CN106076422A - 一种海泡石负载卟啉敏化Bi2WO6可见光催化剂的制备方法 - Google Patents
一种海泡石负载卟啉敏化Bi2WO6可见光催化剂的制备方法 Download PDFInfo
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Abstract
本发明公开了一种海泡石负载卟啉敏化Bi2WO6可见光催化剂的制备方法。本发明以改性海泡石为载体，卟啉为敏化剂修饰Bi2WO6，得到海泡石负载卟啉敏化Bi2WO6可见光催化剂。本发明所得催化剂具有优良的可见光催化活性，能够显著提高光生电子和空穴的分离效率，同时能够显著提高太阳光清洁能源的利用效率。本发明通过比表面积大、性能稳定的改性海泡石负载加强卟啉敏化Bi2WO6，所得复合光催化剂对污染物分子具有明显的吸附和富集作用。
Description
技术领域
本发明属于负载型半导体材料的制备技术领域，具体涉及一种海泡石负载卟啉敏化Bi2WO6光催化复合材料。
背景技术
水污染严重威胁人类健康和生态环境。传统物理、化学和生物降解水处理技术对废水的净化效果不理想且存在二次污染和处理时间长的缺点，因此，亟待发展高效绿色的水污染治理技术。二氧化钛光催化降解废水技术具有降解率高、廉价、无毒、化学稳定性好等优点。然而，由于二氧化钛禁带较宽(3.2 ev)，只能利用太阳光中的紫外光，导致对太阳能的利用效率低。
钨酸铋（Bi2WO6）是一种具有层状结构的窄禁带宽度半导体（禁带宽度：2.69 ev），可以有效利用太阳光中的大部分能量且性能稳定，应用更广泛。但是，纯Bi2WO6光催化剂入射光利用率低和光生电子-空穴复合率较高，对有机废水的降解效率并不理想。现有改性技术主要包括半导体复合、离子掺杂、表面修饰和敏化等方法，目的是降低光催化剂禁带宽度、抑制光生电子-空穴复合。例如：CN 102500390A公开一种氧化铁/钨酸铋复合光催化剂的制备方法，CN 102513096 A公开了一种Mo、F共掺杂的可见光响应钨酸铋光催化剂及其制备方法。半导体复合法的制备工艺相对较复杂。离子掺杂法采用成本较高的贵金属离子掺杂或有毒的Co3+。敏化改性法是一种工艺简单的方法，主要原理是利用具有良好光吸收性能的敏化剂吸收光子形成激发态并将激发态电子传递给光催化剂的导带，H2O或O2俘获电子后形成•O2 -和•OH等强氧化性自由基，降解废水中的有机物。因此，敏化剂可以提高可见光响应并且保持光催化剂的氧化电势。
同时，在光催化降解有机废水过程中，通过多孔载体负载光催化剂有利于提高光催化剂表面对有机污染物的吸附能力和分离催化剂颗粒。例如：CN104383915A公开一种负载型Bi2WO6-TiO2/泡沫金属光催化剂的制备方法，所用的载体为泡沫镍。
发明内容
本发明目的是解决纯Bi2WO6光催化剂入射光利用率低、光生电子-空穴复合率较高及有机物降解率低的问题，提供一种海泡石负载卟啉敏化Bi2WO6可见光催化剂的制备方法。本发明以改性海泡石为光催化剂载体，卟啉为敏化剂修饰Bi2WO6可见光催化剂。通过卟啉敏化提高Bi2WO6对于太阳能的利用率。相对其它敏化染料而言，卟啉具有强捕光性能，有利于提高复合光催化的可见光利用率。同时，通过比表面积大、性能稳定的改性海泡石负载促进Bi2WO6复合光催化剂对污染物分子的吸附和富集作用。
本发明的技术方案为：
一种海泡石负载卟啉敏化Bi2WO6可见光催化剂的制备方法，以改性海泡石为载体，卟啉为敏化剂修饰Bi2WO6，得到海泡石负载卟啉敏化Bi2WO6可见光催化剂；具体包括如下步骤：
（1）分别以Na2WO4·2H2O和Bi(NO3)3·5H2O为W源和Bi源，将两者加入乙醇溶液中，然后加入改性海泡石充分混合，按化学计量比加入卟啉，室温下搅拌2~15小时，然后转入水热釜中，140-180℃反应16~48h；
（2）反应结束后自然冷却至室温，过滤并用无水乙醇和去离子水分别洗涤2~5次，真空干燥，制得海泡石负载卟啉敏化Bi2WO6可见光催化剂。
进一步地，所述的卟啉优选金属卟啉，金属卟啉中的配位金属离子优选Co、Mg或Zn等金属离子；卟啉的吡咯环上的取代基团优选甲基、甲氧基或羟基等。
进一步地，Na2WO4·2H2O、Bi(NO3)3·5H2O与改性海泡石载体的质量比为0.4:1:（4~11）。
进一步地，海泡石通过酸改性、热改性、离子交换改性或复合改性等方法得到改性海泡石。
进一步地，海泡石酸改性的具体制备步骤是：将海泡石加入质量分数为8~15%的盐酸中，室温条件下搅拌1~4h，反应完毕除去上清液并水洗至中性，置于烘箱中烘干再研细，最后在马弗炉中400~500℃煅烧4-6 h，制得酸改性海泡石。
本发明的有益效果为：
（1）本发明的海泡石负载卟啉敏化Bi2WO6光催化剂具有优良的可见光催化活性，能够明显促进光生电子和空穴的分离，同时能够显著提高太阳光清洁能源的利用效率。
（2）本发明的产品能明显加强卟啉敏化Bi2WO6光催化剂对有机废水中污染物分子的吸附和富集能力。
附图说明
图1是实施例1制备的海泡石负载卟啉敏化Bi2WO6可见光催化剂（Co-THPP/Bi2WO6/Sep）及其对比样品的X射线衍射图谱。
图2是实施例1制备的海泡石负载卟啉敏化Bi2WO6复合光催化剂及其对比样品的UV-Vis漫反射光谱图。
图3是实施例1制备的海泡石负载卟啉敏化Bi2WO6复合光催化剂及其对RhB溶液的光催化降解曲线。
具体实施方式
下面结合具体实施例对本发明做进一步详细说明，但本发明并不限于此。
实施例1
Co-THPP/Bi2WO6/酸改性海泡石复合可见光催化剂（Co-THPP/Bi2WO6/Acid-Sep）的制备，包括如下步骤：
（1）缓慢加入提纯海泡石至质量分数为10%的HCl (液固质量比10：1)，室温条件下搅拌2h，反应完毕除去上清液并水洗至中性，置于烘箱中烘干再研细。在马弗炉中500℃煅烧5h，得酸改性海泡石。
（2）用去离子水溶解Na2WO4·2H2O（0.5 g），加入上述改性海泡石（5 g）并搅拌0.5h。按化学计量比加入Bi(NO3)3·5H2O，以及1~3mg的钴-四-(对羟基苯基)卟啉（Co-THPP），室温下搅拌8小时，然后转入水热釜中，150℃反应24 h。
（3）自然冷却步骤（2）所述水热反应产物至室温，过滤并分别用去离子水和无水乙醇洗涤3次，在50℃下真空干燥，得Co-THPP/ Bi2WO6/海泡石复合光催化剂。
称取0.06g上述催化剂，投入100ml 浓度为10mg/L的罗丹明B（RhB）溶液中，用300w氙光灯（灯头处加420nm滤波片）为光源对RhB溶液进行降解。
实施例1制备的海泡石负载卟啉敏化Bi2WO6可见光催化剂（Co-THPP/Bi2WO6/Sep）及其对比样品的X射线衍射图谱如图1所示。图1中，a、b、c三个样品分别对应Bi2WO6、海泡石负载Bi2WO6（Bi2WO6/Sep）和Co卟啉（Co-THPP）。a、b、c三个样品特征峰均与斜方晶系Bi2WO6(JCPDS No. 73-1126)的特征峰完全匹配，其中b和c样品中在26.6°处有微弱的海泡石特征峰，d为改性海泡石（记为Sep）的XRD图谱。由图1可以看出，负载及敏化前后各组分的结构无明显改变。b、c中海泡石峰明显减弱是由于钨酸铋在其表面均匀分散负载引起。
海泡石负载卟啉敏化Bi2WO6复合光催化剂及其对比样品的UV-Vis漫反射光谱图如图2所示。从图2可以看出，海泡石负载及Co-THPP敏化后各催化剂的吸收光谱都明显红移，其中Co-THPP/Bi2WO6/Sep在438nm、550nm和593nm可见光处有强吸收峰。
实施例1制备的海泡石负载卟啉敏化Bi2WO6复合光催化剂及其对RhB溶液的光催化降解曲线如图3所示。此时，a表示空白对照即不加催化剂，b表示加入海泡石负载Bi2WO6（Bi2WO6/Sep）作为光催化剂，c表示在加入Bi2WO6作为光催化剂，d表示海泡石负载卟啉敏化Bi2WO6可见光催化剂（Co-THPP/Bi2WO6/Sep）作为光催化剂。在催化剂总量相同的情况下b、d组的催化剂中活性组分小于c组。由图3可知，在不加催化剂的空白对照a组中，随光反应时间增加，RhB溶液浓度有微降低，这是因为溶质分子本身在光照下存在微弱自降解。对照d、b和c组可知，暗反应阶段（-60 min~0 min）由于载体海泡石的作用，催化剂的对降解分子的吸附能力大大提高，并且d组催化剂金属卟啉的存在对带有正电荷的溶质分子的吸附作用进一步提高。在可见光催化降解阶段（0 min~140 min），Co-THPP/Bi2WO6/Sep降解效果明显提高，d组在140min时，降解率接近100%。
实施例2
MgTHPP/Bi2WO6/酸改性海泡石复合可见光催化剂（Mg-THPP/Bi2WO6/Acid-Sep）的制备，包括如下步骤：
（1）缓慢加入提纯海泡石至质量分数为12%的HCl (液固质量比10：1)，室温条件下搅拌3h，反应完毕除去上清液并水洗至中性，置于烘箱中烘干再研细。在马弗炉中500℃煅烧4h，得酸改性海泡石。
（2）用去离子水溶解Na2WO4·2H2O（0.5 g），加入上述改性海泡石（5 g）并搅拌1h。按化学计量比加入Bi(NO3)3·5H2O，以及1~3mg的镁-四-(对羟基苯基)卟啉（Mg-THPP），室温下搅拌3小时，然后转入水热釜中，180℃反应16 h。
（3）自然冷却步骤（2）所述水热反应产物至室温，过滤并分别用去离子水和无水乙醇洗涤4次，在80℃下真空干燥，得Mg-THPP/ Bi2WO6/海泡石复合光催化剂。
称取0.06g上述催化剂，投入100ml 浓度为10mg/L的罗丹明B（RhB）溶液中，用300w氙光灯（灯头处加420nm滤波片）为光源对RhB溶液进行降解。结果表明，130min左右，降解率接近100%。
实施例3
ZnTHPP/Bi2WO6/酸改性海泡石复合可见光催化剂（Zn-THPP/Bi2WO6/Acid-Sep）的制备，包括如下步骤：
（1）缓慢加入提纯海泡石至质量分数为8%的HCl (液固质量比10：1)，室温条件下搅拌4h，反应完毕除去上清液并水洗至中性，置于烘箱中烘干再研细。在马弗炉中400℃煅烧6h，得酸改性海泡石。
（2）用去离子水溶解Na2WO4·2H2O（0.5 g），加入上述改性海泡石（5 g）并搅拌1.5h。按化学计量比加入Bi(NO3)3·5H2O，以及1~3mg的锌-四-(对羟基苯基)卟啉（Zn-THPP），室温下搅拌15小时，然后转入水热釜中，140℃反应48h。
（3）自然冷却步骤（2）所述水热反应产物至室温，过滤并分别用去离子水和无水乙醇洗涤2次，在60℃下真空干燥，得Mg-THPP/ Bi2WO6/海泡石复合光催化剂。
称取0.06g上述催化剂，投入100ml 浓度为10mg/L的罗丹明B（RhB）溶液中，用300w氙光灯（灯头处加420nm滤波片）为光源对RhB溶液进行降解。结果表明，135min左右，降解率接近100%。
Claims (6)
1.一种海泡石负载卟啉敏化Bi2WO6可见光催化剂的制备方法，其特征在于，以改性海泡石为载体，卟啉为敏化剂修饰Bi2WO6，得到海泡石负载卟啉敏化Bi2WO6可见光催化剂。
2.根据权利要求1所述的海泡石负载卟啉敏化Bi2WO6可见光催化剂的制备方法，其特征在于，包括如下步骤：
（1）分别以Na2WO4·2H2O和Bi(NO3)3·5H2O为W源和Bi源，将两者加入乙醇溶液中，然后加入改性海泡石充分混合，按化学计量比加入卟啉，室温下搅拌2~15小时，然后转入水热釜中，140-180℃反应16~48 h；
（2）反应结束后自然冷却至室温，过滤并用无水乙醇和去离子水分别洗涤2~5次，真空干燥，制得海泡石负载卟啉敏化Bi2WO6可见光催化剂。
3.根据权利要求2所述的海泡石负载卟啉敏化Bi2WO6可见光催化剂的制备方法，其特征在于，所述的卟啉为金属卟啉，金属卟啉中的配位金属离子为Co、Mg或Zn；卟啉的吡咯环上的取代基团为甲基、甲氧基或羟基。
4.根据权利要求2所述的海泡石负载卟啉敏化Bi2WO6可见光催化剂的制备方法，其特征在于，Na2WO4·2H2O、Bi(NO3)3·5H2O与改性海泡石载体的质量比为0.4:1:（4~11）。
5.根据权利要求2所述的海泡石负载卟啉敏化Bi2WO6可见光催化剂的制备方法，其特征在于，海泡石通过酸改性、热改性、离子交换改性或复合改性得到改性海泡石。
6.根据权利要求5所述的海泡石负载卟啉敏化Bi2WO6可见光催化剂的制备方法，其特征在于，海泡石酸改性的具体制备步骤是：将海泡石加入质量分数为8~15%的盐酸中，室温条件下搅拌1~4h，反应完毕除去上清液并水洗至中性，置于烘箱中烘干再研细，最后在马弗炉中400~500℃煅烧4-6 h，制得酸改性海泡石。
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