CN112121797A - 一种磁性TiO2氧化石墨烯复合材料的制备方法 - Google Patents
一种磁性TiO2氧化石墨烯复合材料的制备方法 Download PDFInfo
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Abstract
本发明涉及一种光催化降解水体有机污染物的磁性氧化石墨烯复合材料的制备方法,包括以下步骤:制备Fe3O4磁性核,制备TiO2‑Fe3O4核壳结构,制备氧化石墨烯,将磁性TiO2催化剂分散吸附在氧化石墨烯层上,可改变磁性TiO2催化剂的量制成不同催化剂含量的磁性TiO2氧化石墨烯复合复合材料,本发明将TiO2‑Fe3O4制成核壳结构,有效预防了水体中强氧化物质对Fe3O4磁性的破坏,而氧化石墨烯表面基团不仅增强了该复合材料在水中的分散性,也增强了该复合材料对水体中有机污染物的吸附,有利于TiO2的光催化降解。
Description
技术领域
本发明涉及光催化降解技术领域,具体涉及一种光催化降解水体有机污染物的磁性 TiO2氧化石墨烯复合材料的制备方法。
背景技术
光催化可被称为光诱导反应,该类型的反应通过吸收具有足够能量(等于或高于催化剂的带隙能量的光子来激活。方法的最终目的是使活化电子与氧化剂之间发生反应以生成还原产物,并且使生成的空穴与还原剂之间发生反应以生成氧化产物。光催化降解技术越来越受到重视,特别是含有少量难降解有机物的废水的污水中。该过程有几个优点:(一)完全矿化(二)无废物处理问题(三)成本低(四)只需要温和的温度和压力条件。
能在有光的情况下促进反应在整个反应中不被消耗的固体被称为光催化剂。这些都是半导体。半导体材料是其价带和导带被能隙或带隙分开的材料。[43]半导体(例如TiO2,ZnO,Fe2O3,CdS和ZnS等)可以用于光诱导氧化还原过程的敏化剂。而单一的纳米光催化剂难以分散、吸附性能低、难以分离回收,其中提高对水体中有机污染物的吸附及光催化降解材料的回收是新的重点。
近来,通过利用Fe3O4磁性进行光催化降解材料回收成为热点,但易被水体腐蚀失去活性,水体中污染物难于吸附降解,使得光催化降解效率大打折扣。
发明内容
为了克服上述不足,本发明目的在于提供一种光催化降解水体有机污染物的磁性TiO2氧化石墨烯复合材料的制备方法,有效保护Fe3O4磁性,实现可分离回收,大大的提高了有机污染物的吸附降解效率。
本发明解决其技术问题所采用的技术方案是:一种光催化降解水体有机污染物的磁性TiO2氧化石墨烯复合材料的制备方法,包括以下步骤:
步骤一、制备Fe3O4磁性核
将Fe2+:Fe3+=5.5:1的铁盐制成溶液,超声15min,水浴锅中搅拌升温80℃,调节溶液 PH=12,使Fe3O4结晶,反应一段时间,冷却后用去离子水洗至中性。
步骤二、对Fe3O4进行表面改性
将步骤一中制备的Fe3O4用表面改性进行改善并尽量除去多余的表面改性剂
步骤三、制备TiO2-Fe3O4核壳结构
用共沉淀法制备TiO2-Fe3O4核壳结构,取表面改性过的Fe3O4,用钛酸四丁酯制备TiO2纳米壳
步骤四、磁性TiO2氧化石墨烯复合复合材料
将一定量TiO2-Fe3O4纳米颗粒分散吸附在氧化石墨烯层上,制成不同催化剂含量的磁性TiO2氧化石墨烯复合复合材料。
具体地,所述氧化石墨烯为改良的Hummers法制备的粉末状的氧化石墨烯。
具体地,在步骤一后对Fe3O4进行清洗,取1g制备的Fe3O4,滴加2mL油酸、4mL油胺,磁力搅拌30min,再经离心处理后加入正己烷,超声分散清洗,再加酒精清洗10-15min,然后离心分离。并将剩余产物于60℃干燥6h后研磨成粉末。
具体地,称取0.1g聚丙烯酸溶于30mL二甲基酰胺中,后与分散有0.5gFe3O4的 30mL正己烷混合,超声处理,离心分离,并用酒精和去离子水超声清洗。将经过改性的 Fe3O4加入到8mL的去离子水中,添加0.05g柠檬酸三钠,超声1h,使Fe3O4纳米颗粒充分分散,之后用去离子水离心清洗,除去过量的柠檬酸三钠。最后将所得物质分散在乙醇溶液当中。
具体地,将改性的Fe3O4加入含有30mL乙醇和10mL乙腈烧杯中,超声30min使 Fe3O4颗粒完全分散,并在常温下机械搅拌上述溶液。在搅拌期间,将0.15mL的氨水逐滴加入到A溶液中。制备B溶液:将4mL的钛酸四丁酯分散在13mL的乙醇溶液中,搅拌使其溶解均匀。然后将B溶液逐滴加入到A溶液中,反应2h,得到TiO2-Fe3O4纳米颗粒。将磁铁置于烧杯底部,分离出TiO2-Fe3O4纳米颗粒,除去上清液,剩余溶液离心3min,用乙醇清洗三次。收集并将样品置于60℃的烘箱中,连续干燥12h。
具体实施方式
现在对本发明作进一步详细的说明。
实施例一
一种光催化降解水体有机污染物的磁性TiO2氧化石墨烯复合材料的制备方法,包括以下步骤:
步骤一、制备Fe3O4磁性核
将11ml的1mol/L的氯化亚铁溶液与2ml的1mol/L的氯化铁溶液的混合,超声15min,水浴锅中搅拌升温80℃,调节溶液PH=12,获得Fe3O4结晶,反应一段时间,冷却后用去离子水洗至中性。
步骤二、对Fe3O4进行表面改性
取1g步骤一制备的Fe3O4,滴加2mL油酸、4mL油胺,磁力搅拌30min,再经离心处理后加入正己烷,超声分散清洗,再加酒精清洗15min,然后离心分离。并将剩余产物于60℃干燥6h后研磨成粉末。将0.5gFe3O4超声10min分散在30mL正己烷,称取0.1g聚丙烯酸溶于30mL二甲基酰胺中,加入Fe3O4的正己烷分散液中,超声处理,用酒精和去离子水超声清洗,离心分离后的Fe3O4加入到8mL的去离子水中,添加0.05g柠檬酸三钠,超声1 h,使Fe3O4纳米颗粒充分分散,之后用去离子水离心清洗。
步骤三、制备TiO2-Fe3O4核壳结构
将步骤二得到改性的Fe3O4加入含有30mL乙醇和10mL乙腈烧杯中,超声30min 使Fe3O4颗粒完全分散,并在常温下机械搅拌上述溶液。在搅拌期间,将0.15mL的氨水逐滴加入获得Fe3O4溶液;将4mL的钛酸四丁酯分散在13mL的乙醇溶液中,搅拌使其溶解均匀,并逐滴加入Fe3O4溶液,反应2h,得到TiO2-Fe3O4纳米颗粒。将磁铁置于烧杯底部,分离出TiO2-Fe3O4纳米颗粒,除去上清液,剩余溶液离心3min,用乙醇清洗三次。收集并将样品置于60℃的烘箱中,连续干燥12h。
步骤四、磁性TiO2氧化石墨烯复合复合材料
取0.5g步骤三制得的TiO2-Fe3O4纳米颗粒分散在100ml的2g/L氧化石墨烯水溶液,超声2h,获得含量的磁性TiO2氧化石墨烯复合复合材料。
具体地,所述氧化石墨烯为改良的Hummers法制备的粉末状的氧化石墨烯。
具体地,在步骤一后对Fe3O4进行清洗,取1g制备的Fe3O4,滴加2mL油酸、4mL油胺,磁力搅拌30min,再经离心处理后加入正己烷,超声分散清洗,再加酒精清洗10-15min,然后离心分离。并将剩余产物于60℃干燥6h后研磨成粉末。
具体地,称取0.1g聚丙烯酸溶于30mL二甲基酰胺中,后与分散有0.5gFe3O4的 30mL正己烷混合,超声处理,离心分离,并用酒精和去离子水超声清洗。将经过改性的 Fe3O4加入到8mL的去离子水中,添加0.05g柠檬酸三钠,超声1h,使Fe3O4纳米颗粒充分分散,之后用去离子水离心清洗,除去过量的柠檬酸三钠。最后将所得物质分散在乙醇溶液当中。
具体地,将改性的Fe3O4加入含有30mL乙醇和10mL乙腈烧杯中,超声30min使 Fe3O4颗粒完全分散,并在常温下机械搅拌上述溶液。在搅拌期间,将0.15mL的氨水逐滴加入到A溶液中。制备B溶液:将4mL的钛酸四丁酯分散在13mL的乙醇溶液中,搅拌使其溶解均匀。然后将B溶液逐滴加入到A溶液中,反应2h,得到TiO2-Fe3O4纳米颗粒。将磁铁置于烧杯底部,分离出TiO2-Fe3O4纳米颗粒,除去上清液,剩余溶液离心3min,用乙醇清洗三次。收集并将样品置于60℃的烘箱中,连续干燥12h。
实施例二
一种光催化降解水体有机污染物的磁性TiO2氧化石墨烯复合材料的制备方法,包括以下步骤:
步骤一、制备Fe3O4磁性核
将22ml的1mol/L的氯化亚铁溶液与4ml的1mol/L的氯化铁溶液的混合,超声15min,水浴锅中搅拌升温80℃,调节溶液PH=12,获得Fe3O4结晶,反应一段时间,冷却后用去离子水洗至中性。
步骤二、对Fe3O4进行表面改性
取1g步骤一制备的Fe3O4,滴加2mL油酸、4mL油胺,磁力搅拌30min,再经离心处理后加入正己烷,超声分散清洗,再加酒精清洗15min,然后离心分离。并将剩余产物于60℃干燥6h后研磨成粉末。将0.5gFe3O4超声10min分散在30mL正己烷,称取0.1g聚丙烯酸溶于30mL二甲基酰胺中,加入Fe3O4的正己烷分散液中,超声处理,用酒精和去离子水超声清洗,离心分离后的Fe3O4加入到8mL的去离子水中,添加0.05g柠檬酸三钠,超声1 h,使Fe3O4纳米颗粒充分分散,之后用去离子水离心清洗。
步骤三、制备TiO2-Fe3O4核壳结构
将步骤二得到改性的Fe3O4加入含有30mL乙醇和10mL乙腈烧杯中,超声30min 使Fe3O4颗粒完全分散,并在常温下机械搅拌上述溶液。在搅拌期间,将0.15mL的氨水逐滴加入获得Fe3O4溶液;将4mL的钛酸四丁酯分散在13mL的乙醇溶液中,搅拌使其溶解均匀,并逐滴加入Fe3O4溶液,反应2h,得到TiO2-Fe3O4纳米颗粒。将磁铁置于烧杯底部,分离出TiO2-Fe3O4纳米颗粒,除去上清液,剩余溶液离心3min,用乙醇清洗三次。收集并将样品置于60℃的烘箱中,连续干燥12h。
步骤四、磁性TiO2氧化石墨烯复合复合材料
取0.5g步骤三制得的TiO2-Fe3O4纳米颗粒分散在100ml的2g/L氧化石墨烯水溶液,超声2h,获得含量的磁性TiO2氧化石墨烯复合复合材料。
实施例三
一种光催化降解水体有机污染物的磁性TiO2氧化石墨烯复合材料的制备方法,包括以下步骤:
步骤一、制备Fe3O4磁性核
将11ml的0.5mol/L的氯化亚铁溶液与2ml的0.5mol/L的氯化铁溶液的混合,超声15min,水浴锅中搅拌升温80℃,调节溶液PH=12,获得Fe3O4结晶,反应一段时间,冷却后用去离子水洗至中性。
步骤二、对Fe3O4进行表面改性
取1g步骤一制备的Fe3O4,滴加2mL油酸、4mL油胺,磁力搅拌30min,再经离心处理后加入正己烷,超声分散清洗,再加酒精清洗15min,然后离心分离。并将剩余产物于60℃干燥6h后研磨成粉末。将0.5gFe3O4超声10min分散在30mL正己烷,称取0.1g聚丙烯酸溶于30mL二甲基酰胺中,加入Fe3O4的正己烷分散液中,超声处理,用酒精和去离子水超声清洗,离心分离后的Fe3O4加入到8mL的去离子水中,添加0.05g柠檬酸三钠,超声1 h,使Fe3O4纳米颗粒充分分散,之后用去离子水离心清洗。
步骤三、制备TiO2-Fe3O4核壳结构
将步骤二得到改性的Fe3O4加入含有30mL乙醇和10mL乙腈烧杯中,超声30min 使Fe3O4颗粒完全分散,并在常温下机械搅拌上述溶液。在搅拌期间,将0.15mL的氨水逐滴加入获得Fe3O4溶液;将4mL的钛酸四丁酯分散在13mL的乙醇溶液中,搅拌使其溶解均匀,并逐滴加入Fe3O4溶液,反应2h,得到TiO2-Fe3O4纳米颗粒。将磁铁置于烧杯底部,分离出TiO2-Fe3O4纳米颗粒,除去上清液,剩余溶液离心3min,用乙醇清洗三次。收集并将样品置于60℃的烘箱中,连续干燥12h。
步骤四、磁性TiO2氧化石墨烯复合复合材料
取0.5g步骤三制得的TiO2-Fe3O4纳米颗粒分散在100ml的2g/L氧化石墨烯水溶液,超声2h,获得含量的磁性TiO2氧化石墨烯复合复合材料。
实施例四
一种光催化降解水体有机污染物的磁性TiO2氧化石墨烯复合材料的制备方法,包括以下步骤:
步骤一、制备Fe3O4磁性核
将22ml的0.5mol/L的氯化亚铁溶液与4ml的0.5mol/L的氯化铁溶液的混合,超声15min,水浴锅中搅拌升温80℃,调节溶液PH=12,获得Fe3O4结晶,反应一段时间,冷却后用去离子水洗至中性。
步骤二、对Fe3O4进行表面改性
取1g步骤一制备的Fe3O4,滴加2mL油酸、4mL油胺,磁力搅拌30min,再经离心处理后加入正己烷,超声分散清洗,再加酒精清洗15min,然后离心分离。并将剩余产物于60℃干燥6h后研磨成粉末。将0.5gFe3O4超声10min分散在30mL正己烷,称取0.1g聚丙烯酸溶于30mL二甲基酰胺中,加入Fe3O4的正己烷分散液中,超声处理,用酒精和去离子水超声清洗,离心分离后的Fe3O4加入到8mL的去离子水中,添加0.05g柠檬酸三钠,超声1 h,使Fe3O4纳米颗粒充分分散,之后用去离子水离心清洗。
步骤三、制备TiO2-Fe3O4核壳结构
将步骤二得到改性的Fe3O4加入含有30mL乙醇和10mL乙腈烧杯中,超声30min 使Fe3O4颗粒完全分散,并在常温下机械搅拌上述溶液。在搅拌期间,将0.15mL的氨水逐滴加入获得Fe3O4溶液;将4mL的钛酸四丁酯分散在13mL的乙醇溶液中,搅拌使其溶解均匀,并逐滴加入Fe3O4溶液,反应2h,得到TiO2-Fe3O4纳米颗粒。将磁铁置于烧杯底部,分离出TiO2-Fe3O4纳米颗粒,除去上清液,剩余溶液离心3min,用乙醇清洗三次。收集并将样品置于60℃的烘箱中,连续干燥12h。
步骤四、磁性TiO2氧化石墨烯复合复合材料
取0.5g步骤三制得的TiO2-Fe3O4纳米颗粒分散在100ml的2g/L氧化石墨烯水溶液,超声2h,获得含量的磁性TiO2氧化石墨烯复合复合材料。
本发明不局限于所述实施方式,任何人赢得值在本发明的启示下作出的结构变化,凡是与本发明具有相同或相近的技术方案,均落入本发明的保护范围之内。
本发明未详细描述的技术、形状、构造部分均为公知技术。
Claims (6)
1.磁性TiO2氧化石墨烯复合复合材料的制备方法,其特征包括以下步骤:
步骤一、制备Fe3O4磁性核
将一定比例的Fe3+和Fe2+铁盐制成溶液,超声15min,水浴锅中搅拌升温80℃,调节溶液PH值,使Fe3O4结晶,反应一段时间,冷却后用去离子水洗至中性;
步骤二、对Fe3O4进行表面改性
将步骤一中制备的Fe3O4用表面改性进行改善并尽量除去多余的表面改性剂
步骤三、制备TiO2-Fe3O4核壳结构
用共沉淀法制备TiO2-Fe3O4核壳结构,取表面改性过的Fe3O4,用钛酸四丁酯制备TiO2纳米壳
步骤四、磁性TiO2氧化石墨烯复合复合材料
将一定量TiO2-Fe3O4纳米颗粒分散吸附在氧化石墨烯层上,制成不同催化剂含量的磁性TiO2氧化石墨烯复合复合材料。
2.根据权利要求1所述的磁性TiO2氧化石墨烯复合复合材料的制备方法,其特征在于在所述步骤一中,Fe2+:Fe3+=5.5:1,调节溶液PH=12,使Fe3O4结晶,反应一段时间,冷却后用去离子水洗至中性。
3.根据权利要求1所述的磁性TiO2氧化石墨烯复合复合材料的制备方法,其特征在于在所述步骤二实现对Fe3O4表面改性方法为,在步骤一后对Fe3O4进行清洗,取1g制备的Fe3O4,滴加2mL油酸、4mL油胺,磁力搅拌30min,再经离心处理后加入正己烷,超声分散清洗,再加酒精清洗10-15min,然后离心分离,并将剩余产物于60℃干燥6h后研磨成粉末。
4.根据权利要求1所述的磁性TiO2氧化石墨烯复合复合材料的制备方法,其特征在于在所述步骤二中,表面改性剂为聚丙烯酸、二甲基酰胺中,后与正己烷混合,超声处理,后离心分离,并用酒精和去离子水超声清洗,将经过改性的 Fe3O4加入到 8 mL的去离子水中,添加0.05 g柠檬酸三钠,超声1 h,使 Fe3O4纳米颗粒充分分散,之后用去离子水离心清洗,除去过量的柠檬酸三钠,最后将所得物质分散在乙醇溶液当中。
5.根据权利要求1所述的磁性TiO2氧化石墨烯复合复合材料的制备方法,其特征在于在所述步骤三中制备A溶液:将改性的Fe3O4加入含有30 mL乙醇和10 mL乙腈烧杯中,超声30min使Fe3O4颗粒完全分散,并在常温下机械搅拌上述溶液,在搅拌期间,将0.15 mL的氨水逐滴加入到A溶液中;制备B溶液:将4 mL 的钛酸四丁酯分散在13 mL的乙醇溶液中,搅拌使其溶解均匀;然后将B溶液逐滴加入到A溶液中,反应2 h,得到TiO2-Fe3O4纳米颗粒;将磁铁置于烧杯底部,分离出TiO2-Fe3O4纳米颗粒,除去上清液,剩余溶液离心3 min,用乙醇清洗三次,收集并将样品置于60ºC的烘箱中,连续干燥 12 h。
6.根据权利要求1所述的磁性TiO2氧化石墨烯复合复合材料的制备方法,其特征在于,氧化石墨烯为hummer法制备的粉末状氧化石墨烯。
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