CN105664994A - 一种氨基功能化磁性光催化剂及其制备方法与应用 - Google Patents
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Abstract
本发明属于环保技术领域,具体涉及一种氨基功能化磁性光催化剂及其制备方法与应用。本发明利用乙二胺和Fe3O4反应使之与金属离子形成配合物而延长链结构而最终得到LiBi(WO4)2-Fe3O4,再利用ATPMS作为氨基偶联剂偶联得到氨基功能化磁性光催化剂,使之能够均相分散在水中。本发明可以使分散在水中的光催化剂达到分离效果;氨基功能化的磁性光催化剂可以溶于水因而可以通过均相催化更高效降解有机污染物,本发明涉及工艺简单,无需昂贵的设备,成本投资小,但是对于有机废水降解效果好,无污染,应用前景广阔。
Description
技术领域
本发明属于环保技术领域,具体涉及一种氨基功能化磁性光催化剂及其制备方法与应用。
背景技术
光催化技术作为一种新兴的环境净化技术,它的应用研究已在有机物降解、水质处理、环境保护等领域广泛展开,光催化技术能将难降解有机污染物氧化、分解,直至H2O、CO2和无机盐等,为彻底解决水污染问题提供了新的手段,它在环境污染治理中有广阔的应用前景。
针对有机废水的光催化难降解,普通均相芬顿系统的低pH要求和产生含铁污泥的问题,经对现有技术的相关检索发现,中国发明申请专利号为201510167318.3,发明名称为“LiBi(WO4)2紫外光催化剂的制备方法及其运用”中的LiBi(WO4)2紫外光催化剂就可以解决以上问题。然而,光催化剂分散在水中,在水污染处理中造成了难以分离回收的难题,而现有的技术中的磁性光催化剂已经成功解决该难题。磁性纳米材料不仅具有纳米材料特有的小尺寸效应、表面效应等优点,还具有不同于常规材料的超顺磁性,能够在外加磁场的辅助下轻易的实现分离回收,避免了材料的浪费以及可能造成的危害和污染。因此,磁性纳米颗粒及其复合材料在催化、生物分离、靶向给药、磁共振成像和分析化学等领域具有广阔的应用前景。况且在水污染处理中,多相催化中的催化剂和原料、产物不同相,接触面积小,催化剂用量较大,效率相对较低;而相比之下,均相催化中的反应物、催化剂和产物都在同一相中,接触面积大,催化剂用量少,催化效率高。
发明内容
为了克服现有技术中悬浆型光催化剂难以分离的缺点和不足,本发明的首要目的在于提供一种氨基功能化磁性光催化剂的制备方法。
本发明的另一目的在于提供上述制备方法制备得到的氨基功能化磁性光催化剂,该催化剂可溶于水而达到均相催化提高效率。
本发明的再一目的在于提供上述氨基功能化磁性光催化剂的应用。
本发明的目的通过下述技术方案实现:
一种氨基功能化磁性光催化剂的制备方法,包含如下步骤:
(1)将LiBi(WO4)2和纳米Fe3O4混合,加入乙醇水溶液作为溶剂,并调节体系pH为4~6,超声分散,使团聚的颗粒分散完全;超声分散后加入乙二胺并搅拌0.5h~2h,使之与金属离子形成配合物而延长链结构;然后磁性分离去除固体,得到液体;除杂,干燥,得到LiBi(WO4)2-Fe3O4;
(2)将步骤(1)制得的LiBi(WO4)2-Fe3O4溶于乙醇中,调节溶液pH为9~11;然后同时滴加PMHS(聚甲基含氢硅氧烷)和TEOS(正硅酸乙酯),滴加完成后再滴加ATPMS(氨基功能化有机烷氧基硅烷或3-氨丙基三甲氧基硅烷)作为氨基偶联剂至体系呈溶胶态,然后搅拌反应12h~24h,使PMHS中的活泼氢原子完全被乙氧基取代;随后静置老化2~5天,溶胶完全转化为凝絮体;干燥,除杂,再次干燥,得到氨基功能化磁性光催化剂(LiBi(WO4)2NH2-Fe3O4);
步骤(1)中所述的LiBi(WO4)2和纳米Fe3O4的摩尔比优选为(1:1)~(1:3);
步骤(1)中所述的乙二胺和纳米Fe3O4的摩尔比优选为1:1;
步骤(1)中所述的乙醇水溶液中,无水乙醇和水的体积比优选为(1:1)~(3:2);
步骤(1)中所述的乙醇水溶液应完全浸没LiBi(WO4)2和纳米Fe3O4;
步骤(1)中所述的超声分散的时间优选为0.3~1.0h;
步骤(1)中所述的除杂的条件优选为:1mol·L-1NH4NO3溶液60℃萃取2~4次,再用乙醇清洗1~3次;
步骤(1)中所述的干燥的条件优选为:180℃~220℃真空烘干8h~12h;
步骤(2)中所述的乙醇优选为无水乙醇;
步骤(2)中所述的LiBi(WO4)2-Fe3O4与ATPMS的摩尔比优选为1:1;
步骤(2)中所述的PMHS、TEOS和ATPMS的摩尔比优选为(1:1:2)~(1:1:4);
步骤(2)中所述的搅拌反应的条件优选为:室温下反应12h~24h;
步骤(2)中所述的干燥与再次干燥的条件优选为80℃~110℃下真空干燥24h~48h;
步骤(2)中所述的除杂优选为:去离子水洗涤3~5次,去除固体上残留的未反应物质(例如:调节pH的碱溶液NaOH等);
一种氨基功能化磁性光催化剂,通过上述制备方法制备得到;
所述的氨基功能化磁性光催化剂在光催化领域中的应用;
所述的氨基功能化磁性光催化剂在有机物降解、水质处理或环境保护领域中的应用;
本发明的原理:利用乙二胺和Fe3O4反应使之与金属离子形成配合物而延长链结构而最终得到LiBi(WO4)2-Fe3O4,再利用ATPMS作为氨基偶联剂偶联得到氨基功能化磁性光催化剂(LiBi(WO4)2NH2-Fe3O4),使之能够均相分散在水中。
本发明相对于现有技术具有如下的优点及效果:
(1)本发明制备得到的氨基功能化磁性光催化剂使用后可再次回收利用,可以使分散在水中的光催化剂达到分离效果。
(2)本发明制备得到的氨基功能化磁性光催化剂可以溶于水因而可以通过均相催化更高效降解有机污染物,将本发明制备的氨基功能化磁性光催化剂用于亚甲基蓝废水时,大大加快水有机污染物的处理。
(3)本发明提供的制备方法简单,成本低投资小。
具体实施方式
下面结合实施例对本发明作进一步详细的描述,但本发明的实施方式不限于此。
实施例中的LiBi(WO4)2参照中国发明申请专利号为201510167318.3,发明名称为“LiBi(WO4)2紫外光催化剂的制备方法及其运用”制备得到;
实施例1
(1)将LiBi(WO4)2和纳米Fe3O4按照摩尔比1:1混合,加入乙醇水溶液(无水乙醇和水的体积比为1:1)作为溶剂,并调节体系pH值为4,超声分散0.3h,使团聚的颗粒分散完全;超声分散后加入乙二胺(乙二胺与纳米Fe3O4的摩尔比为1:1),搅拌0.5h,使之与金属离子形成配合物而延长链结构;然后磁性分离去除固体,得到液体;除杂(1mol·L-1NH4NO3溶液60℃萃取2次,再用乙醇清洗3次),180℃真空烘干12h,得到LiBi(WO4)2-Fe3O4;
(2)将步骤(1)制得的LiBi(WO4)2-Fe3O4溶于溶剂无水乙醇中,再加入碱溶液(NaOH溶液),调节溶液pH为9;然后同时滴加PMHS和TEOS,滴加完成后再滴加氨基功能化有机烷氧基硅烷ATPMS作为氨基偶联剂至体系呈溶胶态,其中,ATPMS与LiBi(WO4)2-Fe3O4的摩尔比为1:1,PMHS、TEOS和ATPMS的摩尔比为1:1:2;然后室温下搅拌反应12h,使PMHS中的活泼氢原子完全被乙氧基取代;随后静置老化2天,溶胶完全转化为凝絮体;80℃下真空干燥48h,去离子水洗涤3次,去除固体上残留的NaOH,再次80℃下真空干燥48h,得到氨基功能化磁性光催化剂(LiBi(WO4)2NH2-Fe3O4);
(3)将步骤(2)制得的氨基功能化磁性光催化剂用于降解亚甲基蓝废水:以1.0g/L的亚甲基蓝溶液作为污水模型,在磁力搅拌下分别与UV/H2O2(0.5%(W/W)H2O2)体系(对照)、LiBi(WO4)2NH2-Fe3O4氨基功能化磁性光催化剂(0.5g·L-1)/H2O2(0.5%(W/W)H2O2)/UV体系和LiBi(WO4)2NH2-Fe3O4氨基功能化磁性光催化剂(0.5g·L-1)/UVCWOP体系反应60min后,将样品在外加磁场作用下进行磁力分离,取上层清液,进行吸光度测定。计算出亚甲基蓝溶液的脱色率分别为65%、87%、96%,大大加快水有机污染物的处理。
实施例2
(1)将LiBi(WO4)2和纳米Fe3O4按照摩尔比1:2混合,加入乙醇水溶液(无水乙醇和水的体积比为1.2:1)作为溶剂,并调节体系pH值为5,超声分散0.6h,使团聚的颗粒分散完全;超声分散后加入乙二胺(乙二胺与纳米Fe3O4的摩尔比为1:1),搅拌1h,使之与金属离子形成配合物而延长链结构;然后磁性分离去除固体,得到液体;除杂(1mol·L-1NH4NO3溶液60℃萃取4次,再用乙醇清洗1次),220℃真空烘干8h,得到LiBi(WO4)2-Fe3O4;
(2)将步骤(1)制得的LiBi(WO4)2-Fe3O4溶于溶剂无水乙醇中,再加入碱溶液(NaOH溶液),调节溶液pH为10,然后同时滴加PMHS和TEOS,滴加完成后再滴加氨基功能化有机烷氧基硅烷ATPMS作为氨基偶联剂至体系呈溶胶态,其中,ATPMS与LiBi(WO4)2-Fe3O4的摩尔比为1:1,PMHS、TEOS和ATPMS的摩尔比为1:1:3,然后室温下搅拌反应18h,使PMHS中的活泼氢原子完全被乙氧基取代;随后静置老化3天,溶胶完全转化为凝絮体;110℃下真空干燥24h,去离子水洗涤5次,去除固体上残留的NaOH,再次110℃下真空干燥24h,得到氨基功能化磁性光催化剂(LiBi(WO4)2NH2-Fe3O4);
(3)将步骤(2)制得的氨基功能化磁性光催化剂用于降解亚甲基蓝废水:以1.0g/L的亚甲基蓝溶液作为污水模型,在磁力搅拌下分别与UV/H2O2(0.5%(W/W)H2O2)体系(对照)、LiBi(WO4)2NH2-Fe3O4氨基功能化磁性光催化剂(0.5g·L-1)/H2O2(0.5%(W/W)H2O2)/UV体系和LiBi(WO4)2NH2-Fe3O4氨基功能化磁性光催化剂(0.5g·L-1)/UVCWOP体系反应60min后,将样品在外加磁场作用下进行磁力分离,取上层清液,进行吸光度测定。计算出亚甲基蓝溶液的脱色率分别为65%、87%、97%,大大加快水有机污染物的处理。
实施例3
(1)将LiBi(WO4)2和纳米Fe3O4按照摩尔比1:3混合,加入乙醇水溶液(无水乙醇和水的体积比为3:2)作为溶剂,并调节体系pH值为6,超声分散1.0h,使团聚的颗粒分散完全;超声分散后加入乙二胺(乙二胺与纳米Fe3O4的摩尔比为1:1),搅拌2h,使之与金属离子形成配合物而延长链结构;然后磁性分离去除固体,得到液体;除杂(1mol·L-1NH4NO3溶液60℃萃取3次,再用乙醇清洗2次),200℃真空烘干10h,得到LiBi(WO4)2-Fe3O4;
(2)将步骤(1)制得的LiBi(WO4)2-Fe3O4溶于溶剂无水乙醇中,再加入碱溶液(NaOH溶液),调节溶液pH为11,然后同时滴加PMHS和TEOS,滴加完成后再滴加氨基功能化有机烷氧基硅烷ATPMS作为氨基偶联剂至体系呈溶胶态,其中,ATPMS与LiBi(WO4)2-Fe3O4的摩尔比为1:1,PMHS、TEOS和ATPMS的摩尔比为1:1:4;然后室温下搅拌反应24h,使PMHS中的活泼氢原子完全被乙氧基取代;然后静置老化5天,溶胶完全转化为凝絮体;100℃下真空干燥36h,去离子水洗涤4次,去除固体上残留的NaOH,再次100℃下真空干燥36h,得到氨基功能化磁性光催化剂(LiBi(WO4)2NH2-Fe3O4);
(3)将步骤(2)制得的氨基功能化磁性光催化剂用于降解亚甲基蓝废水:以1.0g/L的亚甲基蓝溶液作为污水模型,在磁力搅拌下分别与UV/H2O2(0.5%(W/W)H2O2)体系(对照)、LiBi(WO4)2NH2-Fe3O4氨基功能化磁性光催化剂(0.5g·L-1)/H2O2(0.5%(W/W)H2O2)/UV体系和LiBi(WO4)2NH2-Fe3O4氨基功能化磁性光催化剂(0.5g·L-1)/UVCWOP体系反应60min后,将样品在外加磁场作用下进行磁力分离,取上层清液,进行吸光度测定。计算出亚甲基蓝溶液的脱色率分别为65%、88%、97%,大大加快水有机污染物的处理。
上述实施例为本发明较佳的实施方式,但本发明的实施方式并不受上述实施例的限制,其他的任何未背离本发明的精神实质与原理下所作的改变、修饰、替代、组合、简化,均应为等效的置换方式,都包含在本发明的保护范围之内。
Claims (10)
1.一种氨基功能化磁性光催化剂的制备方法,其特征在于包含如下步骤:
(1)将LiBi(WO4)2和纳米Fe3O4混合,加入乙醇水溶液作为溶剂,并调节体系pH为4~6,超声分散;超声分散后加入乙二胺并搅拌0.5h~2h;然后磁性分离去除固体,得到液体;除杂,干燥,得到LiBi(WO4)2-Fe3O4;
(2)将步骤(1)制得的LiBi(WO4)2-Fe3O4溶于乙醇中,调节溶液pH为9~11;然后同时滴加PMHS和TEOS,滴加完成后再滴加ATPMS作为氨基偶联剂至体系呈溶胶态,然后搅拌反应12h~24h;随后静置老化2~5天,溶胶完全转化为凝絮体;干燥,除杂,再次干燥,得到氨基功能化磁性光催化剂。
2.根据权利要求1中所述的氨基功能化磁性光催化剂的制备方法,其特征在于:步骤(1)中所述的LiBi(WO4)2和纳米Fe3O4的摩尔比为(1:1)~(1:3)。
3.根据权利要求1中所述的氨基功能化磁性光催化剂的制备方法,其特征在于:步骤(1)中所述的乙二胺和纳米Fe3O4的摩尔比为1:1。
4.根据权利要求1中所述的氨基功能化磁性光催化剂的制备方法,其特征在于:步骤(1)中所述的超声分散的时间为0.3~1.0h。
5.根据权利要求1中所述的氨基功能化磁性光催化剂的制备方法,其特征在于:步骤(2)中所述的LiBi(WO4)2-Fe3O4与ATPMS的摩尔比为1:1。
6.根据权利要求1中所述的氨基功能化磁性光催化剂的制备方法,其特征在于:
步骤(2)中所述的PMHS、TEOS和ATPMS的摩尔比为(1:1:2)~(1:1:4)。
7.根据权利要求1中所述的氨基功能化磁性光催化剂的制备方法,其特征在于:
步骤(2)中所述的搅拌反应的条件为:室温下反应12h~24h。
8.一种氨基功能化磁性光催化剂,其特征在于:通过权利要求1~7任一项所述的制备方法制备得到。
9.权利要求8所述的氨基功能化磁性光催化剂在光催化领域中的应用。
10.权利要求8所述的氨基功能化磁性光催化剂在有机物降解、水质处理或环境保护领域中的应用。
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CN107008506A (zh) * | 2017-03-28 | 2017-08-04 | 浙江大学宁波理工学院 | Fe(III)‑Salen功能化纳米Fe3O4 复合材料、制备方法及其应用 |
Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101602007A (zh) * | 2009-07-14 | 2009-12-16 | 中国科学院上海硅酸盐研究所 | 可见光响应的磁性光催化材料及其制备 |
CN101804335A (zh) * | 2010-05-05 | 2010-08-18 | 中国科学院山西煤炭化学研究所 | 一种吸附二氧化碳的有机-无机多孔复合材料的制备方法 |
CN102319563A (zh) * | 2011-05-30 | 2012-01-18 | 湖南大学 | 一种磁性纳米复合光催化剂及应用 |
CN102489300A (zh) * | 2011-11-18 | 2012-06-13 | 东华大学 | 一种磁性纳米微球光催化复合材料的制备方法 |
CN102659322A (zh) * | 2012-04-06 | 2012-09-12 | 南昌航空大学 | 一种玻璃/pmma微纳界面结构层合材料制备方法 |
CN103111285A (zh) * | 2013-03-24 | 2013-05-22 | 桂林理工大学 | 可见光响应的复合氧化物光催化剂LiBiMo2O8及其制备方法 |
CN103537313A (zh) * | 2013-10-11 | 2014-01-29 | 南京工业大学 | 苯羟基化制苯酚的催化剂及其制备方法 |
CN104801297A (zh) * | 2015-04-09 | 2015-07-29 | 东莞道汇环保科技有限公司 | LiBi(WO4)2紫外光催化剂的制备方法及其运用 |
-
2016
- 2016-02-29 CN CN201610111490.1A patent/CN105664994B/zh active Active
Patent Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101602007A (zh) * | 2009-07-14 | 2009-12-16 | 中国科学院上海硅酸盐研究所 | 可见光响应的磁性光催化材料及其制备 |
CN101804335A (zh) * | 2010-05-05 | 2010-08-18 | 中国科学院山西煤炭化学研究所 | 一种吸附二氧化碳的有机-无机多孔复合材料的制备方法 |
CN102319563A (zh) * | 2011-05-30 | 2012-01-18 | 湖南大学 | 一种磁性纳米复合光催化剂及应用 |
CN102489300A (zh) * | 2011-11-18 | 2012-06-13 | 东华大学 | 一种磁性纳米微球光催化复合材料的制备方法 |
CN102659322A (zh) * | 2012-04-06 | 2012-09-12 | 南昌航空大学 | 一种玻璃/pmma微纳界面结构层合材料制备方法 |
CN103111285A (zh) * | 2013-03-24 | 2013-05-22 | 桂林理工大学 | 可见光响应的复合氧化物光催化剂LiBiMo2O8及其制备方法 |
CN103537313A (zh) * | 2013-10-11 | 2014-01-29 | 南京工业大学 | 苯羟基化制苯酚的催化剂及其制备方法 |
CN104801297A (zh) * | 2015-04-09 | 2015-07-29 | 东莞道汇环保科技有限公司 | LiBi(WO4)2紫外光催化剂的制备方法及其运用 |
Non-Patent Citations (1)
Title |
---|
胡跃飞: "《现代有机合成试剂2还原反应试剂》", 31 July 2011 * |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN107008506A (zh) * | 2017-03-28 | 2017-08-04 | 浙江大学宁波理工学院 | Fe(III)‑Salen功能化纳米Fe3O4 复合材料、制备方法及其应用 |
CN107008506B (zh) * | 2017-03-28 | 2019-10-01 | 浙江大学宁波理工学院 | Fe(III)-Salen功能化纳米Fe3O4复合材料、制备方法及其应用 |
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