/mL纳米铁钴双金属),0.25g/mL纳米铁钴双金属和0.75g/mL水合介孔二氧化硅,分别添加到含有双氧水的血清瓶中。将仅含四溴双酚A的血清瓶作为对照。另外称取复合材料(1g/mL)添加到仅含有四溴双酚A的血清瓶中。
步骤3、将5个血清瓶放在恒温振荡培养箱中。在反应期间,以规定的时间间隔(0、0.2、0.5、1、2、4和6h),收集1mL水样(用0.22μm有机过滤器过滤),并立即用0.5μmL叔丁醇淬灭反应。
步骤4、通过高效液相色谱仪(HPLC-UV)测量剩余四溴双酚A的浓度。
纳米零价铁钴双金属的制备:将0.496g FeSO4·7H2O和0.502g CoSO4·7H2O溶解在95mL水和乙醇的混合溶液中,水和乙醇的体积比是(45-50):(50-45),机械搅拌一段时间以使其完全溶解;在氮气的保护下,向该混合物中以1.5ml/min的速度滴加50mL的10g/LNaBH4溶液,并继续搅拌30min,溶液变成黑色或者深棕色。用磁铁将固体和液体分离,次用去离子水和无水乙醇洗涤,重复洗涤三次,将产物放入40-60℃真空干燥箱,干燥10-12h得到最终样品纳米铁钴双金属。
水合二氧化硅材料的制备:将水合介孔二氧化硅包覆纳米铁钴双金属复合材料放入到2mol/mL的盐酸溶液中刻蚀12h,在3500-4000rpm离心5min后,次用去离子水和无水乙醇洗涤,重复洗涤各三次后获得产物,放入真空干燥箱干燥4h。
如图3所示,为水合介孔二氧化硅、纳米铁钴双金属和水合介孔二氧化硅包覆铁钴双金属复合材料对地下水中四溴双酚A的去处效果图。在反应6小时后,单独的双氧水对四溴双酚A的去除几乎没有影响。水合介孔二氧化硅包覆纳米铁钴双金属复合材料对四溴双酚A去除效率高达97.13%,远高于纳米铁钴双金属的84.49%和单独的纳米铁钴双金属的59.37%。此外,单独的水合介孔二氧化能够去处12%的四溴双酚A。水合介孔二氧化硅包覆纳米铁钴双金属复合材料去除四溴双酚A的速率大于纳米铁钴双金属和水合介孔二氧化硅的总和。该结果表明表明水合介孔二氧化硅与纳米铁钴双金属之间具有协同作用,具有较高的反应活性,能够有效的去处地下水中的四溴双酚A。
实施案例3:
该实施例提供了实施例1所获得水合介孔二氧化硅包覆的铁钴双金属复合材料,以及循环降解的方法。具体包括以下几个步骤:
步骤1、对实施例2中反应后的水合介孔二氧化硅包覆的铁钴双金属复合材料进行磁铁分离,依次用去离子水和无水乙醇洗涤,重复洗涤三次后获得反应后的复合材料;
步骤2、将复合材料添加到含50ml TBBPA(10mg/L)和20mmol/L的双氧水的血清瓶中,调节pH=7。
步骤3、将血清瓶放在恒温振荡培养箱中。在反应期间,以规定的时间间隔(0、0.2、0.5、1、2、4和6h),收集1mL水样(用0.22μm有机过滤器过滤),并立即用0.5μmL叔丁醇淬灭反应。
步骤4、通过电感耦合等离子体发射光谱仪(ICP-OES)测量铁离子和钴离子的浓度。
步骤5、重复以上步骤,循环6次,获得铁离子和钴离子的浓度。
如图4所示显示了不同循环中铁离子和钴离子的浸出浓度。尽管在每个循环之后都观察到了铁和钴离子的浸出,但其浓度仍远低于国际排放标准(<2ppm)。
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 (5)
1.一种水合介孔二氧化硅包裹Fe/Co双金属复合材料的制备方法,其特征在于,包括如下步骤:
步骤1、将0.496g FeSO4·7H2O和0.502g CoSO4·7H2O溶解在95mL水和乙醇的混合溶液中,其中水和乙醇的体积比为(45-50):(50-45),搅拌使之完全溶解;
步骤2、称取0.05g-0.06gNaBH4溶解到50ml的去离子水中,置于三颈烧瓶中。将装NaBH4溶液的三颈烧瓶放入到超声仪中(功率显示50-70%)。有在氮气的保护下,向该溶液中以3mL/min的速度滴加步骤一的混合溶液,滴加完毕后。继续搅拌30-60min,溶液变成黑色或者深棕色,获得纳米铁钴双金属悬浮液;
步骤3、继续向三颈烧瓶中添加5mL NH3.H2O和0.6g十六烷基溴化铵,在600-800rmp的速度下搅拌30min后,加入1mL正硅酸四乙酯搅拌4-6小时;
步骤4、用磁铁把黑色固体和液体分离,依次用去离子水和无水乙醇洗涤,重复洗涤各三次后获得产物;
步骤5、将产物放入40-60℃真空干燥箱中干燥10-12h得到最终样品水合介孔二氧化硅包覆纳米铁钴双金属。
2.根据权利要求1所述的水合介孔二氧化硅包覆纳米铁钴双金属复合材料的制备方法,其特征在于:所述步骤1中,所述铁和钴的摩尔比是1:1。
3.根据权利要求1所述的水合介孔二氧化硅包覆纳米铁钴双金属复合材料的制备方法,其特征在于:在所述步骤2和步骤3中,所述搅拌速度为600-800rpm。
4.根据权利要求1所述的水合介孔二氧化硅包覆纳米铁钴双金属复合材料的制备方法,其特征在于:在所述步骤5中,所述烘干温度为40-60℃,烘干时间为10-12h。
5.一种利用水合介孔二氧化硅包覆纳米铁钴双金属复合材料和双氧水构成的类Fenton体系去除地下水中四溴双酚A的方法,其中,水合介孔二氧化硅包覆纳米铁钴双金属复合材料通过权利要求1-4任意一种制备方法获得,该方法应用于实际污染场地,适用的pH范围在5-9,其中,四溴双酚A的浓度在2~50mg/L;水合介孔二氧化硅包裹纳米铁钴双金属复合材料吸附量为6~12mg/L。
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Application publication date: 20210312 |