CN106582812A - 一种金属锌卟啉轴向功能化二氧化钛的复合光催化剂及其制备方法 - Google Patents
一种金属锌卟啉轴向功能化二氧化钛的复合光催化剂及其制备方法 Download PDFInfo
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- FUTVBRXUIKZACV-UHFFFAOYSA-J zinc;3-[18-(2-carboxylatoethyl)-8,13-bis(ethenyl)-3,7,12,17-tetramethylporphyrin-21,24-diid-2-yl]propanoate Chemical compound [Zn+2].[N-]1C2=C(C)C(CCC([O-])=O)=C1C=C([N-]1)C(CCC([O-])=O)=C(C)C1=CC(C(C)=C1C=C)=NC1=CC(C(C)=C1C=C)=NC1=C2 FUTVBRXUIKZACV-UHFFFAOYSA-J 0.000 claims description 43
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Abstract
本发明属于降解染料废水污染物的光催化材料技术领域,公开了一种金属锌卟啉轴向功能化二氧化钛的复合光催化剂及其制备方法。合成步骤包括:将锐钛矿型二氧化钛与金属锌卟啉在有机溶剂中按比例混合,进行加热回流,然后经过滤、洗涤及干燥后得金属锌卟啉敏化的二氧化钛光催化剂。本发明合成方法简单,所制备复合材料性质稳定、光催化活性高,可作为光催化处理染料废水污染物的环境净化材料。
Description
技术领域
本发明属于降解染料废水污染物的光催化材料技术领域,具体涉及一种新型“有机-无机”金属锌卟啉轴向功能化二氧化钛的复合光催化剂及其制备方法。
背景技术
随着社会经济的快速发展及工业化进程的加快,环境污染问题日益严峻,大量化工原料的消耗和排放,使人们周围的生活环境日益恶化。其中,有机染料污水的色度深、浓度高、毒性大,难于在自然条件下降解,已成为水处理领域的一大难题。因此,开发一种简便有效的方法来降解有机污染物是人类社会急需解决的问题。近年来,光催化降解水中有机污染物为废水的治理提供了新的思路。光催化法反应条件温和、设备简单、二次污染小、易于操作控制、运行成本低,是一种非常有前途的水污染治理技术,越来越受到人们广泛的关注。
目前光催化研究中,研究最多的、同时也被视为最佳材料的是二氧化钛,由于其具有光催化活性高、耐光腐蚀性强、稳定性好、环境友好、价格相对低廉、对人体无毒等优点,在信息、能源、环境等新兴领域表现出广泛的应用前景。但是,二氧化钛自身也缺点,其带隙宽、光谱响应范围窄,只能吸收波长小于387.5nm的紫外光,对太阳光能的利用率仅为4%。如何拓展二氧化钛在可见光区的光谱响应范围,使之具有可见光活性,并提高其对太阳光的总利用效率是制约二氧化钛光催化技术的关键问题。
利用金属卟啉作为敏化剂敏化二氧化钛是提高其可见光催化效果的有效途径之一。将金属卟啉与二氧化钛形成复合物,在光照的条件下就能够使金属卟啉产生的电子由敏化剂输送至二氧化钛半导体的导带,从而使复合物体系的激发波长拓宽至可见光范围,使得对可见光和近红外区的利用成为可能。
发明内容
本发明的目的在于研制一类新型的用于降解染料废水污染物的可见光光催化复合光催化剂,以提高光催化材料对可见光及近红外区域的光谱利用率。
本发明提供了一种金属锌卟啉轴向功能化二氧化钛复合光催化剂的制备方法,步骤简单,容易实现,制备的复合光催化剂光催化性能好。
一种金属锌卟啉轴向功能化二氧化钛的复合光催化剂,由二氧化钛和金属锌卟啉组成,所述金属锌卟啉轴向修饰在异烟酸共价功能化的二氧化钛表面;所述锌卟啉轴向功能化二氧化钛的复合光催化剂的结构为:
一种金属锌卟啉轴向功能化二氧化钛的复合光催化剂的制备方法,包括如下步骤:
步骤A1:将二氧化钛超声分散在极性有机溶剂A中,分散均匀后,再加入异烟酸和N,N’-二环己基碳二酰亚胺,进行酯化反应,反应结束后,将反应物经冷却、过滤、洗涤,干燥,得到白色粉末状产物,即为异烟酸共价功能化的二氧化钛;
步骤A2:超声下,将步骤A1所得产物和金属锌卟啉超声溶解在极性有机溶剂B中,氮气保护下,进行功能化反应,反应结束后,将反应物经冷却、过滤、洗涤,干燥,得到锌卟啉轴向功能化二氧化钛的复合光催化剂ZnTpp/TiO2。
所述制备方法中,步骤A1的极性有机溶剂A为四氢呋喃,步骤A2的极性有机溶剂B为N,N’-二甲基甲酰胺。
所述二氧化钛的晶型为锐钛矿型;
步骤A1中,所述二氧化钛、异烟酸和N,N’-二环己基碳二酰亚胺的质量比为3:10:2;
步骤A2中,步骤A1所的产物和锌卟啉的质量比为8:5。
所述制备方法中超声时间均为半小时。
步骤A1酯化反应的温度为66℃,反应时间为3天;步骤A2功能化反应的温度为80℃,反应时间为2天。
所述过滤为将反应液用0.45μm的尼龙膜进行过滤;所述洗涤为分别用去离子水和二氯甲烷洗涤;所述干燥为真空室温下干燥12小时。
本发明所述的一种金属锌卟啉轴向功能化二氧化钛的复合光催化剂的用途,其特征在于,将所述复合催化剂作为光催化处理染料废水污染物,例如罗丹明B。
本发明的优点是:
(1)本发明的制备方法简单,反应条件温和,过程易于控制,适合扩大化生产的要求;
(2)本发明所制备的复合光催化剂光热稳定性好,活性高,可多次重复使用;
(3)本发明所制备的催化剂对可见光有很好的吸收,在可见光条件下对有机污染物罗丹明B有着良好的降解效果;
(4)本发明所制备复合光催化剂在可见光区对有机污染物罗丹明B表现出比金属锌卟啉和二氧化钛更好的光催化性能,为今后开发制备方法简单,光催化性能高的的复合催化剂提供了新的途径。
附图说明
图1是本发明方法制备的ZnTpp/TiO2复合光催化剂与金属锌卟啉ZnTpp、未敏化的TiO2光催化剂的红外对比图;
图2是本发明方法制备的ZnTpp/TiO2复合光催化剂与未敏化的TiO2光催化剂的XRD对比图;
图3是本发明方法制备的ZnTpp/TiO2复合光催化剂与金属锌卟啉ZnTpp、未敏化的TiO2光催化剂的紫外-可见漫反射光谱对比图;
图4是本发明方法制备的ZnTpp/TiO2复合光催化剂降解罗丹明B水溶液随时间变化的紫外-可见光谱图;
图5是本发明方法制备的ZnTpp/TiO2复合光催化剂与金属锌卟啉ZnTpp、未敏化的TiO2光催化剂降解罗丹明B水溶液降解率随时间变化的曲线图。
具体实施方式
以下通过具体实施例对本发明进行描述或作进一步的说明,并且给出了详细的实施方式和具体的操作过程,其目的在于更好地理解本发明的技术内涵,但本发明的保护范围不限于下述的实施例。
实施例金属锌卟啉轴向功能化二氧化钛复合光催化剂ZnTpp/TiO2的制备:
将二氧化钛(0.15g)超声分散在极性有机溶剂四氢呋喃(10mL)中,分散均匀后,再加入异烟酸(0.5g)和N,N’-二环己基碳二酰亚胺(0.1g),进行酯化反应。反应结束后,待反应液冷却至室温,将反应液用0.45μm的尼龙膜进行过滤,再分别用去离子水和二氯甲烷洗涤,然后室温真空干燥12小时得到白色粉末状产物,即为异烟酸共价功能化的二氧化钛;超声下,将上述步骤所得产物和金属锌卟啉(25mg)溶解在极性有机溶剂N,N’-二甲基甲酰胺中,氮气保护下,进行功能化反应2天。反应液冷却后过滤,得到的淡紫色固体分别用去离子水、二氯甲烷、甲醇和乙醇洗涤,然后在真空中干燥过夜得到锌卟啉轴向功能化二氧化钛的复合光催化剂ZnTpp/TiO2。
图1的红外谱图表明金属锌卟啉ZnTpp修饰在二氧化钛TiO2表面。
图2的XRD谱图表明金属锌卟啉ZnTpp修饰在二氧化钛TiO2表面。
图3的紫外-可见漫反射光谱图表明金属锌卟啉ZnTpp修饰在二氧化钛TiO2表面,并且金属锌卟啉ZnTpp的引入扩展了二氧化钛TiO2在可见光区的吸收。
对比例下面通过对比例对本发明中制备的金属锌卟啉轴向功能化二氧化钛纳米复合光催化剂在可见光下对罗丹明B水溶液的降解百分率说明复合光催化材料的效果。
为了验证本发明所制备金属锌卟啉轴向功能化二氧化钛纳米复合光催化剂ZnTpp/TiO2的潜在应用性,发明人将其与锐钛矿型TiO2、金属锌卟啉ZnTpp在同一光源辐射下,做一系列对比。以罗丹明B水溶液为目标溶液,光催化实验采用的光源为350W卤钨灯。目标溶液置于100mL烧杯内,烧杯与灯垂直放置,二者之间的距离为15厘米。根据光照前后罗丹明B水溶液吸光度的变化计算得到降解百分率,对比结果如图5所示。
图4的谱图表明罗丹明B在光照下逐步分解,并且105分钟后几乎全部降解。
图5的谱图表明ZnTpp/TiO2复合光催化剂具有比金属锌卟啉ZnTpp和未敏化的TiO2更好的降解罗丹明B的光催化效果。
图5是用50mg金属锌卟啉轴向功能化二氧化钛纳米复合光催化剂ZnTpp/TiO2降解50mL10mg/L罗丹明B溶液在光源下溶液吸光率随时间变化的曲线。从图5中可以看出,在350W卤钨灯照射条件下,本发明所制备的金属锌卟啉敏化二氧化钛复合光催化剂ZnTpp/TiO2有比金属锌卟啉ZnTpp和无卟啉敏化催化剂二氧化钛TiO2更高的催化效果。可以看出,在金属锌卟啉为敏化剂和锐钛矿型二氧化钛为载体的协同作用下,本发明所制备的纳米复合光催化剂与现有催化剂相比,光催化效果显著提高。
Claims (8)
1.一种金属锌卟啉轴向功能化二氧化钛的复合光催化剂,其特征在于,由二氧化钛和金属锌卟啉组成,所述金属锌卟啉轴向修饰在异烟酸共价功能化的二氧化钛表面;所述锌卟啉轴向功能化二氧化钛的复合光催化剂的结构为:
2.根据权利要求1所述的一种金属锌卟啉轴向功能化二氧化钛的复合光催化剂的制备方法,其特征在于,包括如下步骤:
步骤A1:将二氧化钛超声分散在极性有机溶剂A中,分散均匀后,再加入异烟酸和N,N’-二环己基碳二酰亚胺,进行酯化反应,反应结束后,将反应物经冷却、过滤、洗涤,干燥,得到白色粉末状产物,即为异烟酸共价功能化的二氧化钛;
步骤A2:超声下,将步骤A1所得产物和金属锌卟啉超声溶解在极性有机溶剂B中,氮气保护下,进行功能化反应,反应结束后,将反应物经冷却、过滤、洗涤,干燥,得到锌卟啉轴向功能化二氧化钛的复合光催化剂ZnTpp/TiO2。
3.根据权利要求2所述的一种金属锌卟啉轴向功能化二氧化钛的复合光催化剂的制备方法,其特征在于,所述制备方法中,步骤A1的极性有机溶剂A为四氢呋喃,步骤A2的极性有机溶剂B为N,N’-二甲基甲酰胺。
4.根据权利要求2所述的一种金属锌卟啉轴向功能化二氧化钛的复合光催化剂的制备方法,其特征在于,所述二氧化钛的晶型为锐钛矿型;
步骤A1中,所述二氧化钛、异烟酸和N,N’-二环己基碳二酰亚胺的质量比为3:10:2;
步骤A2中,步骤A1所的产物和锌卟啉的质量比为8:5。
5.根据权利要求2所述的一种金属锌卟啉轴向功能化二氧化钛的复合光催化剂的制备方法,其特征在于,所述制备方法中超声时间均为半小时。
6.根据权利要求2所述的一种金属锌卟啉轴向功能化二氧化钛的复合光催化剂的制备方法,其特征在于,步骤A1酯化反应的温度为66℃,反应时间为3天;步骤A2功能化反应的温度为80℃,反应时间为2天。
7.根据权利要求2所述的一种金属锌卟啉轴向功能化二氧化钛的复合光催化剂的制备方法,其特征在于,所述过滤为将反应液用0.45μm的尼龙膜进行过滤;所述洗涤为分别用去离子水和二氯甲烷洗涤;所述干燥为真空室温下干燥12小时。
8.根据权利要求1所述的一种金属锌卟啉轴向功能化二氧化钛的复合光催化剂的用途,其特征在于,将所述复合催化剂作为光催化处理染料废水污染物。
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