CN113499791A - 一种负载光催化剂的改性蛭石及其制备方法 - Google Patents
一种负载光催化剂的改性蛭石及其制备方法 Download PDFInfo
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Abstract
本发明公开了一种负载光催化剂的改性蛭石及其制备方法,包括制备活化蛭石、制备环氧改性蛭石、制备氨基改性蛭石、制备Fe改性蛭石、制备Ag3PO4‑ZnO粉末以及制备负载光催化剂的改性蛭石6个步骤,本发明提供的Fe改性蛭石通过氢键缔合和静电作用等作用,对四环素等污染物进行有效吸附,而且铁离子作为助催化剂,具有很强捕获光生电子的能力,进一步加强光催化降解能力,并且提供的Ag3PO4‑ZnO不仅可以吸收更多的可见光,而且可以通过构造异质结来防止光腐蚀,并且能够提高催化剂的循环稳定性,此外,具有很强捕获光生电子能力的铁离子可以接收Ag3PO4产生的光生电子,能够进一步防止光腐蚀。
Description
技术领域
本发明涉及蛭石复合材料技术领域,具体涉及一种负载光催化剂的改性蛭石及其制备方法。
背景技术
四环素是一种传统的抗生素,在农业和医学等领域应用广泛,但是四环素在自然界中很难被降解,导致四环素随着生物链在生物圈中不断积累,对人类健康、动物繁殖和生态系统造成了严重的危害,目前对于四环素的处理方法主要有生物降解法、物理吸附法、氧化还原法等,其中物理吸附法具有操作简单、成本较低等特点,是一种常用的污染物处理方法,光催化剂主要有TiO2、CdS、Ag3PO4、ZnO等,光催化降解法主要是通过光辐射在光催化剂上,电子受到激发和跃迁,产生光生载流子,进一步产生活性极强的羟基自由基等,将污染物降解为无毒的小分子,但是Ag3PO4本身的吸附能力很弱,而且容易发生光腐蚀。
蛭石是一种天然、无毒的矿物质,其储量丰富、廉价易得、生物友好、无污染,并且具有比表面积高、微孔结构丰富、吸附性强等特点,在药物载体、催化剂载体、环保、水污染治理等领域具有广阔的应用前景,为了进一步拓展蛭石的实际应用,需要对其进行化学改性,赋予其独特的功能,以实现对四环素等污染物的吸附降解,并且高比表面积的蛭石可以作为Ag3PO4、ZnO等光催化剂载体,得到具有高吸附性能和光催化降解的双功能的复合材料。
专利文献(CN105413639A)公开了一种生物友好型卵磷脂/蛭石复合材料及其制备方法与应用,所述复合材料的制备方法包括如下步骤:(1)将蛭石加入到去离子水中,随后搅拌并超声使其充分分散;(2)卵磷脂用无水乙醇溶解,然后加入上述去离子水中,所得悬浮液搅拌混合均匀后调节pH至酸性,然后水浴搅拌反应24h,得改性产物溶液;(3)将改性产物溶液离心,所得沉淀洗涤至中性,然后干燥,研磨过筛得到卵磷脂改性蛭石复合材料。本发明的卵磷脂改性蛭石复合材料可作为四环素类抗生素污染治理的吸附剂,具有以下优点:吸附速率快、平衡时间短,吸附效果优异且不受pH值及共存阳离子的影响,材料的环境适应能力强,但该专利没解决如何对四环素进行降解的问题。
发明内容
针对现有技术的不足,本发明的目的在于提供一种负载光催化剂的改性蛭石及其制备方法,解决传统的吸附材料对四环素吸附能力差以及不能进行降解的技术问题。
为了实现上述目的,本发明采取如下技术方案:
一种负载光催化剂的改性蛭石的制备方法,包括如下步骤:
(1)制备活化蛭石:将蛭石加入到碱溶液中,超声分散后进行搅拌预活化处理,然后进行过滤、洗涤和干燥,即得到活化蛭石;
(2)制备环氧改性蛭石:将活化蛭石加入到甲苯溶剂中,超声分散后加入环氧硅烷偶联剂进行反应,待反应结束后,将反应产物进行过滤、洗涤和干燥,即得到环氧改性蛭石;
(3)制备氨基改性蛭石:将环氧改性蛭石和三乙烯四胺加入到丙酮溶剂中,超声分散后进行氨基改性反应,待反应结束后,将反应产物进行过滤、洗涤和干燥,即得到氨基改性蛭石;
(4)制备Fe改性蛭石:将氨基改性蛭石加入到去离子水中,搅拌均匀,然后加入铁源,在室温下进行磁力反应2-3h,待反应结束后,将反应产物进行离心、洗涤、干燥和研磨,即得到Fe改性蛭石;
(5)制备Ag3PO4-ZnO粉末:将AgNO3和ZnO加入到去离子水中,搅拌均匀,然后加入Na2HPO4水溶液进行反应,待反应结束后,将反应产物进行离心、洗涤、干燥和研磨,即得到Ag3PO4-ZnO粉末;
(6)制备负载光催化剂的改性蛭石:将Fe改性蛭石和Ag3PO4-ZnO粉末加入到去离子水中,分散均匀后进行水热反应,待反应完成后,减压蒸馏除去溶剂,即得到负载光催化剂的改性蛭石。
优选的,步骤(1)中,所述碱溶液为氢氧化钠或氢氧化钾溶液,所述碱溶液的质量分数为2-4wt%,预活化处理时间为2-6h。
优选的,步骤(2)中,所述活化蛭石与环氧硅烷偶联剂的质量比为100:25-60,所述环氧硅烷偶联剂为3-缩水甘油醚氧基丙基三乙氧基硅烷、3-缩水甘油醚氧基丙基三甲氧基硅烷或3-[(2,3)-环氧丙氧]丙基甲基二甲氧基硅烷。
优选的,步骤(2)中,反应温度为30-50℃,反应时间为15-30h。
优选的,步骤(3)中,环氧改性蛭石和三乙烯四胺的质量比为100:60-150。
优选的,步骤(3)中,氨基改性反应温度为30-60℃,反应时间为6-12h。
优选的,步骤(4)中,氨基改性蛭石、铁源和去离子水的质量比为5:0.2-5:150-200,所述铁源为FeCl3·6H2O。
优选的,步骤(5)中,AgNO3、ZnO和去离子水的质量比为10:1-5:300-400,Na2HPO4水溶液的浓度为0.005-0.01mol/L,反应时间为24-30h。
优选的,步骤(6)中,Fe改性蛭石、Ag3PO4-ZnO粉末和去离子水的质量比为10:2-3.5:100-120,水热反应温度为80-100℃,水热反应时间为4-6h。
本发明还提供一种由上述制备方法得到的负载光催化剂的改性蛭石。
与现有技术相比,本发明具有如下有益效果:
(1)本发明提供一种负载光催化剂的改性蛭石及其制备方法,本发明用氢氧化钠将蛭石进行预活化处理,通过环氧硅烷偶联剂进行改性,得到环氧改性蛭石,然后引入的环氧基团与三乙烯四胺的氨基发生开环加成反应,得到氨基改性蛭石,从而在蛭石表面引入丰富的氨基和亚氨基,大量的氨基和亚氨基可以作为活性吸附位点,进一步吸附铁离子,形成Fe改性蛭石,Fe改性蛭石通过氢键缔合和静电作用等作用,对四环素等污染物进行有效吸附,而且铁离子作为助催化剂,具有很强捕获光生电子的能力,进一步加强光催化降解能力。
(2)本发明提供一种负载光催化剂的改性蛭石及其制备方法,本发明提供的Ag3PO4-ZnO不仅可以吸收更多的可见光,而且可以通过构造异质结来防止光腐蚀,并且能够提高催化剂的循环稳定性,此外,具有很强捕获光生电子能力的铁离子可以接收Ag3PO4产生的光生电子,能够进一步防止光腐蚀。
具体实施方式
以下通过具体较佳实施例对本发明作进一步详细说明,但本发明并不仅限于以下的实施例。
需要说明的是,无特殊说明外,本发明中涉及到的化学试剂均通过商业渠道购买。
实施例1
一种负载光催化剂的改性蛭石的制备方法,包括如下步骤:
(1)制备活化蛭石:将20g蛭石加入到质量分数为3%的氢氧化钠溶液中,超声分散后进行搅拌预活化处理3h,然后进行过滤、洗涤和干燥,即得到活化蛭石;
(2)制备环氧改性蛭石:将10g活化蛭石加入到200mL甲苯溶剂中,超声分散后加入2.5g3-缩水甘油醚氧基丙基三乙氧基硅烷,在30℃下反应15h,待反应结束后,将反应产物进行过滤、洗涤和干燥,即得到环氧改性蛭石;
(3)制备氨基改性蛭石:将10g环氧改性蛭石和6g三乙烯四胺加入到200mL丙酮溶剂中,超声分散均匀,然后在30℃下反应6h,待反应结束后,将反应产物进行过滤、洗涤和干燥,即得到氨基改性蛭石;
(4)制备Fe改性蛭石:将10g氨基改性蛭石加入到300g去离子水中,搅拌均匀,然后加入0.4gFeCl3·6H2O,在室温下磁力搅拌2h,待反应结束后,将反应产物进行离心、洗涤、干燥和研磨,即得到Fe改性蛭石;
(5)制备Ag3PO4-ZnO粉末:将10gAgNO3和2gZnO加入到300g去离子水中,搅拌均匀,然后加入50mL,0.005mol/L Na2HPO4水溶液进行反应24h,待反应结束后,将反应产物进行离心、洗涤、干燥和研磨,即得到Ag3PO4-ZnO粉末;
(6)制备负载光催化剂的改性蛭石:将10gFe改性蛭石和2.5gAg3PO4-ZnO粉末加入到110g去离子水中,分散均匀后倒入水热反应釜中,在80℃下进行水热反应4h,待反应完成后,减压蒸馏除去溶剂,即得到负载光催化剂的改性蛭石。
实施例2
一种负载光催化剂的改性蛭石的制备方法,包括如下步骤:
(1)制备活化蛭石:将20g蛭石加入到质量分数为3%的氢氧化钠溶液中,超声分散后进行搅拌预活化处理3h,然后进行过滤、洗涤和干燥,即得到活化蛭石;
(2)制备环氧改性蛭石:将10g活化蛭石加入到200mL甲苯溶剂中,超声分散后加入3g3-缩水甘油醚氧基丙基三乙氧基硅烷,在35℃下反应18h,待反应结束后,将反应产物进行过滤、洗涤和干燥,即得到环氧改性蛭石;
(3)制备氨基改性蛭石:将10g环氧改性蛭石和7g三乙烯四胺加入到200mL丙酮溶剂中,超声分散均匀,然后在38℃下反应6h,待反应结束后,将反应产物进行过滤、洗涤和干燥,即得到氨基改性蛭石;
(4)制备Fe改性蛭石:将10g氨基改性蛭石加入到300g去离子水中,搅拌均匀,然后加入2gFeCl3·6H2O,在室温下磁力搅拌2h,待反应结束后,将反应产物进行离心、洗涤、干燥和研磨,即得到Fe改性蛭石;
(5)制备Ag3PO4-ZnO粉末:将10gAgNO3和3gZnO加入到300g去离子水中,搅拌均匀,然后加入50mL,0.005mol/L Na2HPO4水溶液进行反应24h,待反应结束后,将反应产物进行离心、洗涤、干燥和研磨,即得到Ag3PO4-ZnO粉末;
(6)制备负载光催化剂的改性蛭石:将10gFe改性蛭石和2gAg3PO4-ZnO粉末加入到100g去离子水中,分散均匀后倒入水热反应釜中,在80℃下进行水热反应4h,待反应完成后,减压蒸馏除去溶剂,即得到负载光催化剂的改性蛭石。
实施例3
一种负载光催化剂的改性蛭石的制备方法,包括如下步骤:
(1)制备活化蛭石:将20g蛭石加入到质量分数为3%的氢氧化钠溶液中,超声分散后进行搅拌预活化处理3h,然后进行过滤、洗涤和干燥,即得到活化蛭石;
(2)制备环氧改性蛭石:将10g活化蛭石加入到200mL甲苯溶剂中,超声分散后加入3.5g3-缩水甘油醚氧基丙基三乙氧基硅烷,在40℃下反应20h,待反应结束后,将反应产物进行过滤、洗涤和干燥,即得到环氧改性蛭石;
(3)制备氨基改性蛭石:将10g环氧改性蛭石和8g三乙烯四胺加入到200mL丙酮溶剂中,超声分散均匀,然后在40℃下反应8h,待反应结束后,将反应产物进行过滤、洗涤和干燥,即得到氨基改性蛭石;
(4)制备Fe改性蛭石:将10g氨基改性蛭石加入到300g去离子水中,搅拌均匀,然后加入3gFeCl3·6H2O,在室温下磁力搅拌2h,待反应结束后,将反应产物进行离心、洗涤、干燥和研磨,即得到Fe改性蛭石;
(5)制备Ag3PO4-ZnO粉末:将10gAgNO3和3.5gZnO加入到300g去离子水中,搅拌均匀,然后加入50mL,0.005mol/L Na2HPO4水溶液进行反应24h,待反应结束后,将反应产物进行离心、洗涤、干燥和研磨,即得到Ag3PO4-ZnO粉末;
(6)制备负载光催化剂的改性蛭石:将10gFe改性蛭石和2.5gAg3PO4-ZnO粉末加入到100g去离子水中,分散均匀后倒入水热反应釜中,在90℃下进行水热反应4h,待反应完成后,减压蒸馏除去溶剂,即得到负载光催化剂的改性蛭石。
实施例4
一种负载光催化剂的改性蛭石的制备方法,包括如下步骤:
(1)制备活化蛭石:将20g蛭石加入到质量分数为3%的氢氧化钠溶液中,超声分散后进行搅拌预活化处理3h,然后进行过滤、洗涤和干燥,即得到活化蛭石;
(2)制备环氧改性蛭石:将10g活化蛭石加入到200mL甲苯溶剂中,超声分散后加入4g3-缩水甘油醚氧基丙基三乙氧基硅烷,在45℃下反应20h,待反应结束后,将反应产物进行过滤、洗涤和干燥,即得到环氧改性蛭石;
(3)制备氨基改性蛭石:将10g环氧改性蛭石和9g三乙烯四胺加入到200mL丙酮溶剂中,超声分散均匀,然后在60℃下反应10h,待反应结束后,将反应产物进行过滤、洗涤和干燥,即得到氨基改性蛭石;
(4)制备Fe改性蛭石:将10g氨基改性蛭石加入到300g去离子水中,搅拌均匀,然后加入3.5gFeCl3·6H2O,在室温下磁力搅拌2h,待反应结束后,将反应产物进行离心、洗涤、干燥和研磨,即得到Fe改性蛭石;
(5)制备Ag3PO4-ZnO粉末:将10gAgNO3和4gZnO加入到300g去离子水中,搅拌均匀,然后加入50mL,0.005mol/L Na2HPO4水溶液进行反应24h,待反应结束后,将反应产物进行离心、洗涤、干燥和研磨,即得到Ag3PO4-ZnO粉末;
(6)制备负载光催化剂的改性蛭石:将10gFe改性蛭石和2.8gAg3PO4-ZnO粉末加入到100g去离子水中,分散均匀后倒入水热反应釜中,在95℃下进行水热反应4h,待反应完成后,减压蒸馏除去溶剂,即得到负载光催化剂的改性蛭石。
实施例5
一种负载光催化剂的改性蛭石的制备方法,包括如下步骤:
(1)制备活化蛭石:将20g蛭石加入到质量分数为3%的氢氧化钠溶液中,超声分散后进行搅拌预活化处理3h,然后进行过滤、洗涤和干燥,即得到活化蛭石;
(2)制备环氧改性蛭石:将10g活化蛭石加入到200mL甲苯溶剂中,超声分散后加入6g3-缩水甘油醚氧基丙基三乙氧基硅烷,在50℃下反应20h,待反应结束后,将反应产物进行过滤、洗涤和干燥,即得到环氧改性蛭石;
(3)制备氨基改性蛭石:将10g环氧改性蛭石和10g三乙烯四胺加入到200mL丙酮溶剂中,超声分散均匀,然后在60℃下反应10h,待反应结束后,将反应产物进行过滤、洗涤和干燥,即得到氨基改性蛭石;
(4)制备Fe改性蛭石:将10g氨基改性蛭石加入到300g去离子水中,搅拌均匀,然后加入4gFeCl3·6H2O,在室温下磁力搅拌2h,待反应结束后,将反应产物进行离心、洗涤、干燥和研磨,即得到Fe改性蛭石;
(5)制备Ag3PO4-ZnO粉末:将10gAgNO3和5gZnO加入到300g去离子水中,搅拌均匀,然后加入50mL,0.005mol/L Na2HPO4水溶液进行反应24h,待反应结束后,将反应产物进行离心、洗涤、干燥和研磨,即得到Ag3PO4-ZnO粉末;
(6)制备负载光催化剂的改性蛭石:将10gFe改性蛭石和3.5gAg3PO4-ZnO粉末加入到100g去离子水中,分散均匀后倒入水热反应釜中,在95℃下进行水热反应4h,待反应完成后,减压蒸馏除去溶剂,即得到负载光催化剂的改性蛭石。
对比例1
一种负载光催化剂的改性蛭石的制备方法,包括如下步骤:
(1)制备活化蛭石:将20g蛭石加入到质量分数为3%的氢氧化钠溶液中,超声分散后进行搅拌预活化处理3h,然后进行过滤、洗涤和干燥,即得到活化蛭石;
(2)制备环氧改性蛭石:将10g活化蛭石加入到200mL甲苯溶剂中,超声分散后加入3.5g3-缩水甘油醚氧基丙基三乙氧基硅烷,在40℃下反应20h,待反应结束后,将反应产物进行过滤、洗涤和干燥,即得到环氧改性蛭石;
(3)制备氨基改性蛭石:将10g环氧改性蛭石和8g三乙烯四胺加入到200mL丙酮溶剂中,超声分散均匀,然后在40℃下反应8h,待反应结束后,将反应产物进行过滤、洗涤和干燥,即得到氨基改性蛭石;
(4)制备Ag3PO4-ZnO粉末:将10gAgNO3和3.5gZnO加入到300g去离子水中,搅拌均匀,然后加入50mL,0.005mol/L Na2HPO4水溶液进行反应24h,待反应结束后,将反应产物进行离心、洗涤、干燥和研磨,即得到Ag3PO4-ZnO粉末;
(5)制备负载光催化剂的改性蛭石:将10g氨基改性蛭石和2.5gAg3PO4-ZnO粉末加入到100g去离子水中,分散均匀后倒入水热反应釜中,在90℃下进行水热反应4h,待反应完成后,减压蒸馏除去溶剂,即得到负载光催化剂的改性蛭石。
将实施例1-5和对比例1所制备的改性蛭石进行吸附-降解四环素实验,具体步骤如下:分别配置500mL质量浓度为20mg/L的四环素溶液,然后向其中分别加入0.1g实施例1-5和对比例1所制备的改性蛭石,搅拌均匀后,在200W氙灯下进行光照降解过程,然后使用UV754N紫外可见分光光度计测定在不同时间下溶液中四环素的浓度,实验结果如下表所示:
从表中可以看出,本实施例所制备的改性蛭石对四环素具有良好的吸附-光降解率,可以达到90%以上,对比例1中没有进行Fe改性蛭石,其吸附-光降解率明显降低,原因在于Fe改性蛭石通过氢键缔合和静电作用等作用,对四环素进行有效吸附,而且铁离子作为助催化剂,可以接收Ag3PO4产生的光生电子,能够加强光催化降解能力。
最后需要说明的是:以上实施例不以任何形式限制本发明。对本领域技术人员来说,在本发明基础上,可以对其作一些修改和改进。因此,凡在不偏离本发明精神的基础上所做的任何修改或改进,均属于本发明要求保护的范围之内。
Claims (10)
1.一种负载光催化剂的改性蛭石的制备方法,其特征在于,包括如下步骤:
(1)制备活化蛭石:将蛭石加入到碱溶液中,超声分散后进行搅拌预活化处理,然后进行过滤、洗涤和干燥,即得到活化蛭石;
(2)制备环氧改性蛭石:将活化蛭石加入到甲苯溶剂中,超声分散后加入环氧硅烷偶联剂进行反应,待反应结束后,将反应产物进行过滤、洗涤和干燥,即得到环氧改性蛭石;
(3)制备氨基改性蛭石:将环氧改性蛭石和三乙烯四胺加入到丙酮溶剂中,超声分散后进行氨基改性反应,待反应结束后,将反应产物进行过滤、洗涤和干燥,即得到氨基改性蛭石;
(4)制备Fe改性蛭石:将氨基改性蛭石加入到去离子水中,搅拌均匀,然后加入铁源,在室温下进行磁力反应2-3h,待反应结束后,将反应产物进行离心、洗涤、干燥和研磨,即得到Fe改性蛭石;
(5)制备Ag3PO4-ZnO粉末:将AgNO3和ZnO加入到去离子水中,搅拌均匀,然后加入Na2HPO4水溶液进行反应,待反应结束后,将反应产物进行离心、洗涤、干燥和研磨,即得到Ag3PO4-ZnO粉末;
(6)制备负载光催化剂的改性蛭石:将Fe改性蛭石和Ag3PO4-ZnO粉末加入到去离子水中,分散均匀后进行水热反应,待反应完成后,减压蒸馏除去溶剂,即得到负载光催化剂的改性蛭石。
2.根据权利要求1所述的负载光催化剂的改性蛭石的制备方法,其特征在于,步骤(1)中,所述碱溶液为氢氧化钠或氢氧化钾溶液,所述碱溶液的质量分数为2-4wt%,预活化处理时间为2-6h。
3.根据权利要求1所述的负载光催化剂的改性蛭石的制备方法,其特征在于,步骤(2)中,所述活化蛭石与环氧硅烷偶联剂的质量比为100:25-60,所述环氧硅烷偶联剂为3-缩水甘油醚氧基丙基三乙氧基硅烷、3-缩水甘油醚氧基丙基三甲氧基硅烷或3-[(2,3)-环氧丙氧]丙基甲基二甲氧基硅烷。
4.根据权利要求1所述的负载光催化剂的改性蛭石的制备方法,其特征在于,步骤(2)中,反应温度为30-50℃,反应时间为15-30h。
5.根据权利要求1所述的负载光催化剂的改性蛭石的制备方法,其特征在于,步骤(3)中,环氧改性蛭石和三乙烯四胺的质量比为100:60-150。
6.根据权利要求1所述的负载光催化剂的改性蛭石的制备方法,其特征在于,步骤(3)中,氨基改性反应温度为30-60℃,反应时间为6-12h。
7.根据权利要求1所述的负载光催化剂的改性蛭石的制备方法,其特征在于,步骤(4)中,氨基改性蛭石、铁源和去离子水的质量比为5:0.2-5:150-200,所述铁源为FeCl3·6H2O。
8.根据权利要求1所述的负载光催化剂的改性蛭石的制备方法,其特征在于,步骤(5)中,AgNO3、ZnO和去离子水的质量比为10:1-5:300-400,Na2HPO4水溶液的浓度为0.005-0.01mol/L,反应时间为24-30h。
9.根据权利要求1所述的负载光催化剂的改性蛭石的制备方法,其特征在于,步骤(6)中,Fe改性蛭石、Ag3PO4-ZnO粉末和去离子水的质量比为10:2-3.5:100-120,水热反应温度为80-100℃,水热反应时间为4-6h。
10.一种由权利要求1-9所述制备方法得到的负载光催化剂的改性蛭石。
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