CN104307484A - 一种具有呼吸效应的用于富集和催化降解有机物的新型复合材料 - Google Patents
一种具有呼吸效应的用于富集和催化降解有机物的新型复合材料 Download PDFInfo
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Abstract
本发明涉及一种具有呼吸效应的用于富集和催化降解有机物的新型复合材料的制备。具体为以水热法制备MIL-47柔性多孔吸附材料，经过充分的洗涤，净化，活化后，将其加入钛酸丁酯的乙醇溶液中，滴加水解液并不断搅拌，最终制备成可以用于富集和催化降解有机物的TiO2-MIL-47的复合材料。本方法工艺简单，容易操作。经过吸附和降解实验表明，本方法制备复合材料结构规则，孔容量大，对有机物的降解效果良好。此方法中，TiO2和MIL-47的添加比例无任何限制，可根据研究需要或实际应用需要采用任何比例进行负载。
Description
技术领域
本发明涉及一种具有呼吸效应的用于富集和催化降解有机物的新型复合材料，这种复合材料为负载二氧化钛(TiO2)纳米晶的多孔MIL-47颗粒，以水热法合成MIL-47颗粒后，在采用溶胶法对纳米二氧化钛进行负载，最终得到新型复合材料，并以此发展一种快速简易的有机物吸附和降解新方法。
背景技术
MIL-47是一类由金属离子和有机配体通过自组装作用形成的具有呼吸效应的柔性骨架多孔吸附材料。MIL-47具有规则的孔道结构，超大的比表面积(BET比表面积高达1000m2/g)，良好的热稳定性和溶剂稳定性等显著优点，因此，已被广泛使用于样品吸附领域。本发明采用MIL-47这种新型的柔性多孔吸附材料作为吸附剂，来制备用于富集和催化降解有机物的新型复合材料。
自半导体材料用于催化降解有机物取得突破性进展以来，二氧化钛因其催化活性高、化学和生物惰性好、对人体无毒、价廉等独特优点，成为近年来研究最活跃的催化材料。与常规尺寸的二氧化钛相比，纳米二氧化钛具有更高的催化活性和选择性，能够形成强氧化-还原体系，将不易氧化或难以降解的物质氧化分解，该技术已广泛应用于处理染料、造纸等行业产生的有机废水。然而，由于粒径极小，纳米二氧化钛在氧化过程中极易发生流失，因此，寻找能够固定纳米二氧化钛的载体，将吸附、氧化分解结合起来，才更有利于实际生产中的广泛应用。
本发明所设计的新型复合材料是采用具有呼吸效应的柔性多孔材料MIL-47作为吸附基体，在多孔MIL-47材料合成后，采用溶胶法在其孔道内负载具有催化降解活性的纳米二氧化钛，最终制成了新型的用于富集和催化降解有机物的复合材料。本发明的目的在于结合上述两种材料各自的特点和优势，制备一种新型的多功能型复合材料，并将其应用于污水或废水中有机物的吸附和降解过程中。
本专利系国家自然科学基金(No.21305102)，国家级大学生创新创业训练计划(No.201410058026)，天津市高等学校科技发展基金计划(No.2013512)，天津工业大学学生课外学术科技作品竞赛(No.2014341)项目资助。
发明内容
为实现本发明所提供的技术方案是：
以水热法制备MIL-47多孔吸附材料，经过充分的洗涤，净化，活化后，采用研钵将其研碎成颗粒度较为均一的MIL-47粉末。把经过活化后的MIL-47粉末加入到钛酸丁酯的乙醇溶液中，滴加水解液并不断搅拌，合成纳米二氧化钛和MIL-47的复合材料。将复合材料洗涤，净化，活化后，即得到了具有呼吸效应的用于富集和催化降解有机物的新型复合材料。
经过吸附实验表明，本方法制备的TiO2-MIL-47复合物结构规则，孔容量大，对有机物的吸附和催化降解性能良好。
其中，多孔吸附材料MIL-47的水热合成方法为：将三氯化钒，对苯二甲酸溶解于超纯水中，超声使其溶解后，将混合溶液置于聚四氟乙烯反应釜中，在烘箱中进行高温反应。反应结束后，将反应釜冷却，对反应釜中的固体物质进行反复，多次洗涤，随后置于烘箱中烘干备用。
TiO2-MIL-47复合材料的合成方法：称取一定量的MIL-47粉末，加入到钛酸丁酯，乙醇的混合液中，并搅拌均匀。在磁力搅拌条件下，向上述混合液中缓慢滴加乙醇，水，硝酸的混合液，滴加结束后继续搅拌若干小时。反应结束后，离心即可得到白色粘稠状固体。
TiO2-MIL-47复合材料的活化方法：将上述白色粘稠状固体用乙醇洗涤数次，并将固体置于烘箱中烘干，随后在烘箱中高温活化数小时。
TiO2-MIL-47复合材料的使用方法：将经过洗涤，烘干，活化后的复合材料加入到含有有机物或有机染料的废水中，同时对样品溶液进行机械搅拌，使复合材料能够与样品溶液进行充分的接触，同时用高压汞灯对样品溶液进行照射。同时，可以采用气相色谱法，液相色谱法，光谱分析法等，对样品溶液中有机物或有机染料的含量进行测定。
本发明采用具有呼吸效应的柔性多孔材料MIL-47作为吸附基体，在其孔道内负载具有有机物催化降解活性的TiO2纳米晶，制成了新型的具有呼吸效应的用于富集和催化降解有机污染物的复合材料。本发明所涉及的新型复合材料对污水或废水中的有机物具有良好的吸附和降解效果，在实际生产或生活中会具有广泛的应用价值。
具体实施方式
为更好理解本发明，下面结合实施例对本发明做进一步地详细说明，但是本发明要求保护的范围并不局限于实施例表示的范围。
实施例：
以水热法制备MIL-47多孔吸附材料，采用溶胶法将纳米二氧化钛负载于MIL-47吸附材料中，将复合材料净化，活化后，制备成用于富集和催化降解有机物的新型复合材料：
多孔吸附材料MIL-47的水热合成方法为：将1.5729克三氯化钒，0.4153克对苯二甲酸溶解于18毫升超纯水中，超声10分钟使其溶解后，将混合溶液置于30毫升聚四氟乙烯反应釜中，200℃反应96小时。待反应釜冷却，超纯水，乙醇溶液对所得到的金属有机骨架吸附材料进行洗涤，200℃烘干备用。
TiO2-MIL-47复合材料的合成方法：采用研钵将MIL-47研碎成颗粒度较为均一的粉末。称取50mg MIL-47粉末，加入到25ml钛酸丁酯，10ml乙醇的混合液中，室温下搅拌1小时。在磁力搅拌条件下，以1ml/min的速度，向上述混合液中滴加10ml乙醇，4ml水，1ml硝酸的混合液，滴加结束后搅拌12小时。离心即可得到白色粘稠状固体。
TiO2-MIL-47复合材料的活化方法：将上述白色粘稠状固体用乙醇洗涤数次，并将固体置于烘箱中60℃烘干，随后在200℃烘箱中活化3小时。
TiO2-MIL-47复合材料的使用方法：将经过洗涤，烘干，活化后的复合材料加入到含有有机物或有机染料的废水中，同时对样品溶液进行机械搅拌，使复合材料能够与样品溶液进行充分的接触，同时用高压汞灯对样品溶液进行照射。同时，可以采用气相色谱法，液相色谱法，光谱分析法等，对样品溶液中有机物或有机染料的含量进行测定。
Claims (5)
1.一种MIL-47多孔吸附剂，其特征在于：它是采用水热法制备得到的白色固体颗粒，此固体颗粒需先用超纯水反复清洗，以除去未反应的金属盐，再用乙醇反复清洗，除去未反应的对苯二甲酸。
2.一种高比表面积、良好吸附特性的MIL-47吸附剂，其特征在于：将权利要求1所述的MIL-47吸附剂需要200℃高温焙烧数小时。
3.TiO2-MIL-47复合材料的合成方法，其特征在于：将研磨成粉末状的MIL-47加入到钛酸丁酯的乙醇(或其他溶剂)溶液中，经充分搅拌混匀后，再滴加水解液。
4.TiO2-MIL-47复合材料的活化方法，其特征在于：所得复合材料需用乙醇洗涤数次，以除去未反应的钛酸丁酯，净化后的复合材料需要200℃高温焙烧数小时以激活纳米TiO2的催化活性。
5.根据权利要求3所述的TiO2-MIL-47复合材料的合成方法，其特征在于：TiO2和MIL-47的添加比例无任何限制，可根据研究需要或实际应用需要采用任何比例进行负载。
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105251435A (zh) * | 2015-11-24 | 2016-01-20 | 天津工业大学 | 一种具有mtn沸石构型核壳型复合材料制备方法 |
| CN105289510A (zh) * | 2015-11-24 | 2016-02-03 | 天津工业大学 | 一种具有呼吸效应的核壳结构复合材料制备方法 |
| CN107519942A (zh) * | 2016-11-17 | 2017-12-29 | 天津工业大学 | 采用"一锅法"制备具有呼吸效应的新型复合材料 |
| CN107519841A (zh) * | 2016-11-17 | 2017-12-29 | 天津工业大学 | 采用"一锅法"制备具有吸附和催化降解活性的介孔复合材料 |
| CN107537457A (zh) * | 2016-11-17 | 2018-01-05 | 天津工业大学 | 采用"一锅法"制备具有mtn沸石构型的新型复合材料 |
| CN109243829A (zh) * | 2018-09-19 | 2019-01-18 | 东莞理工学院 | 一种染料敏化电池电极及其制备方法和mil-47材料的应用 |
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| CN105251435A (zh) * | 2015-11-24 | 2016-01-20 | 天津工业大学 | 一种具有mtn沸石构型核壳型复合材料制备方法 |
| CN105289510A (zh) * | 2015-11-24 | 2016-02-03 | 天津工业大学 | 一种具有呼吸效应的核壳结构复合材料制备方法 |
| CN107519942A (zh) * | 2016-11-17 | 2017-12-29 | 天津工业大学 | 采用"一锅法"制备具有呼吸效应的新型复合材料 |
| CN107519841A (zh) * | 2016-11-17 | 2017-12-29 | 天津工业大学 | 采用"一锅法"制备具有吸附和催化降解活性的介孔复合材料 |
| CN107537457A (zh) * | 2016-11-17 | 2018-01-05 | 天津工业大学 | 采用"一锅法"制备具有mtn沸石构型的新型复合材料 |
| CN109243829A (zh) * | 2018-09-19 | 2019-01-18 | 东莞理工学院 | 一种染料敏化电池电极及其制备方法和mil-47材料的应用 |
| CN109243829B (zh) * | 2018-09-19 | 2021-04-13 | 东莞理工学院 | 一种染料敏化电池电极及其制备方法和mil－47材料的应用 |
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