CN113134393B - 一种光催化双氯芬酸净化膜及其制备方法 - Google Patents
一种光催化双氯芬酸净化膜及其制备方法 Download PDFInfo
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Abstract
本发明属于污水处理技术领域，公开了一种光催化双氯芬酸净化膜及其制备方法。该制备方法包括：利用熔融电纺制备高弹掺杂聚氨酯纳米纤维膜，并在外表面沉积金属‑有机框架材料MOFs‑YVZr，得到光降解催化膜。该膜在可见光照射下能够高效催化水中双氯芬酸的降解，且适用于不同pH环境。
Description
技术领域
本发明属于污水处理技术领域，具体涉及一种光催化双氯芬酸净化膜及其制备方法。
背景技术
随着全球人口的不断增长，药品和个人护理产品的需求不断增长，人们开始关注其对环境的负面影响。非甾体抗炎药作为个人护理产品中的一类组分，通常用于减轻疼痛和炎症。作为几乎所有药房的非处方药，非甾体抗炎药被广泛使用。因此，它们在环境中的存在不能被忽视，因为它有可能污染饮用水。
双氯芬酸是最受欢迎的非甾体抗炎药之一，可制成片剂、缓释胶囊、注射剂、软膏剂、乳胶剂、栓剂、滴眼剂等口服或局部使用。尽管双氯芬酸具有止痛药的功效，但对地表水来说是一种环境风险，而且被认为是急性毒性最高的非甾体抗炎药之一。有研究指出该药物一旦释放到周围环境，会对活生物体产生负面影响。该药物能通过多种机制对细菌、藻类、秃鹫种群和淡水鱼产生毒性作用。此外，这种有机微量污染物也有可能加剧饮用水系统中颗粒污染物的毒性，这可能会对人类造成更多的健康风险。
为了解决上述问题，双氯芬酸必须在它积累并对人类构成严重威胁之前将其从水体中清除。因此，人们提出了许多有效去除水中双氯芬酸的处理工艺，如吸附法、Fenton氧化降解法、臭氧氧化法和光催化法等。理想情况下，污染物应该通过转化成更小的分子来完全去除。然而，这通常会带来各种挑战，如对高氧化剂的要求、高成本以及存在不利或有毒的副产品。因此，在广泛研究的策略中，吸附法被认为是最常用的方法之一，特别是在饮用水和废水处理方面，因为它具有效率高、工艺简单、成本低、适用于低污染物浓度等优点。目前，人们已经研究了各种潜在的吸附剂，包括沸石、活性炭、石墨烯氧化物、介孔二氧化硅和金属有机框架(MOFs)。在潜在吸附剂中，MOFs具有表面积大、孔径可调性、可定制孔的功能化等优点，被认为是最有前途的吸附剂之一。尽管有这些优势，但需要仔细选择用于双氯芬酸去除的MOFs，特别是它们在水环境中的结构稳定性。这是因为许多MOFs在水环境中不稳定，导致结构降解。另外，仅仅是吸附，当达到吸附饱和时，吸附剂还需更换，增加了操作复杂性和成本。
发明内容
有鉴于此，本发明的目的在于提供一种光催化双氯芬酸净化膜及其制备方法，该膜在可见光照射下能够高效催化水中双氯芬酸的降解。
为了解决上述技术问题，本发明提供了一种光催化双氯芬酸净化膜的制备方法，包括如下步骤：
S1.将钒酸钇和硫酸锆钾三水合物充分混合后煅烧，然后与苯六甲酸三酸酐一同加入到二甲基乙酰胺和甲酸的混合溶剂中，，超声处理至完全溶解，得到金属-有机框架材料MOFs-YVZr合成液；
S2.将氧化钇稳定的氧化锆粉末和热塑性聚氨酯弹性体混合后研磨，得到熔体，将所述熔体真空脱气后通过熔融静电纺丝得到高弹掺杂聚氨酯纳米纤维膜；
S3.取所述高弹掺杂聚氨酯纳米纤维膜，在超声波浴中用丙酮清洗，真空干燥后，浸入所述金属-有机框架材料MOFs-YVZr合成液中，之后悬挂在烘箱中烘干，并冷却至室温，先后用二甲基甲酰胺和甲醇洗涤，真空干燥得光催化双氯芬酸净化膜。
优选的，所述步骤S1中，钒酸钇、硫酸锆钾三水合物、苯六甲酸三酸酐、二甲基乙酰胺和甲酸混合溶剂的比例为(0.163-0.245)g:(0.823-1.235)g:(1.152-1.728)g:25mL。
优选的，所述步骤S1中，煅烧温度为1100-1500℃，煅烧时间为18-24h。
优选的，所述步骤S1中，二甲基乙酰胺和甲酸的混合溶剂中二甲基乙酰胺和甲酸的体积比为1:1-3。
优选的，所述步骤S2中，氧化钇稳定的氧化锆粉末、热塑性聚氨酯弹性体的比例为1:3-5。
优选的，所述步骤S2中，研磨的温度为230-250℃，研磨时间为24-48h。
优选的，所述步骤S2中，熔融静电纺丝条件为：熔体温度230-250℃，纺丝电压20-25kV，流速1.0-1.5mL/h，接收距离20-25cm，环境温度为0-15℃，相对湿度为20-30％。
优选的，所述步骤S3中，高弹掺杂聚氨酯纳米纤维膜、金属-有机框架材料MOFs-YVZr合成液的比例为1g:(50-100)mL。
优选的，所述步骤S3中，烘干温度为100-120℃，烘干时间为12-48h。
本发明还提供了一种上述制备方法制备得到的光催化双氯芬酸净化膜。
与现有技术相比，本发明具有以下有益效果：
1)本发明构建稳定而高效光催化的MOFs：本发明利用钒酸钇、硫酸锆钾煅烧形成以钒、锆、钇多金属离子中心的MOFs无机结构单元。钒和锆金属离子的高价通过强的Lewis酸碱相互作用形成了一个牢固的MOFs结构，钇在高温煅烧时形成钇氧化物进一步稳定了MOFs结构。而且，锆掺杂的钒酸钇作为半导体催化剂还具有较强的可见光诱导氧化还原能力，在λ>420nm的光照下能够利用环境中的氧对还原性底物进行氧化。钒、锆、钇、钾多金属离子中心的MOFs无机结构单元具有窄带隙，有利于将电子从低能价带激发到高能导带上，形成电子-空穴对。电子还原水中的氧，空穴则迁移到表面与双氯芬酸结合，从而使双氯芬酸氧化。
2)利用氧化钇稳定的氧化锆粉末掺杂的热塑性聚氨酯弹性体进行熔融电纺得到的纳米纤维膜，能够适应在不同pH下对双氯芬酸的降解。而且，用氧化钇稳定的氧化锆粉末掺杂活化了纤维表面，有利于MOFs-YVZr沉积生长。
附图说明
图1是实施例1所制得的光催化双氯芬酸净化膜的扫描电镜图。
具体实施方式
为了进一步理解本发明，下面结合实施例对本发明优选实施方案进行描述，但是应当理解，这些描述只是为了进一步说明本发明的特征和优点，而不是对本发明权利要求的限制。
实施例1
一种光催化双氯芬酸净化膜及其制备方法，包括如下步骤：
1.将0.204g钒酸钇和1.029g硫酸锆钾三水合物充分混合后在1200℃下煅烧20h，然后与1.44g苯六甲酸三酸酐一同加入到25mL二甲基乙酰胺和甲酸的体积比为2:1的混合溶剂中，将溶液超声处理至完全溶解，得到金属-有机框架材料MOFs-YVZr合成液。
2.将40g氧化钇稳定的氧化锆粉末和160g热塑性聚氨酯弹性体加入行星研磨机中在240℃下研磨36h后得熔体，将熔体真空脱气后在熔体温度为245℃，纺丝电压为22kV，流速为1.2mL/h，接收距离为22cm，环境温度为10℃，相对湿度为25％的条件下，通过熔融静电纺丝得到高弹掺杂聚氨酯纳米纤维膜。
3.取1g步骤2制得的高弹掺杂聚氨酯纳米纤维膜，在超声波浴中用丙酮清洗，真空干燥后，浸入80mL步骤1制得的金属-有机框架材料MOFs-YVZr合成液中，之后悬挂在110℃烘箱中干燥30h，并冷却至室温，先后用二甲基甲酰胺和甲醇洗涤，真空干燥得光催化双氯芬酸净化膜A(图1)。
实施例2
一种光催化双氯芬酸净化膜及其制备方法，包括如下步骤：
1.将0.163g钒酸钇和0.823g硫酸锆钾三水合物充分混合后在1100℃下煅烧18h，然后与1.152g苯六甲酸三酸酐一同加入到25mL二甲基乙酰胺和甲酸的体积比为3:1的混合溶剂中，将溶液超声处理至完全溶解，得到金属-有机框架材料MOFs-YVZr合成液。
2.将40g氧化钇稳定的氧化锆粉末和120g热塑性聚氨酯弹性体加入行星研磨机中在230℃下研磨24h后得熔体，将熔体真空脱气后在熔体温度为250℃，纺丝电压为20kV，流速为1.0mL/h，接收距离为20cm，环境温度为0℃，相对湿度为30％的条件下，通过熔融静电纺丝得到高弹掺杂聚氨酯纳米纤维膜。
3.取1g步骤2制得的高弹掺杂聚氨酯纳米纤维膜，在超声波浴中用丙酮清洗，真空干燥后，浸入100mL步骤1制得的金属-有机框架材料MOFs-YVZr合成液中，之后悬挂在120℃烘箱中干燥48h，并冷却至室温，先后用二甲基甲酰胺和甲醇洗涤，真空干燥得光催化双氯芬酸净化膜B。
实施例3
一种光催化双氯芬酸净化膜及其制备方法，包括如下步骤：
1.将0.245g钒酸钇和1.235g硫酸锆钾三水合物充分混合后在1500℃下煅烧24h，然后与1.728g苯六甲酸三酸酐一同加入到25mL二甲基乙酰胺和甲酸的体积比为1:1的混合溶剂中，将溶液超声处理至完全溶解，得到金属-有机框架材料MOFs-YVZr合成液。
2.将40g氧化钇稳定的氧化锆粉末和200g热塑性聚氨酯弹性体加入行星研磨机中在250℃下研磨48h后得熔体，将熔体真空脱气后在熔体温度为230℃，纺丝电压为25kV，流速为1.5mL/h，接收距离为25cm，环境温度为15℃，相对湿度为20％的条件下，通过熔融静电纺丝得到高弹掺杂聚氨酯纳米纤维膜。
3.取1g步骤2制得的高弹掺杂聚氨酯纳米纤维膜，在超声波浴中用丙酮清洗，真空干燥后，浸入50mL步骤1制得的金属-有机框架材料MOFs-YVZr合成液中，之后悬挂在100℃烘箱中干燥12h，并冷却至室温，先后用二甲基甲酰胺和甲醇洗涤，真空干燥得光催化双氯芬酸净化膜C。
对比例1
一种纳米纤维膜及其制备方法，包括如下步骤：
1.将1.029g硫酸锆钾三水合物与1.44g苯六甲酸三酸酐一同加入到25mL二甲基乙酰胺和甲酸的体积比为2:1的混合溶剂中，将溶液超声处理至完全溶解，得到金属-有机框架材料MOFs-YVZr合成液。
2.将40g氧化钇稳定的氧化锆粉末和160g热塑性聚氨酯弹性体加入行星研磨机中在240℃下研磨36h后得熔体，将熔体真空脱气后在熔体温度为245℃，纺丝电压为22kV，流速为1.2mL/h，接收距离为22cm，环境温度为10℃，相对湿度为25％的条件下，通过熔融静电纺丝得到高弹掺杂聚氨酯纳米纤维膜。
3.取1g步骤2制得的高弹掺杂聚氨酯纳米纤维膜，在超声波浴中用丙酮清洗，真空干燥后，浸入80mL步骤1制得的金属-有机框架材料MOFs-YVZr合成液中，之后悬挂在110℃烘箱中干燥30h，并冷却至室温，先后用二甲基甲酰胺和甲醇洗涤，真空干燥得纳米纤维膜D。
对比例2
一种纳米纤维膜及其制备方法，包括如下步骤：
1.将0.204g钒酸钇与1.44g苯六甲酸三酸酐一同加入到25mL二甲基乙酰胺和甲酸的体积比为2:1的混合溶剂中，将溶液超声处理至完全溶解，得到金属-有机框架材料MOFs-YVZr合成液。
2.将40g氧化钇稳定的氧化锆粉末和160g热塑性聚氨酯弹性体加入行星研磨机中在240℃下研磨36h后得熔体，将熔体真空脱气后在熔体温度为245℃，纺丝电压为22kV，流速为1.2mL/h，接收距离为22cm，环境温度为10℃，相对湿度为25％的条件下，通过熔融静电纺丝得到高弹掺杂聚氨酯纳米纤维膜。
3.取1g步骤2制得的高弹掺杂聚氨酯纳米纤维膜，在超声波浴中用丙酮清洗，真空干燥后，浸入80mL步骤1制得的金属-有机框架材料MOFs-YVZr合成液中，之后悬挂在110℃烘箱中干燥30h，并冷却至室温，先后用二甲基甲酰胺和甲醇洗涤，真空干燥得纳米纤维膜E。
对比例3
一种纳米纤维膜及其制备方法，包括如下步骤：
1.将0.204g钒酸钇和1.029g硫酸锆钾三水合物充分混合后在1200℃下煅烧20h，然后与1.44g苯六甲酸三酸酐一同加入到25mL二甲基乙酰胺和甲酸的体积比为2:1的混合溶剂中，将溶液超声处理至完全溶解，得到金属-有机框架材料MOFs-YVZr合成液。
2.将160g热塑性聚氨酯弹性体加入行星研磨机中在240℃下研磨36h后得熔体，将熔体真空脱气后在熔体温度为245℃，纺丝电压为22kV，流速为1.2mL/h，接收距离为22cm，环境温度为10℃，相对湿度为25％的条件下，通过熔融静电纺丝得到高弹掺杂聚氨酯纳米纤维膜。
3.取1g步骤2制得的高弹掺杂聚氨酯纳米纤维膜，在超声波浴中用丙酮清洗，真空干燥后，浸入80mL步骤1制得的金属-有机框架材料MOFs-YVZr合成液中，之后悬挂在110℃烘箱中干燥30h，并冷却至室温，先后用二甲基甲酰胺和甲醇洗涤，真空干燥得纳米纤维膜F。
双氯酚酸降解实验
取实施例1-3和对比例1-3的纳米纤维膜样品，剪成15cm×20cm长方形，卷绕后装入层析柱内。配制1mg/mL双氯芬酸钠溶液，用5mol/L盐酸溶液或者氢氧化钠溶液调pH至2.0、4.0、6.0、8.0、10.0。在白天用自然光照和夜晚用日光灯照射条件下，以0.2mL/min的流速将配制的双氯芬酸钠溶液流经层析柱，收集24h，48h和72h流出液，用紫外-可见分光光度计在277nm处测定流出液中的双氯芬酸的浓度，结果如表1所示。
表1双氯酚酸降解实验结果
由表1可知，本发明实施例制备的光催化双氯芬酸净化膜在各pH值的水中能很好地吸附降解双氯芬酸，表现出良好的稳定性。但是对比例制备的纳米纤维膜效果较差。钒酸钇和硫酸锆钾三水合物高温煅烧是形成MOFs半导体催化核心的关键，对比例1和2中不能合成MOFs的核心，因此仅具有微弱的吸附效果且随着时间的积累，吸附达到饱和，流出液中双氯芬酸浓度较大。氧化钇稳定的氧化锆粉末在聚氨酯纳米纤维中的掺入对于金属-有机框架材料MOFs-YVZr的表面沉积至关重要，对比例3制备的纳米纤维由于缺乏氧化钇稳定的氧化锆粉末，无法在其表面有效沉积MOFs-YVZr，所以达不到实施例表现的优异催化降解效果。
本发明提供了一种光催化双氯芬酸净化膜及其制备方法的思路及方法，具体实现该技术方案的方法和途径很多，以上所述仅是本发明的优选实施方式，应当指出，对于本技术领域的普通技术人员来说，在不脱离本发明原理的前提下，还可以做出若干改进和润饰，这些改进和润饰也应视为本发明的保护范围。本实施例中未明确的各组成部分均可用现有技术加以实现。
Claims (10)
1.一种光催化双氯芬酸净化膜的制备方法，其特征在于，包括如下步骤：
S1.将钒酸钇和硫酸锆钾三水合物充分混合后煅烧，然后与苯六甲酸三酸酐一同加入到二甲基乙酰胺和甲酸的混合溶剂中，超声处理至完全溶解，得到金属-有机框架材料MOFs-YVZr合成液；
S2.将氧化钇稳定的氧化锆粉末和热塑性聚氨酯弹性体混合后研磨，得到熔体，将所述熔体真空脱气后通过熔融静电纺丝得到高弹掺杂聚氨酯纳米纤维膜；
S3.取所述高弹掺杂聚氨酯纳米纤维膜，在超声波浴中用丙酮清洗，真空干燥后，浸入所述金属-有机框架材料MOFs-YVZr合成液中，烘干后冷却至室温，先后用二甲基甲酰胺和甲醇洗涤，真空干燥得光催化双氯芬酸净化膜。
2.根据权利要求1所述的制备方法，其特征在于，所述步骤S1中，钒酸钇、硫酸锆钾三水合物、苯六甲酸三酸酐、二甲基乙酰胺和甲酸混合溶剂的比例为(0.163-0.245)g:(0.823-1.235)g:(1.152-1.728)g:25mL。
3.根据权利要求1所述的制备方法，其特征在于，所述步骤S1中，煅烧温度为1100-1500℃，煅烧时间为18-24h。
4.根据权利要求1所述的制备方法，其特征在于，所述步骤S1中，二甲基乙酰胺和甲酸的混合溶剂中二甲基乙酰胺和甲酸的体积比为1-1:3。
5.根据权利要求1所述的制备方法，其特征在于，所述步骤S2中，氧化钇稳定的氧化锆粉末与热塑性聚氨酯弹性体的比例为1:3-5。
6.根据权利要求1所述的制备方法，其特征在于，所述步骤S2中，研磨的温度为230-250℃，研磨时间为24-48h。
7.根据权利要求1所述的制备方法，其特征在于，所述步骤S2中，熔融静电纺丝条件为：熔体温度230-250℃，纺丝电压20-25kV，流速1.0-1.5mL/h，接收距离20-25cm，环境温度为0-15℃，相对湿度为20-30％。
8.根据权利要求1所述的制备方法，其特征在于，所述步骤S3中，高弹掺杂聚氨酯纳米纤维膜、金属-有机框架材料MOFs-YVZr合成液的比例为1g:(50-100)mL。
9.根据权利要求1所述的制备方法，其特征在于，所述步骤S3中，烘干温度为100-120℃，烘干时间为12-48h。
10.根据权利要求1～9任一项所述制备方法制备得到的光催化双氯芬酸净化膜。
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| CN108842304A (zh) * | 2018-08-10 | 2018-11-20 | 西安工程大学 | 一种多孔负载型静电纺纳米光催化纤维膜及其制备方法 |
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| CN109695096A (zh) * | 2018-12-27 | 2019-04-30 | 南京工业大学 | 一种一步法制备空气净化用多级孔纳米纤维膜的方法 |
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| EP3456867A1 (en) * | 2017-09-19 | 2019-03-20 | Tungaloy Corporation | Coated drill |
| CN108842304A (zh) * | 2018-08-10 | 2018-11-20 | 西安工程大学 | 一种多孔负载型静电纺纳米光催化纤维膜及其制备方法 |
| CN109465004A (zh) * | 2018-12-22 | 2019-03-15 | 赵妙妙 | 柔性钇稳定氧化锆纳米纤维膜的制备方法 |
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