CN113908855A - 一种负载型多孔光催化纤维膜的制备方法 - Google Patents
一种负载型多孔光催化纤维膜的制备方法 Download PDFInfo
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Abstract
本发明公开了一种负载型多孔光催化纤维膜的制备方法,其特征在于首先采用微波合成的方法制备硫化铟锡可见光催化剂,然后把此催化剂混合于聚合物溶液中,采用静电纺丝的方法制备出光催化纤维膜,最后采用洗脱致孔剂的方法,制备出多孔光催化纤维膜。本发明一方面采用微波合成的方法制备硫化铟锡可见光催化剂,缩短了反应时间,提高了效率;另一方面采用静电纺丝的技术,制备出负载催化剂可循环利用的光催化纤维膜,解决了粉体催化剂难以回收分离的问题;此外,采用洗脱致孔剂的方法,制备出多孔光催化纤维膜,增大了比表面积,提高了催化剂对污染物的降解效率。
Description
技术领域
本发明涉及一种负载型多孔光催化纤维膜的制备方法,属于光催化降解领域。
背景技术
光催化技术是指利用光源照射半导体材料并迅速产生光生电子和空穴,与吸附在材料表面的水分子、氧气或污染物发生氧化还原的一种光化学反应。自从Fujishima andHonda报道了TiO2光催化电解水实验之后,光催化技术受到了人们广泛的关注。但以TiO2为代表的紫外光响应半导体光催化剂禁带宽度大,只能利用太阳光中仅占5%的紫外光,为了使其具备可见光响应能力,需通过非金属元素掺杂、负载贵金属、染料敏化、构建异质结等策略来减小催化剂的带隙能量、拓宽光谱响应范围。相比于金属氧化物,金属硫化物具有较负的导带位置和较窄的禁带宽度,因此成为了常见的可见光响应的光催化剂,如CdS。但二元硫化物光腐蚀严重、可见光响应范围窄、无法进行能带位置调控等不足,在实际应用中受到限制。三元金属硫化物具有优越的导电性,良好的稳定性,具有较窄的禁带宽度,可见光响应,部分材料的光响应区域可延伸至红外光,因此在产氢、还原CO2、降解污染物、杀菌、还原Cr(VI)等领域具有广阔的前景。硫化铟锡是一种新兴的三元硫族化合物,归属于立方尖晶石型结构,禁带宽度约为2.1 eV,是一种可见光响应的半导体。其导带位置为-0.76 eV,负于超氧自由基的氧化还原电势(·O2 -/O2 = -0.33 eV vs. NHE),因此在产氢、还原CO2、治理环境等方面具有潜在的应用价值。
中国专利CN108404959B描述了一种棒状g-C3N4@SnIn4S8复合光催化剂及其制备方法。该方法首先使用高温煅烧的方法制备了g-C3N4,然后使用水热合成的方法制备了g-C3N4@SnIn4S8粉体复合光催化剂,实现了可见光催化降解盐酸四环素。中国专利CN111250110A描述了一种可见光响应SnIn4S8/TiO2核壳型复合光催化剂的制备方法。该方法采用溶剂热的方法制备了SnIn4S8/TiO2粉体核壳型复合光催化剂,实现了可见光下降解甲基橙、盐酸四环素或光还原Cr(VI)。中国专利CN112295421A描述了一种表面粘接式用于光催化的TiO2/PVDF超滤膜,该方法制备的膜,在紫外灯的照射下,具有光催化和分离的效果。
目前大多数研究者是采用水热(溶剂热)合成的方法制备硫化铟锡催化剂,但此方法耗时较长,往往需要十几小时才能完成;在催化剂的状态方面,目前研究最多的就是粉体催化剂,但它存在难以回收、难以循环利用的问题。
发明内容
本发明的目的是针对现有技术的不足而提供一种负载型多孔光催化纤维膜的制备方法。其特征是使用微波合成的方法制备硫化铟锡可见光催化剂,然后将此催化剂混合于聚合物溶液中,采用静电纺丝法制备出光催化纤维膜,最后采用洗脱致孔剂的方法,制备出多孔光催化纤维膜。微波合成是通过电介质分子将吸收的电磁波转变为热能的一种加热方式,属于体加热方式,温度升高快,并且里外温度相同。它具有诸多优点,如加热速度快;加热均匀,里外同时加热;热能利用率高,节省能源,无公害;反应灵敏;产品质量高等。与传统的加热方法相比,反应速率大大加快,因此倍受人们的青睐。静电纺丝是一种简单的、易操作的、应用比较广泛的技术,它是借助强电场将聚合物分子的溶液喷射出超细纤维的一种技术。它可以快速把聚合物材料制备出聚合物纤维,纤维尺寸可调、制备效率高,所得纤维膜孔隙率高,比表面积大。本发明首先使用微波合成的方法制备硫化铟锡可见光粉体催化剂;然后把此可见光催化剂混合于高分子聚合物溶液中,采用静电纺丝的方法制备出光催化纤维膜;最后洗脱致孔剂,制备出多孔光催化纤维膜。本发明一方面采用微波合成的方法,缩短了反应时间,提高了效率;另一方面采用静电纺丝的技术,解决了粉体催化剂难以循环利用的问题;此外,采用洗脱致孔剂的方法,制备出多孔光催化纤维膜,提高了对污染物的催化效率,为污染物的降解提供了新的思路。
本发明提供的一种负载型多孔光催化纤维膜的制备方法,其特征在于包括以下步骤,所用物料的份数均为重量份数:
(1)硫化铟锡可见光催化剂的制备:将1-5份锡盐,4-18份铟盐,加入到40-80份去离子水中,搅拌20~30 min,加入0.2-0.6份表面活性剂,2-22份的硫化物,持续搅拌20~30min后,将该溶液转入100 mL 聚四氟乙烯内衬的微波反应罐中,密封后置于微波合成仪,在150~180 ℃的条件下,反应5~60 min,待仪器程序降温到55 ℃时,取出反应罐,产物离心分离后,分别用去离子水和无水乙醇反复清洗2-3次,在60-80 ℃条件下,真空干燥6-12个小时;
(2)静电纺丝法制备光催化纤维膜:取1份的高分子聚合物,0.5-2份致孔剂聚乙烯吡咯烷酮,分散在10-20 份二甲基甲酰胺中,室温搅拌12~48 h后,加入0.1-0.5份的上述制备的硫化铟锡可见光催化剂,持续搅拌1~4 h,制得均匀的静电纺丝溶液;将上述溶液转移到静电纺丝装置中,连接喷丝头和高压电源,控制挤出速度,收集器转速,以及喷丝头至收集器之间的距离,最终在收集器上得到光催化纤维膜;
(3)多孔光催化纤维膜的制备:将上述制备的静电纺丝膜,置于去离子水中,60 ℃搅拌6~12 h,洗脱致孔剂,然后分别用去离子水和无水乙醇反复清洗2-3次,在50~80 ℃的条件下,真空干燥,密封包装待用;
(4)光催化降解甲基橙:将上述制备的多孔光催化纤维膜1-2份置于在50 份 10-20 mg/L的甲基橙溶液中,避光静置吸附过夜;然后置于300 W的氙灯下,进行可见光照射,并进行吸光度的测试,经计算该多孔光催化纤维膜降解甲基橙的效率为90%以上。
所述的一种负载型多孔光催化纤维膜的制备方法,其特征在于铟盐为氯化铟、硫酸铟、硝酸铟等无机铟盐中的一种。
所述的一种负载型多孔光催化纤维膜的制备方法,其特征在于表面活性剂为十二烷基苯磺酸钠、十二烷基硫酸钠、溴化十六烷三甲基铵中的一种。
所述的一种负载型多孔光催化纤维膜的制备方法,其特征在于所述的硫化物为硫代乙酰胺、硫脲、赖氨酸中的一种。
所述的一种负载型多孔光催化纤维膜的制备方法,其特征在于所述的高分子聚合物为聚偏二氟乙烯、聚丙烯腈中的一种或组合。
所述的一种负载型多孔光催化纤维膜的制备方法,其特征在于高压电源的电压为15~25 kV,喷丝头至收集器之间的距离为15~20 cm,挤出速度0.1 mL/h~0.3 mL/h,收集器转速100~300 r/min。
本发明与现有技术相比,具有以下积极效果:
(1)采用微波合成技术,与其他方法相比,反应时间较短,操作简单;
(2)采用静电纺丝技术,可将催化剂负载于纤维膜中,解决了粉体材料难以回收、难以循环利用的问题,大大提高了催化剂的利用率;
(3)采用洗脱致孔剂的方法,可将致孔剂从光催化纤维膜上洗脱下来,增大了膜的比表面积,提高了光催化效率。
附图说明
图1是本发明所述的一种负载型光催化纤维膜的扫描电子显微镜(SEM)图。
图2是本发明所述的一种负载型多孔光催化纤维膜的扫描电子显微镜(SEM)图。
具体实施方式
下面通过实施例对本发明进行具体的描述,有必要指出的是以下实施例只是用于对本发明进行进一步的说明,不能理解为对本发明保护范围的限制,该领域的技术熟练人员可根据上述发明的内容做出一些非本质的改进和调整,仍属于本发明的保护范围。
实施例1:
(1)硫化铟锡可见光催化剂的制备:将1份氯化锡,4份氯化铟,加入到40份去离子水中,搅拌20 min后,加入0.2份十二烷基苯磺酸钠,2份硫代乙酰胺,持续搅拌20 min后,将该溶液转入100 mL聚四氟乙烯内衬的微波反应罐中,密封后置于微波合成仪,在150 ℃的条件下,反应5 min,待仪器程序降温到55 ℃时,取出反应罐,产物离心分离后,分别用去离子水和无水乙醇反复清洗2次,在60 ℃条件下,真空干燥12个小时;
(2)静电纺丝法制备光催化纤维膜:取1份聚偏二氟乙烯,0.5份聚乙烯吡咯烷酮,分散在10份二甲基甲酰胺中,室温搅拌12 h后,加入0.1份的上述制备的硫化铟锡可见光催化剂,持续搅拌1 h,制得均匀的静电纺丝溶液;将上述溶液转移到静电纺丝装置中,连接喷丝头和高压电源,控制挤出速度,收集器转速,以及喷丝头至收集器之间的距离,最终在收集器上得到光催化纤维膜;
(3)多孔光催化纤维膜的制备:将上述制备的光催化纤维膜,置于去离子水中,在60℃的条件下搅拌6 h,洗脱致孔剂,然后分别用去离子水和无水乙醇反复清洗2次,在60℃的条件下,真空干燥,密封包装待用;
(4)光催化降解甲基橙:将上述制备的多孔聚合物纤维膜1份置于在50 份 10 mg/L的甲基橙溶液中,避光静置吸附过夜;然后置于300 W的氙灯下,进行可见光照射,并进行吸光度的测试,经计算该多孔光催化纤维膜降解甲基橙的效率为90%以上。
实施例2:
(1)硫化铟锡可见光催化剂的制备:将2份氯化锡,12份硫酸铟,加入到50份去离子水中,搅拌20 min后,加入0.4份十二烷基硫酸钠,4份硫脲,持续搅拌30 min后,将该溶液转入100 mL 聚四氟乙烯内衬的微波反应罐中,密封后置于微波合成仪,在160 ℃的条件下,反应15 min,待仪器程序降温到55 ℃时,取出反应罐,产物离心分离后,分别用去离子水和无水乙醇清洗3次,在70 ℃条件下,真空干燥10个小时;
(2)静电纺丝法制备光催化纤维膜:取0.8份聚偏二氟乙烯,0.2份聚丙烯腈,1份聚乙烯吡咯烷酮,分散在15份二甲基甲酰胺中,室温搅拌20 h后,加入0.2份的上述制备的硫化铟锡可见光催化剂,持续搅拌2 h,制得均匀的静电纺丝溶液;将上述溶液转移到静电纺丝装置中,连接喷丝头和高压电源,控制挤出速度,收集器转速,以及喷丝头至收集器之间的距离,最终在收集器上得到光催化纤维膜;
(3)多孔光催化纤维膜的制备:将上述制备的聚合物纤维膜,置于去离子水中,60℃搅拌10 h,洗脱致孔剂,然后分别用去离子水和无水乙醇清洗3次,在70 ℃的条件下,真空干燥,密封包装待用;
(4)光催化降解甲基橙:将上述制备的多孔光催化纤维膜2份置于在50 份 10 mg/L的甲基橙溶液中,避光静置吸附过夜;然后置于300 W的氙灯下,进行可见光照射,并进行吸光度的测试,经计算该多孔光催化纤维膜降解甲基橙的效率为90%以上。
实施例3:
(1)硫化铟锡可见光催化剂的制备:将5份氯化锡,18份硝酸铟,加入到80份去离子水中,搅拌溶解30 min后,加入0.6份溴化十六烷三甲基铵,22份赖氨酸,持续搅拌30 min后,将该溶液转入100 mL 聚四氟乙烯内衬的微波反应罐中,密封后置于微波合成仪,在180℃的条件下,反应60 min,待仪器程序降温到55 ℃时,取出反应罐,产物离心分离后,分别用去离子水和无水乙醇反复清洗3次,在80 ℃条件下,真空干燥6个小时;
(2)静电纺丝法制备光催化纤维膜:取1份聚偏二氟乙烯,2份聚乙烯吡咯烷酮,分散在20份二甲基甲酰胺中,室温搅拌48 h后,加入0.5份的上述制备的硫化铟锡可见光催化剂,持续搅拌4 h,制得均匀的静电纺丝溶液;将上述溶液转移到静电纺丝装置中,连接喷丝头和高压电源,控制挤出速度,收集器转速,以及喷丝头至收集器之间的距离,最终在收集器上得到光催化纤维膜;
(3)多孔光催化纤维膜的制备:将上述制备的静电纺丝膜,置于去离子水中,60℃搅拌12 h,洗脱致孔剂,然后分别用去离子水和无水乙醇反复清洗,在80 ℃的条件下,真空干燥,密封包装待用;
(4)光催化降解甲基橙:将上述制备的多孔聚合物纤维膜2份置于在50 mL 20 mg/L的甲基橙溶液中,避光静置吸附过夜;然后置于300 W的氙灯下,进行可见光照射,并进行吸光度的测试,经计算该多孔光催化纤维膜降解甲基橙的效率为90%以上。
采用本专利技术制备的负载型多孔光催化纤维膜,与其他方法相比,一方面反应时间较短,操作简单;另一方面此纤维膜可用于降解甲基橙等有机物,达到自清洁的作用;此外,此纤维膜可回收重复利用,提高了使用价值,节约了资源。
Claims (6)
1.一种负载型多孔光催化纤维膜的制备方法,其特征在于包括以下步骤,所用物料的份数均为重量份数:
(1)硫化铟锡可见光催化剂的制备:将1-5份锡盐,4-18份铟盐,加入到40-80份去离子水中,搅拌20~30 min后,加入0.2-0.6份表面活性剂,2-22份的硫化物,持续搅拌20~30 min后,将该溶液转入100 mL 聚四氟乙烯内衬的微波反应罐中,密封后置于微波合成仪,在150~180 ℃的条件下,反应5~60 min,待仪器程序降温到55 ℃时,取出反应罐,产物离心分离后,分别用去离子水和无水乙醇反复清洗2-3次,在60-80 ℃条件下,真空干燥6-12个小时;
(2)静电纺丝法制备光催化纤维膜:取1份高分子聚合物,0.5-2份致孔剂聚乙烯吡咯烷酮,分散在10-20 份二甲基甲酰胺中,室温搅拌12~48 h后,加入0.1-0.5份的上述制备的硫化铟锡可见光催化剂,持续搅拌1~4 h,制得均匀的静电纺丝溶液;将上述溶液转移到静电纺丝装置中,连接喷丝头和高压电源,控制挤出速度,收集器转速,以及喷丝头至收集器之间的距离,最终在收集器上得到光催化纤维膜;
(3)多孔光催化纤维膜的制备:将上述制备的光催化纤维膜,置于去离子水中,60 ℃搅拌6~12 h,洗脱致孔剂聚乙烯吡咯烷酮,然后分别用去离子水和无水乙醇反复清洗2-3次,在50~80 ℃的条件下,真空干燥,密封包装待用;
(4)光催化降解甲基橙:将上述制备的多孔光催化纤维膜1-2份置于在50 份 10-20mg/L的甲基橙溶液中,避光静置吸附过夜;然后置于300 W的氙灯下,进行可见光照射,并进行吸光度的测试,经计算该多孔光催化纤维膜降解甲基橙的效率为90%以上。
2.根据权利要求1所述的一种负载型多孔光催化纤维膜的制备方法,其特征在于铟盐为氯化铟、硫酸铟、硝酸铟等无机铟盐中的一种。
3.根据权利要求1所述的一种负载型多孔光催化纤维膜的制备方法,其特征在于表面活性剂为十二烷基苯磺酸钠、十二烷基硫酸钠、溴化十六烷三甲基铵中的一种。
4.根据权利要求1所述的一种负载型多孔光催化纤维膜的制备方法,其特征在于所述的硫化物为硫代乙酰胺、硫脲、赖氨酸中的一种。
5.根据权利要求1所述的一种负载型多孔光催化纤维膜的制备方法,其特征在于所述的聚合物为聚偏二氟乙烯、聚丙烯腈中的一种或组合。
6.根据权利要求1所述的一种负载型多孔光催化纤维膜的制备方法,其特征在于高压电源的电压为15~25 kV,喷丝头至收集器之间的距离为15~20 cm,挤出速度0.1 mL/h~0.3mL/h,收集器转速100~300 r/min。
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