CN116328804A - 一种碳化钨修饰的封装有钴纳米颗粒的碳纳米管及其在促进pms活化降解抗生素中的应用 - Google Patents
一种碳化钨修饰的封装有钴纳米颗粒的碳纳米管及其在促进pms活化降解抗生素中的应用 Download PDFInfo
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Abstract
本发明公开了一种碳化钨修饰的封装有钴纳米颗粒的碳纳米管及其在促进PMS活化降解抗生素中的应用。本发明将多酸封装在ZIF内,经高温热解得到碳化钨修饰的封装有钴纳米颗粒的碳纳米管,然后应用于催化氧化降解抗生素。本发明的方法制备过程简便、绿色高效、易于回收、底物易于与活性位点充分接触。得到的材料具有优异的孔结构、大的比表面积与规则的形貌,在催化过程中发挥重要的作用;并且催化剂可以通过外加磁场轻松分离,具有良好的循环回收稳定性。该材料不仅在土霉素降解中展现了优异的催化活性,在其他种类的抗生素降解中也展现了>85%的去除效率,为多酸基MOF衍生物在电催化、锂电池和超级电容器等领域的应用提供了可能。
Description
技术领域
本发明属于碳化钨材料制备技术领域,具体涉及一种碳化钨修饰的封装有钴纳米颗粒的碳纳米管及其在促进PMS活化降解抗生素中的应用。
背景技术
在过去的几十年里,来自制药、牲畜或医院的抗生素废水已成为水污染的主要来源,对人类健康和环境构成了重大威胁。因此,探索一种高效、低成本的抗生素去除技术迫在眉睫。近年来,一种特殊的高级氧化法(AOP)在水污染修复中受到越来越多的关注,它主要是通过激活各种过氧化物产生强活性氧(ROSs)来降解有机污染物。以羟基自由基(·OH)为基础的类-芬顿催化体系,以过氧化氢(H2O2)为氧化剂,实现了对抗生素的有效降解。但是,在催化反应的过程中,H2O2的利用率低、工作pH范围窄等问题,严重限制了其实际应用。而基于硫酸盐自由基(SO4 ∙−)的过氧硫酸盐(PMS)的类-芬顿体系因其较高的氧化电位(2.5-3.1 V)、较长的半衰期(30-40 μs)、高选择性和宽的pH响应范围而在水中污染物的降解中引起了越来越多的关注。
目前,已经报道了多种方法用于过硫酸氢钾的活化,其中非均相固体催化剂因其简单、易操作、多用途而受到广泛关注。金属钴化合物被认为是降解有机污染物最有效的PMS活化剂。因为金属钴的引入不仅促进了催化剂表面电子的快速转移,而且有利于活性氧(ROSs)物质的快速生成。但是,催化剂在催化过程中也存在一些问题,例如催化剂对PMS的吸附能力有限会严重影响SO4 ∙−的收率,从而导致常规的钴基材料的吸附能力不尽人意。此外,过渡金属导电性差、金属浸出严重也是制约其实际应用的主要问题。
发明内容
为了解决上述存在的问题,本发明提供了一种碳化钨修饰的封装有钴纳米颗粒的碳纳米管及其在促进PMS活化降解抗生素中的应用。ZIF-67/8的腔直径约为1.16纳米,窗口尺寸为0.34纳米,而尺寸约为1.0纳米的Kegging类型的多酸可以很好地容纳在ZIF的孔道中;本发明利用ZIF-67/8的腔直径与Kegging类型的多酸尺寸很好的相容性,将多酸封装在ZIF内,经高温热解得到碳化钨修饰的封装有钴纳米颗粒的碳纳米管,然后应用于催化氧化降解抗生素。
所述的碳化钨修饰的封装有钴纳米颗粒的碳纳米管为缠绕在一起的碳纳米管结构,小尺寸的碳化钨均匀地负载在碳纳米管上,而钴纳米颗粒均匀地包裹在氮掺杂碳纳米管中,没有聚集。
所述的碳化钨修饰的封装有钴纳米颗粒的碳纳米管的制备方法为:将硝酸锌的甲醇溶液与多酸水溶液混合后加入2-甲基咪唑的甲醇溶液中,老化后离心洗涤,将沉淀再加入2-甲基咪唑的甲醇溶液中,然后加入乙酸钴的甲醇溶液,老化后离心洗涤,沉淀经真空干燥后在氮气氛围下高温焙烧,最后离心洗涤,真空干燥即得。
所述的碳化钨修饰的封装有钴纳米颗粒的碳纳米管的制备方法的具体步骤为:
(a)将0.950-1.90g六水合硝酸锌溶解在20-40 mL甲醇中形成溶液A,将30-120 mg多酸溶解在3-12 mL水中形成溶液B;将B溶液快速加入到A溶液中后室温下搅拌10-20分钟;
(b)将步骤(a)得到的混合溶液快速加入到20-40 mL含2-4 g的2-甲基咪唑的甲醇溶液中,得到浑浊混合物;溶液在室温下老化10-40小时,离心收集沉淀,用水和甲醇洗涤,直到完全去除吸附在表面的多酸;
(c)将步骤(b)得到的沉淀再加入80-240 mL含1.314-3.941 g的 2-甲基咪唑的甲醇溶液中,搅拌2-10 min后加入20-60 mL含0.996-2.989 g的四水乙酸钴的甲醇溶液,继续搅拌0.5-2 h后室温老化10-40h;离心收集产物,用乙醇洗涤真空干燥得到紫色粉末;
(d)将步骤(c)得到的粉末在氮气氛围下750-1000 oC焙烧2-5 h得到黑色粉末,随后用水和乙醇溶液离心洗涤,真空干燥,即得碳化钨修饰的封装有钴纳米颗粒的碳纳米管。
所述的多酸为磷钨酸。化学式为H3PW12O40。
将上述制备的碳化钨修饰的封装有钴纳米颗粒的碳纳米管应用于催化氧化降解抗生素。具体操作步骤为:将碳化钨修饰的封装有钴纳米颗粒的碳纳米管加入土霉素溶液中,20-50oC搅拌反应0.5-3h;再加入过氧硫酸盐,20-50oC条件下搅拌反应0-20 min。
所述的土霉素溶液的浓度为20-200 ppm;pH值为3.0-11.0。
所述的碳化钨修饰的封装有钴纳米颗粒的碳纳米管的加入量为0.01-0.1mg/mL。
所述的过氧硫酸盐的加入量为0.002-0.2mg/mL。
所述的过氧硫酸盐为过硫酸氢钾。
本发明制备的碳化钨修饰的封装有钴纳米颗粒的碳纳米管,缠绕在一起的碳纳米管具有理想的介孔结构,不仅可以很好地阻止了纳米颗粒的聚集和流出,还可以暴露更多的活性位点,促进底物与活性位点接触发生反应,更大程度上提高了活性位点的利用率;该碳纳米管材料具有良好导电性,可以促进PMS活化过程中的电子转移,促进抗生素的氧化降解;合成的催化剂材料具有较大的比表面积和孔体积,使抗生素分子更容易扩散富集在活性位点附近,减少了反应中传质扩散的影响;碳化钨的掺入可以有效提高材料的电导率、孔体积和PMS吸附活性,促进了PMS活化过程中电子转移并促进SO4 ∙−和1O2的生成;碳化钨和钴的协同相互作用,促进两者之间的电子转移,可以有效促进PMS的活化与活性氧物种的生成。
本发明的方法制备过程简便、绿色高效、易于回收、底物易于与活性位点充分接触。得到的碳化钨修饰的封装有钴纳米颗粒的碳纳米管具有优异的孔结构、大的比表面积与规则的形貌,在催化过程中发挥重要的作用;并且催化剂可以通过外加磁场轻松分离,具有良好的循环回收稳定性。该材料不仅在土霉素降解中展现了优异的催化活性,在其他种类的抗生素降解中也展现了>85%的去除效率,为多酸基MOF衍生物在电催化、锂电池和超级电容器等领域的应用提供了可能。
附图说明
图1为实施例1的WC-Co@NCNTs催化剂的合成过程示意图。
图2为实施例1的WC-Co@NCNTs催化剂的SEM和TEM图。
图3为实施例1的WC-Co@NCNTs催化剂的XRD图。
图4为实施例1的WC-Co@NCNT催化氧化降解土霉素的效果图。
图5为实施例1的WC-Co@NCNT催化氧化降解土霉素的机理示意图。
具体实施方式
实施例1
制备WC-Co@NCNTs催化剂:
(1)将六水合硝酸锌(950 mg)溶解在甲醇(20 mL)溶液中,形成溶液A。将H3PW12O40(60 mg)溶解在水(3 mL)中形成溶液B。将溶液B加入到溶液A中,在室温下大力搅拌15分钟。然后将2-甲基咪唑(2 g)的甲醇(20 mL)溶液加入到上述溶液中,得到浑浊混合物。溶液在室温下老化24小时,离心收集沉淀,用水和甲醇洗涤,直到完全去除吸附在表面的PW12。
(2)上述得到的湿样,不进行干燥处理直接用于下一步的实验。首先加入2-甲基咪唑的甲醇溶液(1.314 g,80 mL)中,搅拌5 min后加入到四水乙酸钴的甲醇溶液(0.996 g,20 mL)中。搅拌1 h后,室温陈化24 h。离心收集产物,用乙醇溶液(3 × 30 mL)洗涤。得到的样品在真空60℃下干燥12小时,得到紫色粉末。
(3)将上述得到的紫色粉末置于管式炉中,然后在流动的氮气中以5 oC/min的速度加热至900 oC,恒温3小时,然后自然冷却至室温,将得到的黑色粉末用水(3×30毫升)和乙醇溶液(3×30毫升)分别离心洗涤,在60 oC真空下干燥12 h,得到碳化钨修饰的封装有钴纳米颗粒的碳纳米管,记为WC-Co@NCNTs。
催化氧化土霉素:
配制100ppm的土霉素溶液50 mL,用HCl调节pH至5.0,加入WC-Co@NCNTs催化剂3mg到上述溶液中,在室温条件下搅拌1小时后,加入过硫酸氢钾(加入后过硫酸氢钾浓度为1.0 mg/mL)后剧烈搅拌15分钟后,取3 ml反应液,经0.22 μm PTFE注射器过滤器过滤后立即进行高效液相色谱(HPLC)测试。测试得到的土霉素的去除率为99.5%。
外加磁场分离催化剂WC-Co@NCNTs,然后进行降解OTC的循环实验,重复操作10次后,其催化效果没有下降。
配置100ppm的土霉素溶液50 mL,用HCl调节pH至5.0,加入Co@NCNTs催化剂3 mg到上述溶液中,在室温条件下搅拌1小时后,加入过硫酸氢钾(加入后过硫酸氢钾浓度为1.0mg/mL)后剧烈搅拌15分钟后,取3 ml反应液,经0.22 μm PTFE注射器过滤器过滤后立即进行高效液相色谱(HPLC)测试。测试得到的土霉素的去除率为88.1%。
配置100ppm的土霉素溶液50 mL,用HCl调节pH至5.0,加入WC-Co@NCNTs催化剂3mg到上述溶液中,在室温条件下搅拌1小时后,加入双氧水(加入后H2O2浓度为1.0 mg/mL)后剧烈搅拌15分钟后,取3 ml反应液,经0.22 μm PTFE注射器过滤器过滤后立即进行高效液相色谱(HPLC)测试。测试得到的土霉素的去除率为93.0%。
Claims (10)
1.一种碳化钨修饰的封装有钴纳米颗粒的碳纳米管,其特征在于,所述的碳化钨修饰的封装有钴纳米颗粒的碳纳米管为缠绕在一起的碳纳米管结构,小尺寸的碳化钨均匀地负载在碳纳米管上,而钴纳米颗粒均匀地包裹在氮掺杂碳纳米管中,没有聚集。
2.一种碳化钨修饰的封装有钴纳米颗粒的碳纳米管的制备方法,其特征在于,所述的制备方法的具备操作为:将硝酸锌的甲醇溶液与多酸水溶液混合后加入2-甲基咪唑的甲醇溶液中,老化后离心洗涤,将沉淀再加入2-甲基咪唑的甲醇溶液中,然后加入乙酸钴的甲醇溶液,老化后离心洗涤,沉淀经真空干燥后在氮气氛围下高温焙烧,最后离心洗涤,真空干燥即得。
3.一种碳化钨修饰的封装有钴纳米颗粒的碳纳米管的制备方法,其特征在于,所述制备方法的具体步骤为:
(a)将0.950-1.90g六水合硝酸锌溶解在20-40 mL甲醇中形成溶液A,将30-120 mg多酸溶解在3-12 mL水中形成溶液B;将B溶液快速加入到A溶液中后室温下搅拌10-20分钟;
(b)将步骤(a)得到的混合溶液快速加入到20-40 mL含2-4 g的2-甲基咪唑的甲醇溶液中,得到浑浊混合物;溶液在室温下老化10-40小时,离心收集沉淀,用水和甲醇洗涤,直到完全去除吸附在表面的多酸;
(c)将步骤(b)得到的沉淀再加入80-240 mL含1.314-3.941 g的 2-甲基咪唑的甲醇溶液中,搅拌2-10 min后加入20-60 mL含0.996-2.989 g的四水乙酸钴的甲醇溶液,继续搅拌0.5-2 h后室温老化10-40h;离心收集产物,用乙醇洗涤真空干燥得到紫色粉末;
(d)将步骤(c)得到的粉末在氮气氛围下750-1000 oC焙烧2-5 h得到黑色粉末,随后用水和乙醇溶液离心洗涤,真空干燥,即得碳化钨修饰的封装有钴纳米颗粒的碳纳米管。
4.根据权利要求2或3所述的制备方法,其特征在于,所述的多酸为磷钨酸。
5.根据权利要求2或3所述的方法制备得到的碳化钨修饰的封装有钴纳米颗粒的碳纳米管催化氧化降解抗生素的应用。
6.根据权利要求5所述的应用,其特征在于,所述催化氧化降解抗生素的具体操作步骤为:将碳化钨修饰的封装有钴纳米颗粒的碳纳米管加入土霉素溶液中,20-50oC搅拌反应0.5-3h;再加入过氧硫酸盐,20-50oC条件下搅拌反应0-20 min。
7.根据权利要求6所述的应用,其特征在于,所述的土霉素溶液的浓度为20-200 ppm;pH值为3.0-11.0。
8.根据权利要求6所述的应用,其特征在于,所述的碳化钨修饰的封装有钴纳米颗粒的碳纳米管的加入量为0.01-0.1mg/mL。
9.根据权利要求6所述的应用,其特征在于,所述的过氧硫酸盐的加入量为0.002-0.2mg/mL。
10.根据权利要求6所述的应用,其特征在于,所述的过氧硫酸盐为过硫酸氢钾。
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