CN115318239A - 表面沉积超顺磁纳米粒的鲍鱼壳羟基磷灰石多孔微球及其制备方法 - Google Patents
表面沉积超顺磁纳米粒的鲍鱼壳羟基磷灰石多孔微球及其制备方法 Download PDFInfo
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- 239000002105 nanoparticle Substances 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000001509 sodium citrate Substances 0.000 claims abstract description 16
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 claims abstract description 16
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Abstract
本发明属于无机材料制备技术领域,具体涉及表面沉积超顺磁纳米粒的鲍鱼壳羟基磷灰石多孔微球的制备方法。该微球以废弃鲍鱼壳和纳米四氧化三铁为主要原料,以柠檬酸钠为模板剂,通过水热合成自组装形成具有磁性的羟基磷灰石微球,将此羟基磷灰石微球作为可回收性高效吸附剂应用于水溶液染料、离子、原油等的吸附中。本发明凭借四氧化三铁本身独特的超顺磁性,可利用磁铁等磁性物质收集,且制备方法简便,实现了废弃鲍鱼壳的高值化利用,达到了“变废为宝”的目的,工艺简单,成本低廉,易于推广,具有良好的经济效益和生态效益。
Description
技术领域
本发明属于无机材料制备技术领域,具体涉及一种成本低廉、制备简单、绿色环保、具有可回收性、可作为高效吸附剂的表面沉积超顺磁纳米粒的鲍鱼壳羟基磷灰石多孔微球及其制备方法。
背景技术
随着工业发展,水源污染问题日益严重,寻找低成本高效率的强效吸附剂是解决污染问题的重点。如未能及时除污,将会导致重金属元素不断富集,对环境造成巨大影响。常见除污方法以化学沉淀、膜分离、活性炭吸附、离子交换等传统方法为主。这些传统方法难以避免成本高、效果差等问题。因此,找寻新的低成本高效吸附剂是净化除污领域亟待解决的一项问题。
本发明从解决废弃贝壳污染与废水污染的角度出发,以鲍鱼壳为钙源,纳米四氧化三铁为磁性原料制备的高效吸附剂,该吸附剂具有良好的多孔微球结构,粒径为3-10μm,孔径约7nm,吸附率较高。鲍鱼壳成本低廉,来源广泛;包覆致密硅层的纳米四氧化三铁,具备超顺磁性且不易腐蚀氧化。本发明赋予羟基磷灰石磁性和可回收性,制备方法简便,实现了废弃鲍鱼壳的高值化利用,有望成为一种绿色环保的新型吸附剂。
发明内容
本发明的目的在于解决鲍鱼壳大量废弃、利用率与附加值低的问题以及废水污染问题,提供一种具有高效吸附性能的表面沉积超顺磁纳米粒的鲍鱼壳羟基磷灰石多孔微球及其制备方法,其制备工艺简单,成本低廉,吸附染料效果良好。
为实现上述目的,本发明采用如下技术方案:
表面沉积超顺磁纳米粒的鲍鱼壳羟基磷灰石多孔微球的制备方法,首先制备包覆硅层的纳米四氧化三铁;其后对鲍鱼壳的表层物质进行冲洗,然后风干,研磨筛选获得鲍鱼壳粉末;将鲍鱼壳粉末溶于醋酸溶液中,搅拌至无气泡产生,而后进行离心得到上清液;取上清液,向其中滴加磷酸溶液,搅拌,然后添加柠檬酸钠、尿素并持续搅拌至完全溶解;向体系中加入包覆硅层的纳米四氧化三铁,充分搅拌;倒入高压反应釜中进行水热反应;反应结束后,自然冷却至室温,水洗、醇洗磁吸分离,干燥,最后得到所述的表面沉积超顺磁纳米粒的鲍鱼壳羟基磷灰石多孔微球。
具体包括以下步骤:
(1)配制乙醇和水混合溶液,加入超声分散的纳米四氧化三铁分散液,超声15min;
(2)将步骤(1)体系装入三颈烧瓶,置于磁力搅拌器中搅拌,搅拌过程中(180~200rpm)快速加入氨水,搅拌10min;
(3)向步骤(2)体系中缓慢滴加硅酸四已酯,持续机搅8h;
(4)将步骤(3)体系进行醇洗磁吸分离至上清液澄清,得到包覆硅层的纳米四氧化三铁Fe@Si;
(5)用流水冲洗鲍鱼壳,去除鲍鱼壳的表层物质,然后自然风干;
(6)将风干后的鲍鱼壳粉碎研磨筛选,获得鲍鱼壳粉末;
(7)将鲍鱼壳粉末溶于醋酸溶液中,搅拌至无气泡产生,而后用离心机(8000rpm,5min)进行离心得到上清液;
(8)将步骤(7)得到的上清液定容至50ml,而后用注射泵以50ml/h的滴加速度向其中缓慢滴加0.06mol/L磷酸溶液,并置于磁力搅拌器(200~300rpm)搅拌1h;
(9)向步骤(8)搅拌后的溶液中添加柠檬酸钠、尿素并置于磁力搅拌器(200~300rpm)持续搅拌20min至完全溶解;
(10)向步骤(9)制得的反应液中加入步骤(4)所得的包覆硅层的纳米四氧化三铁,室温下搅拌(350rpm)1h;
(11)将步骤(10)制得的反应体系倒入高压反应釜中并置于90℃恒温干燥箱中进行水热反应40h;
(12)反应结束后,自然冷却至室温,水洗、醇洗磁吸分离,60℃干燥2h,得到所述的表面沉积超顺磁纳米粒的鲍鱼壳羟基磷灰石多孔微球。
各步骤的工艺参数如下:
步骤(1)中乙醇用量为105ml,去离子水为35ml,纳米四氧化三铁分散液为1.2~1.3ml,浓度为0.5g/ml。
步骤(2)中氨水用量为2ml,氨水的质量分数为27%,快速加入。
步骤(3)中硅酸四已酯用量为3ml,注射器缓慢滴加。
步骤(7)中醋酸溶液的浓度为10vol .%。
步骤(7)中的鲍鱼壳粉末与步骤(8)中磷酸的用量需保证Ca/P摩尔比为n(Ca2+)/n(PO4 3-)= 1 .67:1添加。
步骤(9)中柠檬酸钠用量为0 .236g,尿素使用量为6g。
步骤(12)中产物用去离子水洗离3次,再用无水乙醇洗涤2~3次,磁吸洗涤分离。
本发明的显著优点在于:
(1)本发明具体涉及一种不产生二次污染的对染料等具有高效吸附性能的表面沉积超顺磁纳米粒的鲍鱼壳羟基磷灰石多孔微球的制备方法。以废弃鲍鱼壳和纳米四氧化三铁为主要原料,以柠檬酸钠为模板剂,通过水热合成自组装形成具有磁性的羟基磷灰石微球,将此羟基磷灰石微球作为吸附剂应用于水溶液染料的吸附中,表现出良好的吸附性,吸附率可达74%。本发明凭借四氧化三铁本身独特的超顺磁性,可利用磁铁等磁性物质收集,具有可回收性,且制备方法简便,达到了“变废为宝”的目的。
(2)本发明原料来源广泛,开发了废弃贝壳的高附加值利用,有效减轻了环境负担,减少了贝壳污染与浪费,且成本低廉、可再生效率高,具有良好的生态效益和经济价值。
(3)用Fe3O4等材料制备磁性微球,作为高效吸附剂,想法较为新颖,目前在该方面研究较少。
附图说明
图1为实施例1制得的表面沉积超顺磁纳米粒的鲍鱼壳羟基磷灰石多孔微球的扫描电子显微镜图谱(50000×);
图2为实施例2制得的表面沉积超顺磁纳米粒的鲍鱼壳羟基磷灰石多孔微球的扫描电子显微镜图谱(16000×);
图3为实施例2制得的表面沉积超顺磁纳米粒的鲍鱼壳羟基磷灰石多孔微球的扫描电子显微镜图谱(60000×)。
具体实施方式
为了使本发明所述的内容更加便于理解,下面结合具体实施方式对本发明所述的技术方案做进一步的说明,但是下述的实例仅仅是本发明其中的例子而已,并不代表本发明所限定的权利保护范围,本发明的权利保护范围以权利要求书为准。
实施例1(纳米四氧化三铁未包覆硅层)
(1)用流水冲洗鲍鱼壳,去除鲍鱼壳的表层物质,然后自然风干;
(2)将风干后的鲍鱼壳粉碎研磨筛选,获得鲍鱼壳粉末;
(3)将0.05g鲍鱼壳粉末溶于20ml 10vol .%醋酸溶液中,搅拌至无气泡产生,而后用离心机(8000rpm,5min)进行离心得到上清液;
(4)将步骤(3)得到的上清液定容至50ml,而后用注射泵以50ml/h的滴加速度向其中缓慢滴加0.06mol/L磷酸溶液50ml,并置于磁力搅拌器(200rpm)搅拌1h;
(5)向步骤(4)搅拌后的溶液中添加0.236g柠檬酸钠、6g尿素并置于磁力搅拌器(200rpm)持续搅拌20min至完全溶解;
(6)向步骤(5)制得的反应液中加入纳米四氧化三铁分散液3ml(浓度为0.5g/ml),室温下搅拌(350rpm)1h;
(7)将步骤(6)制得的反应液倒入高压反应釜中并置于90℃恒温干燥箱中进行水热反应40h;
(8)反应结束后,自然冷却至室温,水洗3次、醇洗3次磁吸分离,60℃干燥2h,得到所述的表面沉积超顺磁纳米粒的鲍鱼壳羟基磷灰石多孔微球。
实施例2
(1)配制105ml乙醇和35ml水的混合溶液,加入超声分散的纳米四氧化三铁分散液1.2ml(浓度为0.5g/ml),超声15min;
(2)将步骤(1)溶液装入三颈烧瓶,置于磁力搅拌器中搅拌,搅拌过程中(180rpm)快速加入2ml氨水(质量分数为27%),搅拌10min;
(3)向步骤(2)溶液中缓慢滴加3ml硅酸四已酯,持续机搅(180rpm)8h;
(4)将步骤(3)中溶液醇洗磁吸分离至上清液澄清,得到包覆硅层的纳米四氧化三铁;
(5)用流水冲洗鲍鱼壳,去除鲍鱼壳的表层物质,然后自然风干;
(6)将风干后的鲍鱼壳粉碎研磨筛选,获得鲍鱼壳粉末;
(7)将0.05g鲍鱼壳粉末溶于20ml 10vol .%醋酸溶液中,搅拌至无气泡产生,而后用离心机(8000rpm,5min)进行离心得到上清液;
(8)将步骤(7)得到的上清液定容至50ml,而后用注射泵以50ml/h的滴加速度向其中缓慢滴加0.06mol/L磷酸溶液50ml,并置于磁力搅拌器(200rpm)搅拌1h;
(9)向步骤(8)搅拌后的溶液中添加0.236g柠檬酸钠、6g尿素并置于磁力搅拌器(200rpm)持续搅拌20min至完全溶解;
(10)向步骤(9)制得的反应液中加入步骤(4)所得的包覆硅层的纳米四氧化三铁3ml,室温下搅拌(350rpm)1h;
(11)将步骤(10)制得的反应液倒入高压反应釜中并置于90℃恒温干燥箱中进行水热反应40h;
(12)反应结束后,自然冷却至室温,水洗3次、醇洗3次磁吸分离,60℃干燥2h,得到所述的表面沉积超顺磁纳米粒的鲍鱼壳羟基磷灰石多孔微球。
实施例3
(1)配制105ml乙醇和35ml水的混合溶液,加入超声分散的纳米四氧化三铁分散液1.2ml(浓度为0.5g/ml),超声15min;
(2)将步骤(1)溶液装入三颈烧瓶,置于磁力搅拌器中搅拌,搅拌过程中(180rpm)快速加入2ml氨水(质量分数为27%),搅拌10min;
(3)向步骤(2)溶液中缓慢滴加3ml硅酸四已酯,持续机搅(180rpm)8h;
(4)将步骤(3)中溶液醇洗磁吸分离至上清液澄清,得到包覆硅层的纳米四氧化三铁Fe@Si;
(5)用流水冲洗鲍鱼壳,去除鲍鱼壳的表层物质,然后自然风干;
(6)将风干后的鲍鱼壳粉碎研磨筛选,获得鲍鱼壳粉末;
(7)将0.05g鲍鱼壳粉末溶于20ml 10vol .%醋酸溶液中,搅拌至无气泡产生,而后用离心机(8000rpm,5min)进行离心得到上清液;
(8)将步骤(7)得到的上清液定容至50ml,而后用注射泵以50ml/h的滴加速度向其中缓慢滴加0.06mol/L磷酸溶液50ml,并置于磁力搅拌器(200rpm)搅拌1h;
(9)向步骤(8)搅拌后的溶液中添加0 .236g柠檬酸钠、6g尿素并置于磁力搅拌器(200rpm)持续搅拌20min至完全溶解;
(10)向步骤(9)制得的反应液中加入步骤(4)所得的包覆硅层的纳米四氧化三铁5ml,室温下搅拌(350rpm)1h;
(11)将步骤(10)制得的反应液倒入高压反应釜中并置于90℃恒温干燥箱中进行水热反应40h;
(12)反应结束后,自然冷却至室温,水洗3次、醇洗2次磁吸分离,60℃干燥2h,得到所述的表面沉积超顺磁纳米粒的鲍鱼壳羟基磷灰石多孔微球。
实施例4
(1)配制105ml乙醇和35ml水的混合溶液,加入超声分散的纳米四氧化三铁分散液1.2ml(浓度为0.5g/ml),超声15min;
(2)将步骤(1)溶液装入三颈烧瓶,置于磁力搅拌器中搅拌,搅拌过程中(180rpm)快速加入2ml氨水(质量分数为27%),搅拌10min;
(3)向步骤(2)溶液中缓慢滴加3ml硅酸四已酯,持续机搅(180rpm)8h;
(4)将步骤(3)中溶液醇洗磁吸分离至上清液澄清,得到包覆硅层的纳米四氧化三铁Fe@Si;
(5)用流水冲洗鲍鱼壳,去除鲍鱼壳的表层物质,然后自然风干;
(6)将风干后的鲍鱼壳粉碎研磨筛选,获得鲍鱼壳粉末;
(7)将0.05g鲍鱼壳粉末溶于20ml 10vol .%醋酸溶液中,搅拌至无气泡产生,而后用离心机(8000rpm,5min)进行离心得到上清液;
(8)将步骤(7)得到的上清液定容至50ml,而后用注射泵以50ml/h的滴加速度向其中缓慢滴加0.06mol/L磷酸溶液50ml,并置于磁力搅拌器(200rpm)搅拌1h;
(9)向步骤(8)搅拌后的溶液中添加0 .236g柠檬酸钠、6g尿素并置于磁力搅拌器(200rpm)持续搅拌20min至完全溶解;
(10)向步骤(9)制得的反应液中加入步骤(4)所得的包覆硅层的纳米四氧化三铁7ml,室温下搅拌(350rpm)1h;
(11)将步骤(10)制得的反应液倒入高压反应釜中并置于90℃恒温干燥箱中进行水热反应40h;
(12)反应结束后,自然冷却至室温,水洗3次、醇洗3次磁吸分离,60℃干燥2h,得到所述的表面沉积超顺磁纳米粒的鲍鱼壳羟基磷灰石多孔微球。
以上所述仅为本发明的较佳实施例,凡依本发明申请专利范围所做的均等变化与修饰,皆应属本发明的涵盖范围。
Claims (10)
1.表面沉积超顺磁纳米粒的鲍鱼壳羟基磷灰石多孔微球,其特征在于:以废弃鲍鱼壳和纳米四氧化三铁为主要原料,利用柠檬酸钠作为模板剂,结合水热合成技术制备表面沉积超顺磁纳米粒的鲍鱼壳羟基磷灰石多孔微球。
2.根据权利要求1所述的表面沉积超顺磁纳米粒的鲍鱼壳羟基磷灰石多孔微球的制备方法,其特征在于:首先制备包覆硅层的纳米四氧化三铁;其后对鲍鱼壳的表层物质进行冲洗,然后风干,研磨筛选获得鲍鱼壳粉末;将鲍鱼壳粉末溶于醋酸溶液中,搅拌至无气泡产生,而后进行离心得到上清液;取上清液,向其中滴加磷酸溶液,搅拌,然后添加柠檬酸钠、尿素并持续搅拌至完全溶解;向体系中加入包覆硅层的纳米四氧化三铁,充分搅拌;倒入高压反应釜中进行水热反应;反应结束后,自然冷却至室温,水洗、醇洗磁吸分离,干燥,最后得到所述的表面沉积超顺磁纳米粒的鲍鱼壳羟基磷灰石多孔微球。
3.根据权利要求2所述的表面沉积超顺磁纳米粒的鲍鱼壳羟基磷灰石多孔微球的制备方法,其特征在于:具体包含以下步骤:
(1)配制乙醇和水混合溶液,加入超声分散的纳米四氧化三铁分散液,超声15min;
(2)向步骤(1)体系中快速加入氨水,搅拌10min;
(3)向步骤(2)体系中缓慢滴加硅酸四已酯,持续搅拌8h;
(4)将步骤(3)体系进行醇洗磁吸分离,得到包覆硅层的纳米四氧化三铁;
(5)用流水冲洗鲍鱼壳,去除表层物质,然后自然风干;
(6)将风干后的鲍鱼壳粉碎研磨筛选,获得鲍鱼壳粉末;
(7)将鲍鱼壳粉末溶于醋酸溶液中,搅拌至无气泡产生,而后进行离心得到上清液;
(8)将步骤(7)得到的上清液定容至50ml,而后向其中缓慢滴加磷酸溶液,搅拌1h;
(9)向步骤(8)搅拌后的溶液中添加柠檬酸钠、尿素并持续搅拌20min至完全溶解;
(10)向步骤(9)制得的反应液中加入步骤(4)所得的包覆硅层的纳米四氧化三铁,室温下搅拌1h;
(11)将步骤(10)制得的反应体系倒入高压反应釜中并置于恒温干燥箱中进行水热反应;
(12)反应结束后,自然冷却至室温,水洗、醇洗磁吸分离,干燥,得到所述的表面沉积超顺磁纳米粒的鲍鱼壳羟基磷灰石多孔微球。
4.根据权利要求3所述的表面沉积超顺磁纳米粒的鲍鱼壳羟基磷灰石多孔微球的制备方法,其特征在于:步骤(1)中乙醇用量为105ml,去离子水为35ml,纳米四氧化三铁分散液为1.2~1.3ml,浓度为0.5g/ml;步骤(2)中氨水用量为2ml。
5.根据权利要求3所述的表面沉积超顺磁纳米粒的鲍鱼壳羟基磷灰石多孔微球的制备方法,其特征在于:步骤(3)中硅酸四已酯用量为3ml,反应期间转速为180~200rpm。
6.根据权利要求3所述的表面沉积超顺磁纳米粒的鲍鱼壳羟基磷灰石多孔微球的制备方法,其特征在于:步骤(7)中醋酸溶液的浓度为10vol .%,离心转数为8000rpm,离心时间为5min。
7.根据权利要求3所述的表面沉积超顺磁纳米粒的鲍鱼壳羟基磷灰石多孔微球的制备方法,其特征在于:步骤(7)中的鲍鱼壳粉末与步骤(8)中磷酸的用量需保证Ca/P摩尔比为n(Ca2+)/n(PO4 3-)= 1 .67:1。
8.根据权利要求3所述的表面沉积超顺磁纳米粒的鲍鱼壳羟基磷灰石多孔微球的制备方法,其特征在于:步骤(8)中的磷酸溶液浓度为0.06mol/L,滴加速度为50ml/h。
9.根据权利要求3所述的表面沉积超顺磁纳米粒的鲍鱼壳羟基磷灰石多孔微球的制备方法,其特征在于:步骤(9)中柠檬酸钠用量为0.236g,尿素使用量为6g,搅拌转速200~300rpm。
10.根据权利要求3所述的表面沉积超顺磁纳米粒的鲍鱼壳羟基磷灰石多孔微球的制备方法,其特征在于:步骤(11)中水热反应温度为90℃,时间为40h。
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