CN108745420A - 一种可降解废水中酚类污染物的纳米二氧化钛光催化剂 - Google Patents
一种可降解废水中酚类污染物的纳米二氧化钛光催化剂 Download PDFInfo
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Abstract
本发明属于多相光催化氧化技术降解废水中有机污染物技术领域,具体涉及一种可降解废水中酚类污染物的纳米二氧化钛光催化剂,其制备方法包括含氧化石墨粉的复合材料的制备、纳米二氧化钛颗粒的加工以及纳米二氧化钛光催化剂合成。本发明相比现有技术具有以下优点:通过有效复合使其相互作用形成了掺杂能级,增加了有效的电荷分离,减少了二氧化钛的能带宽度,增加了光的透射率,进而增加光能利用率,促使催化剂光能利用率的提高,能避免光腐蚀现象,能够快速吸附污染物,催化剂较大的比表面积以及高空隙结构也会吸附更多的污染物分子,提高了对废水中酚类污染物的降解效果。
Description
技术领域
本发明属于多相光催化氧化技术降解废水中有机污染物技术领域,具体涉及一种可降解废水中酚类污染物的纳米二氧化钛光催化剂。
背景技术
工业废水和城市居民生活用水是我国水污染的主要污染源一直,随着近年工业的飞速发展和经济的腾飞,含有高浓度的有机废水污染日益严重,有机废水主要来源于工业生产的纺织染料、表面活性剂、防污化合物等,医院产生的抗生素、类固醇等药物和农业生产中农药、除草剂等,然而传统的自然吸附、反向渗透、凝固和生物降解能力远远不够,只是将污染物转移到另一个地方或另一个阶段,极易造成二次污染,对人类健康构成严重威胁,酚类污染物作为一个典型的代表,若长期饮用被酚污染的水会出现慢性中毒,引起头痛、头晕、疲劳、失眠、耳鸣、贫血以及神经系统病症,甚至会导致致癌,所以含酚废水的处理显得日益重要;目前,对含酚废水的处理方法主要有物理、化学、生化及组合技术,但均存在一些缺陷;多相光催化氧化技术已被证实能够妥善处理废水中不同的持久性有机污染物移出或矿化成CO2和H2O,TiO2作为一种典型的氧化物半导体材料,具有活性高、光稳定性好、对人体无毒、成本低、应用工艺流程简单、操作条件容易控制、无二次污染等优越性能而成为最具潜力的绿色催化剂,但由于其具有较宽的能带宽度导致光能利用率低,另一方面,TiO2导带上光生电子和价带上光生空穴复合率高导致光电子效率低;针对TiO2存在的缺陷,现有技术通常通过贵金属、过渡金属及过渡金属氧化物的掺杂改善,但贵金属资源稀缺、价格昂贵限制了其使用范围。
发明内容
本发明的目的是针对现有的问题,提供了一种可降解废水中酚类污染物的纳米二氧化钛光催化剂。
本发明是通过以下技术方案实现的:一种可降解废水中酚类污染物的纳米二氧化钛光催化剂,其制备方法包括以下内容:
(1)含氧化石墨粉的复合材料的制备:将壳聚糖溶于水中制成质量浓度为3-4g/100mL的壳聚糖水溶液,然后加入相当于壳聚糖水溶液重量8-10%的醋酸,搅拌40-60分钟得到凝胶,然后在温度为85-95℃的条件下处理6-8小时,自然冷却后得到凝胶溶液;然后在凝胶溶液中加入相当于其重量2.5-3.5%的氧化石墨粉、0.2-0.8%的钠基化粘土,升温至60℃,以800-1000转/分钟的速度搅拌3-4小时,自然冷却后,在温度为46-48℃、湿度为50-60%的条件下干燥处理6小时,然后在氮气氛围中,在80-90℃、1.4-1.6MPa的条件下反应4小时,然后研磨成粉,过80目筛备用;
(2)纳米二氧化钛颗粒的加工:将纳米二氧化钛置于质量浓度为2-4%的尿素溶液中,磁力搅拌6-10分钟,取出后在管式炉中通入氮气保护,在温度为500-600℃的条件下煅烧1-2小时即得;
(3)纳米二氧化钛光催化剂合成:将含氧化石墨粉的复合材料、纳米二氧化钛颗粒、直径为500-700nm的二氧化铈纳米纤维、甲胺以重量比4-6:1-2:0.1-0.5:600-800的重量配比混合,在温度为160-180℃的条件下搅拌反应3小时,停止加热,过滤得到产物,用蒸馏水冲洗4-6分钟后得到
具体的,所述步骤(1)在制备凝胶过程中,周期性的使用超声震荡,超声振荡频率为80-100Hz,震荡周期为30秒。
具体的,所述氧化石墨粉由改进的Hummers法制备,其粒径为2-18μm,硫含量小于1%,氧含量为49-50%。
具体的,所述钠基化粘土的粘土为蒙脱土、凹凸棒土、蛭石中的任意一种,钠基化粘土的CEC为80-100mmol/100g。
具体的,所述步骤(2)中煅烧温度的升温速度为40℃/分钟;所述纳米二氧化钛颗粒的粒径为20-80nm。
所述直径为500-700nm的二氧化铈纳米纤维采用静电纺丝法合成,其合成方法参照董相廷课题组的制备方法,先合成PVP/硝酸铈复合纤维,然后在温度为950-1050℃的条件下煅烧,形成表面为多孔形貌的纤维结构,具有很高的表面积和较小的孔径,能够有助于增加光的透射率,同时能够有助于吸附更多的污染物分子。
石墨烯不仅价格低廉,而且具有片层结构和良好的热稳定性和导电性,氧化石墨烯含有羟基、环氧基、羰基、羧基等多种官能团,还能被小分子插层或剥离,能有效改善复合材料的性能,本发明中通过与壳聚糖在特定条件下复合,所得到的复合材料具有热稳定性,能够与二氧化钛纳米颗粒有效结合,形成有介孔结构的复合材料,缩短电荷载体扩散到催化剂表面活性位点的距离,使二氧化钛纳米颗粒表面的光生电子能快速转移到复合材料,进而能够有效提高光电效率。
本发明相比现有技术具有以下优点:通过有效复合使其相互作用形成了掺杂能级,增加了有效的电荷分离,减少了二氧化钛的能带宽度,增加了光的透射率,进而增加光能利用率,促使催化剂光能利用率的提高,同时由于催化剂表面的氢氧基增加,能够加快电荷载体向催化剂表面扩散,还能避免光腐蚀现象,进而能够快速吸附污染物,催化剂较大的比表面积以及高空隙结构也会吸附更多的污染物分子,使光催化效果增加,进而提高了对废水中酚类污染物的降解效果。
具体实施方式
实施例 1
一种可降解废水中酚类污染物的纳米二氧化钛光催化剂,其制备方法包括以下内容:
(1)含氧化石墨粉的复合材料的制备:将壳聚糖溶于水中制成质量浓度为3.5g/100mL的壳聚糖水溶液,然后加入相当于壳聚糖水溶液重量9%的醋酸,搅拌50分钟得到凝胶,然后在温度为90℃的条件下处理7小时,自然冷却后得到凝胶溶液;然后在凝胶溶液中加入相当于其重量3%的氧化石墨粉、0.5%的钠基化粘土,升温至60℃,以900转/分钟的速度搅拌3.5小时,自然冷却后,在温度为47℃、湿度为55%的条件下干燥处理6小时,然后在氮气氛围中,在85℃、1.5MPa的条件下反应4小时,然后研磨成粉,过80目筛备用;
(2)纳米二氧化钛颗粒的加工:将纳米二氧化钛置于质量浓度为3%的尿素溶液中,磁力搅拌8分钟,取出后在管式炉中通入氮气保护,在温度为550℃的条件下煅烧1.5小时即得;
(3)纳米二氧化钛光催化剂合成:将含氧化石墨粉的复合材料、纳米二氧化钛颗粒、直径为500-700nm的二氧化铈纳米纤维、甲胺以重量比5:1.5:0.3:700的重量配比混合,在温度为170℃的条件下搅拌反应3小时,停止加热,过滤得到产物,用蒸馏水冲洗5分钟后得到
具体的,所述步骤(1)在制备凝胶过程中,周期性的使用超声震荡,超声振荡频率为90Hz,震荡周期为30秒;所述氧化石墨粉由改进的Hummers法制备,其粒径为2-18μm,硫含量小于1%,氧含量为49-50%;所述钠基化粘土的粘土为蒙脱土,钠基化粘土的CEC为80-100mmol/100g;所述步骤(2)中煅烧温度的升温速度为40℃/分钟;所述纳米二氧化钛颗粒的粒径为20-80nm。
实施例 2
一种可降解废水中酚类污染物的纳米二氧化钛光催化剂,其制备方法包括以下内容:
(1)含氧化石墨粉的复合材料的制备:将壳聚糖溶于水中制成质量浓度为4g/100mL的壳聚糖水溶液,然后加入相当于壳聚糖水溶液重量8%的醋酸,搅拌60分钟得到凝胶,然后在温度为85℃的条件下处理6小时,自然冷却后得到凝胶溶液;然后在凝胶溶液中加入相当于其重量2.5%的氧化石墨粉、0.8%的钠基化粘土,升温至60℃,以1000转/分钟的速度搅拌4小时,自然冷却后,在温度为46℃、湿度为60%的条件下干燥处理6小时,然后在氮气氛围中,在90℃、1.4MPa的条件下反应4小时,然后研磨成粉,过80目筛备用;
(2)纳米二氧化钛颗粒的加工:将纳米二氧化钛置于质量浓度为4%的尿素溶液中,磁力搅拌10分钟,取出后在管式炉中通入氮气保护,在温度为500℃的条件下煅烧2小时即得;
(3)纳米二氧化钛光催化剂合成:将含氧化石墨粉的复合材料、纳米二氧化钛颗粒、直径为500-700nm的二氧化铈纳米纤维、甲胺以重量比4:2:0.5:800的重量配比混合,在温度为160℃的条件下搅拌反应3小时,停止加热,过滤得到产物,用蒸馏水冲洗4分钟后得到
具体的,所述步骤(1)在制备凝胶过程中,周期性的使用超声震荡,超声振荡频率为100Hz,震荡周期为30秒;所述氧化石墨粉由改进的Hummers法制备,其粒径为2-18μm,硫含量小于1%,氧含量为49-50%;所述钠基化粘土的粘土为凹凸棒土,钠基化粘土的CEC为80-100mmol/100g;所述步骤(2)中煅烧温度的升温速度为40℃/分钟;所述纳米二氧化钛颗粒的粒径为20-80nm。
实施例 3
一种可降解废水中酚类污染物的纳米二氧化钛光催化剂,其制备方法包括以下内容:
(1)含氧化石墨粉的复合材料的制备:将壳聚糖溶于水中制成质量浓度为3g/100mL的壳聚糖水溶液,然后加入相当于壳聚糖水溶液重量10%的醋酸,搅拌40分钟得到凝胶,然后在温度为95℃的条件下处理8小时,自然冷却后得到凝胶溶液;然后在凝胶溶液中加入相当于其重量3.5%的氧化石墨粉、0.2%的钠基化粘土,升温至60℃,以800转/分钟的速度搅拌3小时,自然冷却后,在温度为48℃、湿度为50%的条件下干燥处理6小时,然后在氮气氛围中,在80℃、1.6MPa的条件下反应4小时,然后研磨成粉,过80目筛备用;
(2)纳米二氧化钛颗粒的加工:将纳米二氧化钛置于质量浓度为2%的尿素溶液中,磁力搅拌6分钟,取出后在管式炉中通入氮气保护,在温度为600℃的条件下煅烧1小时即得;
(3)纳米二氧化钛光催化剂合成:将含氧化石墨粉的复合材料、纳米二氧化钛颗粒、直径为500-700nm的二氧化铈纳米纤维、甲胺以重量比6:1:0.1:600的重量配比混合,在温度为180℃的条件下搅拌反应3小时,停止加热,过滤得到产物,用蒸馏水冲洗6分钟后得到
具体的,所述步骤(1)在制备凝胶过程中,周期性的使用超声震荡,超声振荡频率为80Hz,震荡周期为30秒;所述氧化石墨粉由改进的Hummers法制备,其粒径为2-18μm,硫含量小于1%,氧含量为49-50%;所述钠基化粘土的粘土为蛭石,钠基化粘土的CEC为80-100mmol/100g;所述步骤(2)中煅烧温度的升温速度为40℃/分钟;所述纳米二氧化钛颗粒的粒径为20-80nm。
设置对照组1,纳米二氧化钛直接作催化剂;设置对照组2,将实施例1中含氧化石墨粉的复合材料制备过程中的钠基化粘土去掉,其余内容不变;设置对照组3,将实施例1中步骤(2)去掉,直接选用等量的粒径为20-80nm的纳米二氧化钛颗粒替代,其余内容不变;设置对照组4,将实施例1中直径为500-700nm的二氧化铈纳米纤维去掉,其余内容不变;设置对照组5,将实施例1中直径为500-700nm的二氧化铈纳米纤维替换成直径为200nm的二氧化铈纳米纤维(具体方法为将其制备过程中的煅烧温度降至400℃),其余内容不变;
样品光催化性能测试实验,具体实验步骤:按照分组每组称取0.2g于100mL的试管中,加入25mL蒸馏水,超声10分钟使其均匀分散,取5mL上清液,作为检测参比溶液,加入质量浓度为0.001mol/L的45mL苯酚溶液,在磁力搅拌器下充分混合后在黑暗环境中处理30分钟,得到混合溶液,然后取5mL混合溶液作为紫外检测0min的降解液,最后,开启250W、λmax=561nm的超高压汞灯,进行光解实验,分别在光照60min、120min、180min、240min、300min、360min时刻取反应液,离心后取上清液用于紫外检测,研究悬浮液中苯酚的降解情况,苯酚降解率的计算公式为η ( 苯酚降解率) = (c0-ct) /c0×100%,此处将60min、180min、360min时刻取出反应液的检测结果,得到以下表格:
表1
降解率(%) | 60min | 180min | 360min |
实施例1 | 28.5 | 63.7 | 98.5 |
实施例2 | 28.2 | 62.9 | 97.8 |
实施例3 | 28.4 | 63.5 | 98.3 |
对照组1 | 6.8 | 11.3 | 19.3 |
对照组2 | 26.5 | 59.4 | 96.1 |
对照组3 | 22.8 | 57.6 | 93.5 |
对照组4 | 13.7 | 50.9 | 85.4 |
对照组5 | 21.5 | 56.2 | 96.2 |
通过表1中数据可以看出,本发明中相比直接使用纳米二氧化钛颗粒的光催化作用增强,能够更快速、有效的降解废水中酚类污染物,适于推广使用。
Claims (7)
1.一种可降解废水中酚类污染物的纳米二氧化钛光催化剂,其特征在于,其制备方法包括以下内容:
(1)含氧化石墨粉的复合材料的制备:将壳聚糖溶于水中制成质量浓度为3-4g/100mL的壳聚糖水溶液,然后加入相当于壳聚糖水溶液重量8-10%的醋酸,搅拌40-60分钟得到凝胶,然后在温度为85-95℃的条件下处理6-8小时,自然冷却后得到凝胶溶液;然后在凝胶溶液中加入相当于其重量2.5-3.5%的氧化石墨粉、0.2-0.8%的钠基化粘土,升温至60℃,以800-1000转/分钟的速度搅拌3-4小时,自然冷却后,在温度为46-48℃、湿度为50-60%的条件下干燥处理6小时,然后在氮气氛围中,在80-90℃、1.4-1.6MPa的条件下反应4小时,然后研磨成粉,过80目筛备用;
(2)纳米二氧化钛颗粒的加工:将纳米二氧化钛置于质量浓度为2-4%的尿素溶液中,磁力搅拌6-10分钟,取出后在管式炉中通入氮气保护,在温度为500-600℃的条件下煅烧1-2小时即得;
(3)纳米二氧化钛光催化剂合成:将含氧化石墨粉的复合材料、纳米二氧化钛颗粒、直径为500-700nm的二氧化铈纳米纤维、甲胺以重量比4-6:1-2:0.1-0.5:600-800的重量配比混合,在温度为160-180℃的条件下搅拌反应3小时,停止加热,过滤得到产物,用蒸馏水冲洗4-6分钟后得到。
2.如权利要求1所述一种可降解废水中酚类污染物的纳米二氧化钛光催化剂,其特征在于,所述步骤(1)在制备凝胶过程中,周期性的使用超声震荡,超声振荡频率为80-100Hz,震荡周期为30秒。
3.如权利要求1所述一种可降解废水中酚类污染物的纳米二氧化钛光催化剂,其特征在于,所述氧化石墨粉由改进的Hummers法制备,其粒径为2-18μm,硫含量小于1%,氧含量为49-50%。
4.如权利要求1所述一种可降解废水中酚类污染物的纳米二氧化钛光催化剂,其特征在于,所述钠基化粘土的粘土为蒙脱土、凹凸棒土、蛭石中的任意一种,钠基化粘土的CEC为80-100mmol/100g。
5.如权利要求1所述一种可降解废水中酚类污染物的纳米二氧化钛光催化剂,其特征在于,所述步骤(2)中煅烧温度的升温速度为40℃/分钟。
6.如权利要求1所述一种可降解废水中酚类污染物的纳米二氧化钛光催化剂,其特征在于,所述直径为500-700nm的二氧化铈纳米纤维采用静电纺丝法合成。
7.如权利要求1所述一种可降解废水中酚类污染物的纳米二氧化钛光催化剂,其特征在于,所述纳米二氧化钛颗粒的粒径为20-80nm。
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