CN106268706A - 一种磁性纳米无机砷吸附剂的制备方法及其应用 - Google Patents
一种磁性纳米无机砷吸附剂的制备方法及其应用 Download PDFInfo
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- 239000003463 adsorbent Substances 0.000 title claims abstract description 57
- 229910052785 arsenic Inorganic materials 0.000 title claims abstract description 50
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 title claims abstract description 50
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 229910002518 CoFe2O4 Inorganic materials 0.000 claims abstract description 64
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 45
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 28
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000002122 magnetic nanoparticle Substances 0.000 claims abstract description 22
- 229910003321 CoFe Inorganic materials 0.000 claims abstract description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000008239 natural water Substances 0.000 claims abstract description 9
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 claims abstract description 7
- VHKFFPOTSWQHPK-UHFFFAOYSA-N C(C)O.C1(=CC(=CC(=C1)C(=O)O)C(=O)O)C(=O)O Chemical compound C(C)O.C1(=CC(=CC(=C1)C(=O)O)C(=O)O)C(=O)O VHKFFPOTSWQHPK-UHFFFAOYSA-N 0.000 claims abstract description 6
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims abstract description 6
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims abstract description 6
- 229940097267 cobaltous chloride Drugs 0.000 claims abstract description 6
- 230000004048 modification Effects 0.000 claims abstract description 6
- 238000012986 modification Methods 0.000 claims abstract description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 6
- 235000017281 sodium acetate Nutrition 0.000 claims abstract description 6
- 239000001632 sodium acetate Substances 0.000 claims abstract description 6
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- AQRRVVAHUPXEMW-UHFFFAOYSA-L ethanol;iron(2+);dichloride Chemical compound [Cl-].[Cl-].[Fe+2].CCO AQRRVVAHUPXEMW-UHFFFAOYSA-L 0.000 claims description 6
- 238000002955 isolation Methods 0.000 claims description 6
- 229920001030 Polyethylene Glycol 4000 Polymers 0.000 claims description 5
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- 239000007789 gas Substances 0.000 claims 1
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- 239000013291 MIL-100 Substances 0.000 description 5
- 150000002500 ions Chemical class 0.000 description 5
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
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- QJZYHAIUNVAGQP-UHFFFAOYSA-N 3-nitrobicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic acid Chemical compound C1C2C=CC1C(C(=O)O)C2(C(O)=O)[N+]([O-])=O QJZYHAIUNVAGQP-UHFFFAOYSA-N 0.000 description 1
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- IQFVPQOLBLOTPF-HKXUKFGYSA-L congo red Chemical compound [Na+].[Na+].C1=CC=CC2=C(N)C(/N=N/C3=CC=C(C=C3)C3=CC=C(C=C3)/N=N/C3=C(C4=CC=CC=C4C(=C3)S([O-])(=O)=O)N)=CC(S([O-])(=O)=O)=C21 IQFVPQOLBLOTPF-HKXUKFGYSA-L 0.000 description 1
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- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
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- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
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- 239000010452 phosphate Substances 0.000 description 1
- -1 sulfate radical Chemical class 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
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Abstract
一种磁性纳米无机砷吸附剂的制备方法，所述吸附剂为具有介孔核壳结构的CoFe2O4@MIL‑100(Fe)，步骤如下：1)将氯化钴、氯化铁、醋酸钠、聚乙二醇‑6000溶于乙二醇中，160℃水热反应16小时制得介孔CoFe2O4磁性纳米粒子；2)将CoFe2O4纳米粒子加入到巯基乙酸的乙醇溶液中，氮气保护搅拌24小时进行表面改性；3)将改性后的CoFe2O4交替浸泡在氯化铁和均苯三酸乙醇溶液中，通过层层自组装的方法制得目标物。本发明的优点是：制备工艺简单、易于实施、成本低；该磁性纳米吸附剂对无机砷去除效率高，抗干扰能力强，可在无需任何前处理的条件下实现天然水中三价砷与五价砷的同时高效去除。
Description
技术领域
本发明属于纳米材料制备领域和水污染处理领域，尤其涉及一种磁性纳米无机砷吸附剂的制备方法及其应用。
背景技术
砷(As)广泛分布于自然界中，天然水中的无机砷[As(V)和As(III)]污染已成为一个世界性的难题。当前全世界有超过一亿人仍在饮用砷污染地下水，而长期饮用砷污染水对人体存在极大的危害，世界卫生组织(WHO)已经颁布法令严格控制了饮用水中的砷含量。因此，开发一种经济、高效、环境友好、适用范围广的吸附剂去除天然水中的无机砷对人类健康十分重要。
目前，报道的无机砷吸附剂主要有以下几种类型：活性炭纳米材料，如，1)C.L.Chuang,M.Fan,M.Xu,R.C.Brown,S.Sung,B.Saha,C.P.Huang,Chemosphere 2005,61(4):478-483；2)W.F.Chen,R.Parette,J.Y.Zou,F.S.Cannon,B.A.Dempsey,WaterRes.2007,41(9):1851-1858；基于Fe3O4的磁性纳米材料，如，3)L.Guo,P.Ye,J.Wang,F.Fu,Z.Wu,J.Hazard.Mater.2015，298：28-35；4)L.Feng,M.Cao,X.Ma,Y.Zhu,C.Hu,J.Hazard.Mater.2012，217：439-446；5)W.Jiang,X.Chen,Y.Niu,B.Pan,J.Hazard.Mater.2012，243：319-325；基于TiO2的纳米材料，如，6)M.Pena,X.Meng,G.P.Korfiatis,C.Jing,Environ.Sci.Technol.2006，40：1257-1262；7)W.W.Bennett,P.R.Teasdale,J.G.Panther,D.T.Welsh,D.F.Jolley,Anal.Chem.2010，82：7401-7407；8)J.Cui,J.Du,S.Yu,C.Jing,T.Chan,Environ.Sci.Pollut.R.2015，22：8224-8234。虽然这些吸附剂具有较简单的制备工艺、较低廉的制备成本等优点，但同时存在吸附效率低、抗干扰能力差、应用范围窄、不易回收等缺点。因此，有必要制备新型的、具有较强抗干扰能力的高效无机砷吸附剂。
发明内容
本发明的目的是针对上述存在问题，提供一种工艺简单、易于实施、成本低廉的磁性纳米无机砷吸附剂的制备方法及其应用。
本发明的技术方案：
一种磁性纳米无机砷吸附剂的制备方法，所述磁性纳米无机砷吸附剂为具有介孔核壳结构的CoFe2O4@MIL-100(Fe)，步骤如下：
1)将氯化钴、氯化铁、醋酸钠和聚乙二醇-6000溶于乙二醇中，在50℃条件下搅拌20分钟后转入反应釜，160℃水热反应16小时，将黑色沉淀磁性分离并用乙醇和水分别洗涤2次，真空干燥制得介孔CoFe2O4磁性纳米粒子；
2)将上述介孔CoFe2O4磁性纳米粒子加入到浓度为0.58mM的巯基乙酸的乙醇溶液中，氮气保护下、室温搅拌24小时进行表面改性，用乙醇洗净表面残留的巯基乙酸，制得改性的MAA-CoFe2O4；
3)在70℃条件下将上述改性的MAA-CoFe2O4交替浸泡在氯化铁-乙醇溶液中15分钟和均苯三酸-乙醇溶液中30分钟，经过10个循环的层层自组装包裹后，磁性分离用乙醇洗涤2次，真空干燥后制得磁性纳米无机砷吸附剂CoFe2O4@MIL-100(Fe)。
所述步骤1)中氯化钴、氯化铁、醋酸钠、聚乙二醇-6000与乙二醇的用量比为148.7mg:337.9mg:900.0mg:500.0mg:10mL。
所述步骤2)中介孔CoFe2O4磁性纳米粒子与巯基乙酸的乙醇溶液的用量比为50.0mg:10mL。
所述步骤3)中氯化铁-乙醇溶液和均苯三酸-乙醇溶液的浓度均为50mM，改性的MAA-CoFe2O4与氯化铁-乙醇溶液的用量比为50.0mg:10mL，改性的MAA-CoFe2O4与均苯三酸-乙醇溶液的用量比为50.0mg:10mL。
一种所制备的磁性纳米无机砷吸附剂的应用，用于高效去除天然水中无机砷。
本发明的优点是：
该介孔核壳结构磁性纳米吸附剂制备工艺简单、易于实施、成本低廉、吸附效率高、抗干扰能力强、pH应用范围广，具有无需复杂样品前处理、无干扰、高效去除天然水中无机砷的应用潜力。
附图说明
图1为CoFe2O4磁性纳米粒子和CoFe2O4@MIL-100(Fe)磁性纳米吸附剂的形貌图，其中：A为CoFe2O4磁性纳米粒子透射电镜图；B为CoFe2O4磁性纳米粒子高分辨率透射电镜图；C为CoFe2O4@MIL-100(Fe)磁性纳米吸附剂透射电镜图；D为CoFe2O4@MIL-100(Fe)磁性纳米吸附剂高分辨率透射电镜图；插图为两种磁性纳米粒子的动态光散射粒径分布。
图2为CoFe2O4磁性纳米粒子(a)和CoFe2O4@MIL-100(Fe)磁性纳米吸附剂(b)的性质表征，其中：A为其红外光谱图；B为其热重表征图；C为其磁滞回线的表征图；D为其X射线粉末衍射图；E为氮气吸附比表面积表征图；F为孔径分布表征图。
图3为样品pH和离子强度以及干扰离子对不同吸附剂去除天然水中无机砷效率的影响，其中：A，B分别为不同pH值下CoFe2O4(a)，MIL-100(Fe)(b)，CoFe2O4@MIL-100(Fe)(c)对As(V)和As(III)的去除效率；C，D为CoFe2O4@MIL-100(Fe)在0.2M NaCl离子强度下对As(V)和As(III)的去除效率；E，F为不同干扰离子对CoFe2O4和CoFe2O4@MIL-100(Fe)去除As(V)和As(III)效率的影响。
图4为CoFe2O4磁性纳米粒子(a)和CoFe2O4@MIL-100(Fe)磁性纳米吸附剂(b)的zeta电位图。
图5为CoFe2O4@MIL-100(Fe)磁性纳米吸附剂对无机砷的吸附动力学和热力学曲线，其中：A,B为不同As(V)和As(III)浓度0.1mg L-1(a)，1mg L-1(b)，10mg L-1(c)下，0.5gL-1CoFe2O4@MIL-100(Fe)磁性纳米吸附剂的吸附动力学曲线，插图为吸附初始30min或60min内吸附动力学曲线的放大图；C,D为不同温度25℃(a)，40℃(b)，50℃(c)条件下，0.5gL-1CoFe2O4@MIL-100(Fe)磁性纳米吸附剂对As(V)和As(III)的吸附热力学曲线。
图6为两种简单的水处理模式实际应用照片，其中：A,B为CoFe2O4@MIL-100(Fe)磁性纳米吸附剂静态吸附实际应用照片；C,D为将CoFe2O4@MIL-100(Fe)磁性纳米吸附剂封装于滤头内的动态吸附模式实际应用照片；E,F为经滤头处理前后实际水样对比照片。
具体实施方式
实施例：
一种磁性纳米无机砷吸附剂的制备方法，所述磁性纳米无机砷吸附剂为具有介孔核壳结构的CoFe2O4@MIL-100(Fe)，步骤如下：
1)将148.7mg氯化钴、337.9mg氯化铁、900.0mg醋酸钠、500.0mg聚乙二醇-6000溶于10mL乙二醇中，在50℃条件下搅拌20分钟形成均一棕色溶液后转入反应釜，160℃水热反应16小时，得到的黑色沉淀经磁性分离并用乙醇和水各洗涤2次，真空干燥制得介孔CoFe2O4磁性纳米粒子；
2)将50mg上述介孔CoFe2O4磁性纳米粒子加入到10mL 0.58mM巯基乙酸(MAA)的乙醇溶液中，氮气保护，室温搅拌24小时进行表面改性，用乙醇洗净表面残留的巯基乙酸，制得改性后的MAA-CoFe2O4；
3)在70℃条件下将上述改性后的MAA-CoFe2O4交替浸泡在10mL 50mM氯化铁乙醇溶液中15分钟和10mL 50mM均苯三酸乙醇溶液中30分钟，每一步之间均用乙醇洗净表面残留药品，经过10个循环层层自组装包裹后，磁性分离，乙醇洗涤2次，空干燥制得介孔核壳结构CoFe2O4@MIL-100(Fe)。
图1为CoFe2O4磁性纳米粒子和CoFe2O4@MIL-100(Fe)磁性纳米吸附剂的形貌图，其中：A为CoFe2O4磁性纳米粒子透射电镜图；B为CoFe2O4磁性纳米粒子高分辨率透射电镜图；C为CoFe2O4@MIL-100(Fe)磁性纳米吸附剂透射电镜图；D为CoFe2O4@MIL-100(Fe)磁性纳米吸附剂高分辨率透射电镜图；插图为两种磁性纳米粒子的动态光散射粒径分布。说明CoFe2O4@MIL-100(Fe)磁性纳米吸附剂具有良好的介孔性质与核壳结构。
图2为CoFe2O4磁性纳米粒子(a)和CoFe2O4@MIL-100(Fe)磁性纳米吸附剂(b)的性质表征，其中：A为其红外光谱图；B为其热重表征图；C为其磁滞回线的表征图；D为其X射线粉末衍射图；ABCD四个表征图证明了MIL-100(Fe)壳已成功包覆在CoFe2O4磁性纳米粒子核的外层，且CoFe2O4@MIL-100(Fe)磁性纳米吸附剂能够容易的实现磁性回收分离。E为氮气吸附比表面积表征图和F为孔径分布表征图。说明该CoFe2O4@MIL-100(Fe)磁性纳米吸附剂具有较大的比表面积和良好的介孔结构，具有作为天然水无机砷的高效吸附剂的应用潜力。
图3为pH，离子强度及干扰离子对不同吸附剂去除天然水中无机砷效率的影响，其中：A，B分别为不同pH值下0.5mg L-1CoFe2O4(a)，MIL-100(Fe)(b)，CoFe2O4@MIL-100(Fe)(c)对1mg L-1As(V)和As(III)的去除效率，说明CoFe2O4@MIL-100(Fe)磁性纳米吸附剂具有宽的pH应用范围；C，D为0.5mg L-1CoFe2O4@MIL-100(Fe)在0.2M NaCl离子强度下对1mg L-1As(V)和As(III)的去除效率，说明CoFe2O4@MIL-100(Fe)磁性纳米吸附剂具有强的抗离子强度干扰能力；E，F为不同干扰离子(1mM硫酸根，碳酸根，硅酸根，刚果红，0.1mM磷酸根，50mg L-1腐殖酸)对0.5mg L-1CoFe2O4和CoFe2O4@MIL-100(Fe)去除1mg L-1As(V)和As(III)效率的影响，说明包覆上MIL-100(Fe)壳后，吸附剂的抗干扰能力得到了显著提高。图3证明了CoFe2O4@MIL-100(Fe)磁性纳米吸附剂在吸附去除无机砷方面的应用潜力，可直接应用于天然水中无机砷的高效去除而无需任何前处理。
图4为CoFe2O4磁性纳米粒子(a)和CoFe2O4@MIL-100(Fe)磁性纳米吸附剂(b)的zeta电位图。包覆上MIL-100(Fe)壳后，吸附剂的zeta电位显著下降，说明由于MOFs壳的静电排斥作用，可以起到提高吸附剂的抗干扰离子能力的作用。
图5为CoFe2O4@MIL-100(Fe)磁性纳米吸附剂对无机砷的吸附动力学和热力学曲线，其中：A,B为不同As(V)和As(III)浓度0.1mg L-1(a)，1mg L-1(b)，10mg L-1(c)下，0.5gL-1CoFe2O4@MIL-100(Fe)磁性纳米吸附剂的吸附动力学曲线，插图为吸附初始30min或60min内吸附动力学曲线的放大图；C,D为不同温度25℃(a)，40℃(b)，50℃(c)条件下，0.5gL-1CoFe2O4@MIL-100(Fe)磁性纳米吸附剂对As(V)和As(III)的吸附热力学曲线。证明该吸附剂对天然水中无机砷的吸附速率快[对于0.1mg L-1As(V)和As(III)，2分钟内即可达到吸附平衡]，吸附容量高[As(V)的饱和吸附容量为114.8mg g-1，As(III)的饱和吸附容量为143.6mg g-1]，具有实际应用的潜力。
将实施例中制备的CoFe2O4@MIL-100(Fe)磁性纳米吸附剂用于实际水样，实现天然水中无机砷的吸附去除：
实际高砷水样取自山西山阴(无机砷浓度约为0.5mg L-1)。在静态吸附实验中，将1g CoFe2O4@MIL-100(Fe)磁性纳米吸附剂加入到500mL高砷实际水样中，吸附12h后磁性分离回收，用ICP-MS测量水样中残留无机砷浓度；在动态吸附实验中，将50mg CoFe2O4@MIL-100(Fe)磁性纳米吸附剂封装于0.2μm滤头内，用注射器将50mL高砷天然水样从滤头缓慢推出，ICP-MS测量水样中残留无机砷浓度。
图6为两种简单的水处理模式实际应用照片，其中：A,B为CoFe2O4@MIL-100(Fe)磁性纳米吸附剂静态吸附实际应用照片，经过静态吸附后，实际水样中残留的砷浓度降低至4.2μg L-1，符合饮用水安全标准(低于10μg L-1)，且吸附剂易于磁性回收分离；C,D为将CoFe2O4@MIL-100(Fe)磁性纳米吸附剂封装于滤头内的动态吸附模式实际应用照片，E,F为经滤头处理前后实际水样对比照片，经过动态吸附后，实际水样中残留的砷浓度降低至8.6μg L-1，符合饮用水安全标准，且浑浊度由4.9降低至1.2NTU，水质得到了明显提升。图6说明CoFe2O4@MIL-100(Fe)磁性纳米吸附剂具有吸附去除天然水中无机砷的实际应用潜力。
Claims (5)
1.一种磁性纳米无机砷吸附剂的制备方法，其特征在于所述磁性纳米无机砷吸附剂为具有介孔核壳结构的CoFe2O4@MIL-100(Fe)，步骤如下：
1)将氯化钴、氯化铁、醋酸钠和聚乙二醇-6000溶于乙二醇中，在50℃条件下搅拌20分钟后转入反应釜，160℃水热反应16小时，将黑色沉淀磁性分离并用乙醇和水分别洗涤2次，真空干燥制得介孔CoFe2O4磁性纳米粒子；
2)将上述介孔CoFe2O4磁性纳米粒子加入到浓度为0.58mM的巯基乙酸的乙醇溶液中，氮气保护下、室温搅拌24小时进行表面改性，用乙醇洗净表面残留的巯基乙酸，制得改性的MAA-CoFe2O4；
3)在70℃条件下将上述改性的MAA-CoFe2O4交替浸泡在氯化铁-乙醇溶液中15分钟和均苯三酸-乙醇溶液中30分钟，经过10个循环的层层自组装包裹后，磁性分离用乙醇洗涤2次，真空干燥后制得磁性纳米无机砷吸附剂CoFe2O4@MIL-100(Fe)。
2.根据权利要求1所述磁性纳米无机砷吸附剂的制备方法，其特征在于：所述步骤1)中氯化钴、氯化铁、醋酸钠、聚乙二醇-6000与乙二醇的用量比为148.7mg:337.9mg:900.0mg:500.0mg:10mL。
3.根据权利要求1所述磁性纳米无机砷吸附剂的制备方法，其特征在于：所述步骤2)中介孔CoFe2O4磁性纳米粒子与巯基乙酸的乙醇溶液的用量比为50.0mg:10mL。
4.根据权利要求1所述磁性纳米无机砷吸附剂的制备方法，其特征在于：所述步骤3)中氯化铁-乙醇溶液和均苯三酸-乙醇溶液的浓度均为50mM，改性的MAA-CoFe2O4与氯化铁-乙醇溶液的用量比为50.0mg:10mL，改性的MAA-CoFe2O4与均苯三酸-乙醇溶液的用量比为50.0mg:10mL。
5.一种权利要求1所制备的磁性纳米无机砷吸附剂的应用，其特征在于：用于高效去除天然水中无机砷。
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