CN113441179B - 一种噻吩修饰的共价三嗪骨架材料及其制备与应用 - Google Patents
一种噻吩修饰的共价三嗪骨架材料及其制备与应用 Download PDFInfo
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Abstract
本发明提供了一种噻吩修饰的共价三嗪骨架材料,按如下方法制备得到:将对苯二甲腈和对噻吩基苯甲腈均匀混合,得到混合粉末,‑5~0℃、惰性气体氛围条件下,将混合粉末加到三氟甲磺酸中搅拌100~120min,接着于110~120℃下反应30~40min,之后经水洗、离心分离得到沉淀物,将沉淀物干燥、研磨、筛分,即得;本发明噻吩修饰的共价三嗪骨架材料结构中不含金属元素,没有金属溶出的危害,应用于有机污染废水的催化氧化降解处理,去除效果好,拓宽了可见光的利用范围以及不同pH水质的适用范围,并且结构稳定,使用寿命长,能实现催化剂的重复利用。
Description
技术领域
本发明涉及一种噻吩修饰的共价三嗪骨架材料及其制备方法,以及在可见光下处理难降解有机污染废水方面的应用。
背景技术
难降解有机污染废水如酚类、染料以及医疗废水具有废水成分复杂、污染物浓度高、降解难且对环境和人类危害大等特点,而传统的废水处理技术不能对这些废水进行高效、深度的处理。芬顿技术作为一种经典的高级氧化技术在处理水中难降解有机污染物的应用越来越广泛。但是其存在pH使用范围窄(一般为pH 2-4)、会产生大量铁污泥、H2O2的利用率较低、催化剂回收难以及催化剂寿命短等弊端。因此迫切需要继续开发一类高活性、高稳定性及宽适用范围的催化剂。
活化过硫酸盐高级氧化技术是近年来发展起来的一种以硫酸根自由基和羟基自由基为主要活性物质降解污染物的新型高级氧化技术。硫酸根自由基氧化能力较强、氧化无选择性,其氧化产物硫酸根对于水环境中微生物、水生生物影响较小。目前,常用的异相类芬顿催化剂有金属氧化物、贵金属半导体等,在可见光下具有较宽的波长范围和较好的可见光响应性能,但其存在金属溶出以及制备成本高的缺点。
发明内容
针对难降解有机污染废水(尤其含双酚A污染水体)采用现有常规污水处理效果差的问题,本发明创新性地提出了一种噻吩修饰的共价三嗪骨架材料活化过硫酸盐水处理高级氧化技术,并对噻吩修饰的共价三嗪骨架材料的制备方法和应用条件进行说明。本发明制备的催化剂材料,利用其结构特征、基团性能特征和可见光催化性能等特点,在光助条件下活化过硫酸盐产生硫酸根自由基,实现对难降解污染物的强化去除。
本发明提供的一种无金属的具有可见光响应的催化剂,其分子间/分子内含有电子供体(噻吩基团)和电子受体(氰基基团),能诱导并加速分子间/分子内电荷转移。此外,引入供体-受体后能提高催化剂的可见光吸收能力,拓宽可见光的利用范围以及不同pH水质的适用范围,该双重调控策略改变了传统三嗪环中的均匀电荷分布,从而极大地促进了对有机污染物的降解反应。
本发明催化剂耐酸、耐碱且具有良好使用寿命,以过硫酸盐作为氧化剂,在可见光下氧化降解难降解有机污染物具有很高的去除效果,有效避免了传统芬顿法中pH有效值范围窄、过氧化氢的利用率低、易造成铁离子二次污染的问题。
本发明的技术方案如下:
一种噻吩修饰的共价三嗪骨架材料,按如下方法制备得到:
将对苯二甲腈和对噻吩基苯甲腈均匀混合(可采用球磨机或石英研钵),得到混合粉末,-5~0℃、惰性气体(例如氩气)氛围条件下,将混合粉末加到三氟甲磺酸中搅拌100~120min,接着于110~120℃下反应30~40min,之后经水洗、离心分离得到沉淀物,将沉淀物干燥、研磨、筛分(200~300目),得到所述噻吩修饰的共价三嗪骨架材料;
所述对苯二甲腈与对噻吩基苯甲腈的摩尔比为9~49:1;
所述对苯二甲腈与三氟甲磺酸的摩尔比为8~16:1。
本发明中,反应原料对苯二甲腈和对噻吩基苯甲腈的结构式如下:
本发明所述噻吩修饰的共价三嗪骨架材料可用于有机污染废水的催化氧化降解处理。所述有机污染废水例如含酚类(双酚A)污染水体、染料废水、医疗废水等。
具体应用的方法为:
向废水中加入氧化剂过硫酸盐,超声使其溶解,然后加入噻吩修饰的共价三嗪骨架材料,超声分散均匀后,于300W氙灯照射下磁力搅拌反应10~90min,完成对水中有机污染物的降解;
所述过硫酸盐为单过硫酸钾、过硫酸钾或过硫酸钠;过硫酸盐在废水中的浓度为0.2~1.0mM;
所述噻吩修饰的共价三嗪骨架材料在废水中的浓度为0.1~0.5g/L。
与现有技术相比,本发明的有益效果在于:
1、本发明一种噻吩修饰的共价三嗪骨架催化剂与传统催化剂相比,分子结构中不含金属元素,没有金属溶出的危害;
2、本发明异相芬顿催化剂降解双酚A废水效果好,具有很高的去除效果;
3、本发明异相芬顿催化剂结构稳定,使用寿命长,能实现催化剂的重复利用。
附图说明
图1本发明实施例1制得的催化剂的TEM图。
图2本发明实施例1制得的催化剂的傅里叶红外FT-IR图。
图3本发明实施例1制得的催化剂的碳谱图。
图4本发明实施例1制得的催化剂的异相芬顿降解不同难降解有机污染物曲线图。
具体实施方式
下面通过具体实施例进一步描述本发明,但本发明的保护范围并不仅限于此。
实施例1一种噻吩修饰的共价三嗪骨架催化剂的制备
(1)将对苯二甲腈(0.98g,7.8mmol)和对噻吩基苯甲腈(0.02g,0.16mmol),按照49:1的摩尔比用石英研钵(50mL)均匀混合;
(2)在15mL石英管中装入转子并往其中通入氩气20min以达到排出空气的目的,在此基础上,将石英管置于-2℃冰水浴锅中,并加入三氟甲磺酸(4mL,0.78mmol);
(3)开启磁力搅拌器,将(1)中的混合粉末缓慢加入(2)中石英管中,得到混合液;
(4)在氩气氛围下,(3)中混合液在冰水浴中剧烈(400-500r/min)搅拌110min;
(5)将(4)中石英管置于110℃烘箱中30min;
(6)反应完毕后,多次重复水洗、离心分离得到沉淀物;
(7)将沉淀物干燥;
(8)干燥后的样品研磨、筛分得到所述催化剂。
实施例2催化氧化降解双酚A
将初始浓度为10ppm的100mL双酚A置于200mL反应器中,然后加入0.5mM单过硫酸钾,超声均匀后加入0.02g实施例1制备的催化剂,于300W氙灯照射和150r/min的条件下搅拌反应90min,由图3可知,双酚A的去除率达到100%。
实施例3
本实施例与实施例1不同之处为:步骤(1)中对苯二甲腈和对噻吩基苯甲腈按照19:1的摩尔比用球磨机机械均匀混合。其他步骤及参数与实施例1相同。
实施例4
本实施例与实施例1不同之处为:步骤(1)中对苯二甲腈和对噻吩基苯甲腈按照9:1的摩尔比用球磨机机械均匀混合。其他步骤及参数与实施例1相同。
实施例5
本实施例与实施例2不同之处为:将初始浓度为10ppm的100mL诺氟沙星置于200mL反应器中进行降解反应。其他步骤及参数与实施例2相同,90min后其去除率达100%。
实施例6
本实施例与实施例2不同之处为:将初始浓度为10ppm的100mL卡马西平置于200mL反应器中进行降解反应。其他步骤及参数与实施例2相同,90min后其去除率达100%。
实施例7
本实施例与实施例2不同之处为:将初始浓度为10ppm的100mL环丙沙星置于200mL反应器中进行降解反应。其他步骤及参数与实施例2相同,90min后其去除率达95%。
实施例8
本实施例与实施例2不同之处为:将初始浓度为10ppm的100mL 2,4-二氯苯氧乙酸置于200mL反应器中进行降解反应。其他步骤及参数与实施例2相同,90min后其去除率达72%。
Claims (6)
1.一种噻吩修饰的共价三嗪骨架材料,其特征在于,按如下方法制备得到:
将对苯二甲腈和对噻吩基苯甲腈均匀混合,得到混合粉末,-5~0℃、惰性气体氛围条件下,将混合粉末加到三氟甲磺酸中搅拌100~120min,接着于110~120℃下反应30~40min,之后经水洗、离心分离得到沉淀物,将沉淀物干燥、研磨、筛分,得到所述噻吩修饰的共价三嗪骨架材料;
所述对苯二甲腈与对噻吩基苯甲腈的摩尔比为9~49:1。
2.如权利要求1所述噻吩修饰的共价三嗪骨架材料,其特征在于,所述对苯二甲腈与三氟甲磺酸的摩尔比为8~16:1。
3.如权利要求1所述噻吩修饰的共价三嗪骨架材料在有机污染废水的催化氧化降解处理中的应用。
4.如权利要求3所述的应用,其特征在于,所述应用的方法为:
向废水中加入氧化剂过硫酸盐,超声使其溶解,然后加入噻吩修饰的共价三嗪骨架材料,超声分散均匀后,于300W氙灯照射下磁力搅拌反应10~90min,完成对水中有机污染物的降解;
所述过硫酸盐为单过硫酸钾、过硫酸钾或过硫酸钠。
5.如权利要求4所述的应用,其特征在于,所述过硫酸盐在废水中的浓度为0.2~1.0mM。
6.如权利要求4所述的应用,其特征在于,所述噻吩修饰的共价三嗪骨架材料在废水中的浓度为0.1~0.5g/L。
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