CN108144599A - 一种铋基复合光催化剂降解印染废水的处理工艺 - Google Patents
一种铋基复合光催化剂降解印染废水的处理工艺 Download PDFInfo
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Abstract
本发明公开了一种光催化降解印染废水的处理工艺,其采用的光催化剂为铋纳米团簇‑铋纳米粒子/TiO2/石墨烯复合光催化剂。该催化剂首先制得氧化石墨烯,然后在其片层上负载具有光催化活性的TiO2,再将铋纳米团簇修饰到负载有TiO2的石墨烯片层上,并对其进行光还原,该复合光催化剂针对印染废水具有高催化降解活性。本发明解决了现有技术中印染废水降解效率低的问题,适用于降解印染废水中的有机染料。
Description
技术领域
本发明涉及一种光催化降解印染废水的处理工艺,采用铋纳米团簇-铋纳米粒子/TiO2/石墨烯复合光催化剂,该光催化剂的组成和特殊结构使其具有高效的光催化降解活性,该处理工艺具有操作简单、成本低廉、降解效率高等优点。
背景技术
在纺织印染加工过程中,大量使用了污染环境和对人体有害的助剂,这些助剂大多以液体的形态排放,不可避免地进入水体环境,造成水体污染。如罗丹明B染料具有致癌和致突变性,含有罗丹明B的废水色度深、有机污染物含量高、生物降解性差,用常规的方法如物理吸附法、芬顿法等难以治理,导致污染水质长期恶化,严重危害水体环境和人类的健康,因此对这类废水的降解处理显得十分重要和紧迫。
近年来大量新型环保材料应运而生。纳米TiO2材料正是这种能够净化环境和高效利用太阳能的绿色功能材料。它不仅具有氧化能力强、优异的化学稳定性、能量消耗第、无后续二次污染等优点,而且还具有价格低廉、无毒无害、可长期使用等特点,因此近年来备受光催化科研工作者的青睐和关注,并且将其广泛应用于新能源领域如染料敏华太阳能电池、光解水产氢、微波吸附、光吸附、生物医药处理、光伏电池、光催化、锂离子电池等。
但半导体TiO2材料也存在一些严重的缺陷,例如纯TiO2光催化剂的光生电子空穴对的寿命短,光吸收范围窄和光转换效率低,限制了固体粉末催化剂的应用。所以需要对纳米二氧化钛的形貌进行修饰和改性研究,提高其对太阳光吸收效率已经迫在眉睫。因此,合理地运用太阳能和半导体氧化物制备氢能和有效地治理环境将受到人们越来越多的重视。
铋系光催化剂近年来受到广泛关注。近年来,具有特定结构及原子数目的超小型金属纳米团簇因其有别于普通纳米粒子的独特光电性质而被人们广泛关注。由于纳米团簇的粒径与费米波长或导带电子的德布罗意波长相近,量子效应使其具有类似金属有机分子的能级性质。这种离散的电子月前使得金属纳米团簇具有阶梯状光吸收、荧光发射等性质,因而作为光敏剂或助催化剂在光催化应用中具有良好前景。
石墨烯是一种能隙为零的半金属,在光催化领域,由于石墨烯具有独特的电子特性,极大的比表面积和较高的透明度使其成为合成复合光催化剂的理想载体,石墨烯的电子迁移率非常高,利用石墨烯对光催化剂进行改性,不但可以实现宽波段的光吸收,而且还能使电荷在转移过程中与催化剂更加匹配,提高其光催化性能;其次是石墨烯具有独特的二维面结构而具有较大的比表面积,当形成复合物时能够诱导产生对污染物强烈的吸附作用,有利于光催化降解的进一步进行。
发明内容
为了克服上述现有技术的缺点,本发明的目的在于提供一种光催化降解印染废水的处理工艺,其采用光催化的方式降解其中的染料,所采用的光催化剂为铋纳米团簇-铋纳米粒子/TiO2/石墨烯复合光催化剂。
实现本发明的技术方案:采用一种可见光降解的方式处理印染废水,并制备了一种具有优异光催化降解活性的铋纳米团簇-铋纳米粒子/TiO2/石墨烯复合光催化剂。
该可见光降解印染废水的处理工艺,包括如下步骤:
将铋纳米团簇-铋纳米粒子/TiO2/石墨烯复合光催化剂加入到一定浓度的印染废水中,充分搅拌并调节溶液pH=3.0~4.5,将混合溶液转入玻璃瓶中,黑暗环境中暗反应0.2~1h,然后在400W~700W的氙灯下进行常温、搅拌可见光催化降解反应0.5~2.5h。
该铋纳米团簇-铋纳米粒子/TiO2/石墨烯复合光催化剂的制备方法,具体是按以下步骤完成的:
一、氧化石墨烯的制备:
在200~350mg石墨粉、1.0~2.5g硝酸钠的混合溶液中,加入10~30mL 98wt%的浓硫酸,在<5℃的温度下搅拌,让其在烧杯中反应1.5~2.0 h;将高锰酸钾研磨成粉末,然后在0.5h内,于烧杯中加入1.5~2.5g粉末,在<5℃中反应1.5~3.0h;将烧杯放在恒温箱中升温到45~60℃,然后恒温1.5~2.5h,恒温结束后向烧杯中加入40~60mL去离子水,再将温度升至80~100℃,恒温10~30min;然后把烧杯中的溶液冷却到室内温度,加入80~120mL去离子水稀释,溶液变为亮黄色,之后再加入10~15mL 35wt%的过氧化氢溶液;然后进行过滤,将滤渣用300~400mL 5wt%的盐酸洗涤,用抽气泵抽干重复洗涤三次,然后再用去离子水洗涤三次,最后用透析袋透析两天,之后放入真空干燥箱内在80℃下干燥20h,最后研磨粉末得到氧化石墨烯;
二、石墨烯-纳米二氧化钛复合物的制备:
取上述制得的氧化石墨烯10~30mg,再加入10~30mL去离子水,利用超声波处理器在60W功率下超声处理30~60min,便可得到质量浓度为1mg/mL的氧化石墨烯溶液;将4.0~6.0g十六烷基三甲基溴化铵溶解在5~20mL正戊醇和40~65mL正己烷的混合溶液中,得到十六烷基三甲基氯化铵溶液;将十六烷基三甲基氯化铵溶液加入到氧化石墨烯溶液的同时,在室温下搅拌30min后,倒入高压反应釜中,放置在烘箱中,200℃恒温6h;将恒温后的产物放入旋转蒸发器中减压处理并沉淀,除去有机溶剂,得到的沉淀反复用去离子水和无水乙醇洗涤2~5次,除去表面活性剂和其他杂质,得到的最终产物放置在80℃条件下干燥1~4h,即得到石墨烯-纳米二氧化钛复合物;
三、铋纳米团簇-铋纳米粒子/TiO2/石墨烯复合光催化剂的制备:
将硝酸铋溶于水中,加还原型谷胱甘肽搅拌至无色,然后于70℃下回流24h,加入乙腈纯化后,离心、洗涤、干燥,得到固体铋纳米团簇,将所得固体铋纳米团簇重新分散到水中,得到铋纳米团簇溶液;将石墨烯-纳米二氧化钛复合物和铋纳米团簇溶液在弱酸性条件下混合搅拌4h,离心、洗涤、干燥,得到铋纳米团簇/TiO2/石墨烯;将其置于真空环境中、牺牲剂存在的条件下进行光照,得到所述铋纳米团簇-铋纳米粒子/TiO2/石墨烯复合光催化剂。
步骤三中所用硝酸铋与还原型谷胱甘肽的重量比为1:1;弱酸条件为pH值为4;所述石墨烯-纳米二氧化钛复合物和固体铋纳米团簇的重量比为100:2~100:8;所述光照的波长为300nm~800nm,照射时间为3~60h,以利用光照条件的不同使铋纳米团簇经不同程度的原位转化,得到具有不同粒径的铋纳米粒子,所述牺牲剂为乳酸。
碱性艳绿,呈绿色,易溶于乙醇,用于棉、蚕丝、腈纶、麻和纸张的染色,如果在水中存在会造成水体污染,因此选择碱性艳绿作为目标污染物来模拟评估催化材料的催化效率。
与现有技术相比,本发明具有以下优点:
1、与现有技术相比,本发明光催化处理印染废水的方法操作简单,反应条件容易控制、成本低廉,具有潜在的工业化应用前景;
2、本发明的光催化剂中,将铋纳米团簇-铋纳米粒子/TiO2嵌于具有极大比表面积和优异导电性的石墨烯的表面,促进光催化剂实现宽波段的光吸收,并且利用石墨烯片层优异的导电性使得光生电子能及时扩散、减缓了光生电子和空穴的复合,并且电荷在转移过程中与活性组分更加匹配,提高了光催化活性,进而提升了印染废水中污染物的降解效率;
3、本发明通过控制气氛、添加牺牲剂、照射波长及光照时间等条件,可以控制铋纳米团簇到铋纳米粒子的原位转化程度,使所得铋纳米团簇-铋纳米粒子/TiO2/石墨烯复合光催化剂具有不同的纳米铋粒径,从而实现对催化剂光催化活性及印染废水的降解效率的调控;
4、本发明复合光催化剂制备方法简单、绿色,无需高温高压,且能以太阳光能为能量源,有利于环境和能源的可持续发展。
具体实施方式
下面结合具体实施例对本发明作进一步阐述本发明的方案。
实施例1
一、氧化石墨烯的制备:
在350mg石墨粉、2.4g硝酸钠的混合溶液中,加入21mL 98wt%的浓硫酸,在<5℃的温度下搅拌,让其在烧杯中反应1.8h;将高锰酸钾研磨成粉末,然后在0.5h内,于烧杯中加入2.0g粉末,在<5℃中反应1.8h;将烧杯放在恒温箱中升温到48℃,然后恒温2.2h,恒温结束后向烧杯中加入45mL去离子水,再将温度升至85℃,恒温15min;然后把烧杯中的溶液冷却到室内温度,加入80mL去离子水稀释,溶液变为亮黄色,之后再加入13mL 35wt%的过氧化氢溶液;然后进行过滤,将滤渣用400mL 5wt%的盐酸洗涤,用抽气泵抽干重复洗涤3次,然后再用去离子水洗涤3次,最后用透析袋透析2天,之后放入真空干燥箱内在80℃下干燥20h,最后研磨粉末得到氧化石墨烯;
二、石墨烯-纳米二氧化钛复合物的制备:
取上述制得的氧化石墨烯25mg,再加入25mL去离子水,利用超声波处理器在60W功率下超声处理40min,便可得到质量浓度为1mg/mL的氧化石墨烯溶液;将6.0g十六烷基三甲基溴化铵溶解在15mL正戊醇和55mL正己烷的混合溶液中,得到十六烷基三甲基氯化铵溶液;将十六烷基三甲基氯化铵溶液加入到氧化石墨烯溶液的同时,在室温下搅拌30min后,倒入高压反应釜中,放置在烘箱中,200℃恒温6h;将恒温后的产物放入旋转蒸发器中减压处理并沉淀,除去有机溶剂,得到的沉淀反复用去离子水和无水乙醇洗涤3次,除去表面活性剂和其他杂质,得到的最终产物放置在80℃条件下干燥1.5h,即得到石墨烯-纳米二氧化钛复合物,记为样品A;
三、铋纳米团簇-铋纳米粒子/TiO2/石墨烯复合光催化剂的制备:
将硝酸铋溶于水中,加还原型谷胱甘肽搅拌至无色,然后于70℃下回流24h,加入乙腈纯化后,离心、洗涤、干燥,得到固体铋纳米团簇,将所得固体铋纳米团簇重新分散到水中,得到铋纳米团簇溶液;按石墨烯-纳米二氧化钛复合物A与铋纳米团簇的质量比100:5将石墨烯-纳米二氧化钛复合物和铋纳米团簇溶液在pH值为4的条件下混合搅拌4h,离心、洗涤、干燥,得到铋纳米团簇/TiO2/石墨烯,记为样品B;将其置于真空环境中、乳酸存在的条件下进行5h的光照还原,得到所述铋纳米团簇-铋纳米粒子/TiO2/石墨烯复合光催化剂,记为样品C。
具体的测试方法如下:配制三份200mL浓度均为8mg/mL的碱性艳绿溶液作为印染废水的模型,分别向其中加入0.01g实施例1中制备的石墨烯-纳米二氧化钛复合物A、未经光照还原的铋纳米团簇/TiO2/石墨烯B和经过光照还原的铋纳米团簇-铋纳米粒子/TiO2/石墨烯复合光催化剂C,充分搅拌并分别调节溶液pH值为4.0,随后将混合溶液分别装入玻璃瓶中,黑暗环境中各自暗反应0.5h,然后在500W的氙灯照射下,考察不同时间催化剂对污染废水的净化程度,具体数据参见下表1:
表1. 不同样品对碱性艳绿的降解活性
由表1中的数据分析可知,相比未经过铋纳米团簇修饰的石墨烯-纳米二氧化钛复合物,经过铋纳米团簇修饰但未经光照还原的铋纳米团簇/TiO2/石墨烯对碱性艳绿的降解活性有了大幅提升,这是由于铋纳米团簇均匀分散在负载有纳米二氧化钛的石墨烯片层上,增加了光生电子的传导及光生电子与空穴的分离效率,而经过光还原的铋纳米团簇-铋纳米粒子/TiO2/石墨烯复合光催化剂的光催化活性在同等条件下均有了进一步提升,能够高效地完成对含有染料的印染废水的高效处理。
以上所述,仅为本发明较佳的具体实施方式,但本发明的保护范围并不局限于此,任何熟悉本技术领域的技术人员在本发明揭露的技术范围内,根据本发明的技术方案及其发明构思加以等同替换或改变,都应涵盖在本发明的保护范围之内。
Claims (10)
1.一种可见光降解印染废水的处理工艺,其特征在于,包括如下步骤:将铋纳米团簇-铋纳米粒子/TiO2/石墨烯复合光催化剂加入到一定浓度的印染废水中,充分搅拌并调节溶液pH=3.0~4.5,将混合溶液转入玻璃瓶中,黑暗环境中暗反应0.2~1h,然后在400W~700W的氙灯下进行常温、搅拌可见光催化降解反应0.5~2.5h。
2.如权利要求1所述的可见光降解印染废水的处理工艺,其特征在于,所述印染废水中含有碱性艳绿。
3.如权利要求1所述的可见光降解印染废水的处理工艺,其特征在于,所述的铋纳米团簇-铋纳米粒子/TiO2/石墨烯复合光催化剂的制备方法包括如下步骤:在200~350mg石墨粉、1.0~2.5g硝酸钠的混合溶液中,加入10~30mL 98wt%的浓硫酸,在<5℃的温度下搅拌,让其在烧杯中反应1.5~2.0 h;将高锰酸钾研磨成粉末,然后在0.5h内,于烧杯中加入1.5~2.5g粉末,在<5℃中反应1.5~3.0h;将烧杯放在恒温箱中升温到45~60℃,然后恒温1.5~2.5h,恒温结束后向烧杯中加入40~60mL去离子水,再将温度升至80~100℃,恒温10~30min;然后把烧杯中的溶液冷却到室内温度,加入80~120mL去离子水稀释,溶液变为亮黄色,之后再加入10~15mL 35wt%的过氧化氢溶液;然后进行过滤,将滤渣用300~400mL5wt%的盐酸洗涤,用抽气泵抽干重复洗涤三次,然后再用去离子水洗涤三次,最后用透析袋透析两天,之后放入真空干燥箱内在80℃下干燥20h,最后研磨粉末得到氧化石墨烯。
4.如权利要求1所述的可见光降解印染废水的处理工艺,其特征在于,所述的铋纳米团簇-铋纳米粒子/TiO2/石墨烯复合光催化剂的制备方法包括如下步骤:取上述制得的氧化石墨烯10~30mg,再加入10~30mL去离子水,利用超声波处理器在60W功率下超声处理30~60min,便可得到质量浓度为1mg/mL的氧化石墨烯溶液;将4.0~6.0g十六烷基三甲基溴化铵溶解在5~20mL正戊醇和40~65mL正己烷的混合溶液中,得到十六烷基三甲基氯化铵溶液;将十六烷基三甲基氯化铵溶液加入到氧化石墨烯溶液的同时,在室温下搅拌30min后,倒入高压反应釜中,放置在烘箱中,200℃恒温6h;将恒温后的产物放入旋转蒸发器中减压处理并沉淀,除去有机溶剂,得到的沉淀反复用去离子水和无水乙醇洗涤2~5次,除去表面活性剂和其他杂质,得到的最终产物放置在80℃条件下干燥1~4h,即得到石墨烯-纳米二氧化钛复合物。
5.如权利要求1所述的可见光降解印染废水的处理工艺,其特征在于,所述的铋纳米团簇-铋纳米粒子/TiO2/石墨烯复合光催化剂的制备方法包括如下步骤:将硝酸铋溶于水中,加还原型谷胱甘肽搅拌至无色,然后于70℃下回流24h,加入乙腈纯化后,离心、洗涤、干燥,得到固体铋纳米团簇,将所得固体铋纳米团簇重新分散到水中,得到铋纳米团簇溶液;将石墨烯-纳米二氧化钛复合物和铋纳米团簇溶液在弱酸性条件下混合搅拌4h,离心、洗涤、干燥,得到铋纳米团簇/TiO2/石墨烯;将其置于真空环境中、牺牲剂存在的条件下进行光照,得到所述铋纳米团簇-铋纳米粒子/TiO2/石墨烯复合光催化剂。
6.如权利要求5所述的可见光降解印染废水的处理工艺,其特征在于,硝酸铋与还原型谷胱甘肽的重量比为1:1。
7.如权利要求5所述的可见光降解印染废水的处理工艺,其特征在于,弱酸条件为pH值为4。
8.如权利要求5所述的可见光降解印染废水的处理工艺,其特征在于,所述石墨烯-纳米二氧化钛复合物和固体铋纳米团簇的重量比为100:2~100:8。
9.如权利要求5所述的可见光降解印染废水的处理工艺,其特征在于,所述光照的波长为300nm~800nm,照射时间为3~60h,以利用光照条件的不同使铋纳米团簇经不同程度的原位转化,得到具有不同粒径的铋纳米粒子。
10.如权利要求5所述的可见光降解印染废水的处理工艺,其特征在于,所述牺牲剂为乳酸。
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CN107469804A (zh) * | 2016-06-08 | 2017-12-15 | 中国科学院金属研究所 | 一种纳米颗粒铋负载的二氧化钛基复合光催化材料及其制备方法和应用 |
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CN109225283A (zh) * | 2018-10-23 | 2019-01-18 | 河北师范大学 | 石墨烯/二氧化钛/碘氧化铋三元复合物及其制备方法和应用 |
CN109317131A (zh) * | 2018-10-23 | 2019-02-12 | 重庆工商大学 | 一种硅藻土基复合材料及其制备方法 |
CN111468178A (zh) * | 2020-05-18 | 2020-07-31 | 山东师范大学 | 一种金属改性zsm-5分子筛催化剂及其制备方法与应用 |
CN111468178B (zh) * | 2020-05-18 | 2022-07-12 | 山东师范大学 | 一种金属改性zsm-5分子筛催化剂及其制备方法与应用 |
CN115976876A (zh) * | 2022-12-09 | 2023-04-18 | 华中科技大学 | 一种负载铋纳米粒子的石墨烯纸、制备及重金属检测应用 |
CN115976876B (zh) * | 2022-12-09 | 2024-02-02 | 华中科技大学 | 一种负载铋纳米粒子的石墨烯纸、制备及重金属检测应用 |
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