CN116393131A - 一种mil-88衍生磁性碳纳米材料及其制备方法和应用 - Google Patents
一种mil-88衍生磁性碳纳米材料及其制备方法和应用 Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 26
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- 239000002086 nanomaterial Substances 0.000 title claims abstract description 23
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- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 13
- 229940044631 ferric chloride hexahydrate Drugs 0.000 claims abstract description 11
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- NQXWGWZJXJUMQB-UHFFFAOYSA-K iron trichloride hexahydrate Chemical group O.O.O.O.O.O.[Cl-].Cl[Fe+]Cl NQXWGWZJXJUMQB-UHFFFAOYSA-K 0.000 claims abstract description 11
- 239000001530 fumaric acid Substances 0.000 claims abstract description 9
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims abstract description 9
- QGUAJWGNOXCYJF-UHFFFAOYSA-N cobalt dinitrate hexahydrate Chemical compound O.O.O.O.O.O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QGUAJWGNOXCYJF-UHFFFAOYSA-N 0.000 claims abstract description 8
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- GSDSWSVVBLHKDQ-UHFFFAOYSA-N 9-fluoro-3-methyl-10-(4-methylpiperazin-1-yl)-7-oxo-2,3-dihydro-7H-[1,4]oxazino[2,3,4-ij]quinoline-6-carboxylic acid Chemical compound FC1=CC(C(C(C(O)=O)=C2)=O)=C3N2C(C)COC3=C1N1CCN(C)CC1 GSDSWSVVBLHKDQ-UHFFFAOYSA-N 0.000 description 14
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- HVENHVMWDAPFTH-UHFFFAOYSA-N iron(3+) trinitrate hexahydrate Chemical compound O.O.O.O.O.O.[Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HVENHVMWDAPFTH-UHFFFAOYSA-N 0.000 description 1
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Abstract
本发明涉及一种MIL‑88衍生磁性碳纳米材料及其制备方法和应用，所述制备方法通过水热‑碳化为基本工艺，以六水合硝酸钴为Co2+来源，以六水合氯化铁为Fe3+为MIL‑88金属配体，以富马酸为有机配体，原位水热合成Co@MIL‑88的基础上通过一次碳化合成MIL‑88衍生磁性碳纳米材料。本发明所述的制备方法具有工艺简单、可操作性强、制备周期短、收率高且易于实现工业化生产的特点。
Description
技术领域
本发明涉及一种MIL-88衍生磁性碳纳米材料及其制备方法和应用，属于MOF衍生材料制备的技术领域。
技术背景
药品和个人护理产品(PPCPs)，包括抗炎化合物、抗生素和激素，通过工厂、医院和城市污水处理厂的污水逐渐扩散到水环境中。氧氟沙星(OFX)作为一种广谱氟喹诺酮类抗生素，临床上常用来治疗细菌感染，但OFX的过度使用和滥用导致其被排放到自然水体中，影响非目标微生物的生长从而导致微生态系统失衡。对于抗生素废水治理，传统的吸附法、生物法并无法实现高效的去除。想比之下，高级氧化技术(AOPs)表现出高效的处理效果，过氧化氢(H2O2)、过氧单硫酸盐(PMS)、和过氧二硫酸盐(PDS)等氧化剂活化过程中产生的羟基自由基(HO·,Eo＝1.9-2.7V)、硫酸根自由基(SO4 ·-,Eo＝2.6-3.1V)、超氧自由基(·O2-,Eo＝0.33V)和单线态氧(1O2,Eo＝2.2V)能够有效降解污染物。
然而，虽然非均相催化反应能够最大程度地降低均相反应过程中金属离子对自然环境造成的二次污染，但粉末非均相催化剂的回收难问题却抑制了非均相催化反应在实际生产中的进一步应用。针对该问题，赋予催化剂磁性提高其回收利用效率是解决粉末催化剂回收难问题的关键。
MOFs是金属有机骨架化合物(英文名称Metal organic Frameworks)的简称。是由无机金属中心(金属离子或金属簇)与桥连的有机配体通过自组装相互连接，形成的一类具有周期性网络结构的晶态多孔材料。MOFs是一种有机-无机杂化材料，也称配位聚合物(coordination polymer)，它既不同于无机多孔材料，也不同于一般的有机配合物。兼有无机材料的刚性和有机材料的柔性特征，具有良好的化学稳定性和热稳定性。此外，材料比表面积大且孔道结构稳定，故而在气体存运、载药、催化、物质分离等方面具有良好的应用前景。MIL-88作为一种典型的Fe基MOF材料，虽然由于MIL-88自身的电子传递性能焦瑞，但在已经实现Fe活性位点均匀分布的前提下却能够作为前驱体和支撑CoFe2O4的形成，赋予催化剂磁性和催化性能。
发明内容
针对上述问题，本发明的目的在于提供一种MIL-88衍生磁性碳纳米材料及及其制备方法和应用。
一方面，本发明提供了一种MIL-88衍生磁性碳纳米材料，所述的材料组成结构通式为CoFexOy@C-Z，所述的x为Fe3+和Co2+的摩尔比，y为O和Co2+的摩尔比，Z为制备碳化温度。
另一方面，本发明提供了一种MIL-88衍生磁性碳纳米材料及其制备方法，基于水热-碳化法，以六水合硝酸钴为Co2+来源，以六水合氯化铁为Fe3+为MIL-88金属配体，以富马酸为有机配体，原位水热合成Co@MIL-88的基础上通过一次碳化合成MIL-88衍生磁性碳纳米材料。通过调整加入的Co2+的量制备钙钛矿型(CoFeO3)和尖晶石型(CoFe2O4)铁酸钴碳纳米材料。
本发明的目的可通过以下技术方案实现：
1)取一定量去离子水与烧杯中，加热后依次加入六水合硝酸钴，六水合氯化铁和富马酸，超声并搅拌一段时间后将混合液转移到水热反应釜中，60-80℃反应8-24h后，得到棕红色沉淀。取出用无水乙醇和去离子水多次离心洗涤后60℃真空干燥12-24h后得到前驱体。
2)将前驱体充分研磨后置于管式炉中，300-700℃N2氛围下煅烧120-360min后得到MIL-88衍生磁性碳纳米材料。
作为本发明的一种优选，步骤1)中去离子水的温度为50～70℃。
作为本发明的一种优选，步骤1)中的六水合氯化铁的用量为50～250mM，六水合硝酸钴的用量为50～500mM，六水合氯化铁和富马酸的摩尔比为1:0.5～1:2。
作为本发明的一种优选，步骤1)中的超声时间为10～20min，搅拌时间为60～180min。
作为本发明的一种优选，步骤1)中的混合液占水热反应釜内胆总容量的50％～75％(V/V)。
作为本发明的一种优选，步骤1)中的离心洗涤的无水乙醇和去离子水的温度为50～70℃。
作为本发明的一种优选，步骤1)中的水热反应时间为12～24h，真空干燥时间为8-12h。
作为本发明的一种优选，步骤2)中管式炉的升温温度为1～10℃/min。
作为本发明的一种优选，步骤2)中N2纯度为99.999％(V/V)
作为本发明的一种优选，步骤2)中的煅烧时间为120-360min。
按照本发明上述限定方法制备得到的一种MIL-88衍生磁性碳纳米材料协同氧化剂过一硫酸钾(PMS)和双氧水(H2O2)应用于水体中抗生素的降解。
所述的水体中的抗生素为氧氟沙星。
所述的水体中的抗生素浓度为5～20mg/L。
与现有技术相比，本发明的有益效果如下：
本发明的一种MIL-88衍生磁性碳纳米材料，所述制备方法通过水热-碳化为基本工艺，以MIL-88为前驱体通过一次碳化合成MIL-88衍生磁性碳纳米材料。本发明所述的制备方法具有工艺简单、可操作性强、制备周期短、收率高且易于实现工业化生产的特点。同时，本发明利用MIL-88上已预先均匀分布的Fe位点作为Fe3+实现了活性位点的高度分散，同时在前驱体碳化后形成的碳层为材料提供了有效支撑避免了活性组分的流失，并赋予了材料磁性使得材料能够快速从水体中分离回收催化剂。
附图说明：
图1：CoFe2O4@C-500的TEM图。
制备过程中合成的CoFe2O4呈现均匀分布并在CoFe2O4的外层能够观察到明显的碳层。
图2：CoFe2O4@C-500的HR-TEM图。
从图中能够明显的观察到归属于CoFe2O4的晶格条纹，表明材料的合成成功。
图3：CoFe2O4@C-500的TEM-mapping图。
具体实施方式
结合具体实施例对本发明作进一步说明，但本发明的保护范围并不限于此。
实施例1
取100mL去离子水并加热至60℃，依次加入5mmol的六水合氯化铁，5mmol的六水合硝酸钴和5mmol的富马酸，超声10min并机械搅拌120min后移入150mL水热反应釜，60℃反应12h后收集底部沉淀，用50℃无水乙醇离心洗涤3次后60℃真空干燥8h后得到前驱体。
将前躯体充分研磨后置于管式炉中，以1℃/min的升温速率升温至300℃碳化120min后得到CoFeO3@C-300磁性碳纳米材料。
将上述制备得到的CoFeO3@C-300磁性碳纳米材料用于活化PMS降解氧氟沙星(OFX)，PMS浓度为2mM，OFX浓度为10mg/L，温度为20℃，pH为7，催化剂投加量为0.2g/L。反应40min后OFX的降解效率达到85.3％。
实施例2
取100mL去离子水并加热至60℃，依次加入，10mmol的六水合氯化铁，5mmol的六水合硝酸钴和5mmol的富马酸，超声15min并机械搅拌150min后移入200mL水热反应釜，60℃反应16h后收集底部沉淀，用60℃无水乙醇离心洗涤4次后70℃真空干燥10h后得到前驱体。
将前躯体充分研磨后置于管式炉中，以2℃/min的升温速率升温至500℃碳化160min后得到CoFe2O4@C-500磁性碳纳米材料，TEM图见图1，HR-TEM图见图2，TEM-mapping图见图3。
将上述制备得到的CoFe2O4@C-500磁性碳纳米材料用于活化PMS降解OFX，PMS浓度为2mM，OFX浓度为20mg/L，温度为30℃，pH为7，催化剂投加量为0.3g/L。反应40min后OFX的降解效率达到91.2％。
实施例3
取150mL去离子水并加热至70℃，依次加入15mmol的六水合氯化铁，10mmol的六水合硝酸铁和15mmol的富马酸，超声20min并机械搅拌180min后移入200mL水热反应釜，70℃反应24h后收集底部沉淀，用60℃无水乙醇离心洗涤5次后60℃真空干燥10h后得到前驱体。
将前躯体充分研磨后置于管式炉中，以5℃/min的升温速率升温至600℃碳化180min后得到CoFeO3@C-600磁性碳纳米材料。
将上述制备得到的CoFeO3@C-600磁性碳纳米材料用于活化H2O2降解OFX，H2O2浓度为5mM，OFX浓度为5mg/L，温度为25℃，pH为7，催化剂投加量为0.3g/L。反应60min后OFX的降解效率达到87.2％。
Claims (10)
1.一种MIL-88衍生磁性碳纳米材料的制备方法，其特征在于包括你如下步骤：
1)向去离子水中依次加入六水合硝酸钴，六水合氯化铁和富马酸，超声并搅拌一段时间后将混合液转移到水热反应釜中，60-80℃反应8-24h后，得到棕红色沉淀，取出用无水乙醇和去离子水多次离心洗涤后60℃真空干燥8-12h后得到前驱体；
2)将前驱体充分研磨后置于管式炉中，300-700℃N2氛围下煅烧120-360min后得到MIL-88衍生磁性碳纳米材料。
2.根据权利要求1所述的制备方法，其特征在于步骤1)中去离子水的温度为50～75℃，优选60～70℃。
3.根据权利要求1所述的制备方法，其特征在于步骤1)中去离子水中六水合氯化铁的终浓度为为50～250mmol，六水合硝酸钴的用量为50～500mmol六水合氯化铁和富马酸的摩尔比为1:0.5～1:2。
4.根据权利要求1所述的制备方法，其特征在于步骤1)中的超声时间为10～20min，搅拌时间为60～180min。
5.根据权利要求1所述的制备方法，其特征在于步骤1)中的混合液占水热反应釜内胆总容量的50％～75％(V/V)。
6.根据权利要求1所述的制备方法，其特征在于步骤1)中的离心洗涤的无水乙醇和去离子水的温度为50～70℃。
7.根据权利要求1所述的制备方法，其特征在于步骤1)中的水热反应时间为12～24h，真空干燥时间为8-12h。
8.根据权利要求1所述的制备方法，其特征在于步骤2)中管式炉的升温温度为1～10℃/min。
9.按照权利要求1～8中任一项所述的制备方法制备的MIL-88衍生磁性碳纳米材料。
10.权利要求9所述的MIL-88衍生磁性碳纳米材料在协同氧化剂降解水体中抗生素中的应用；所述的氧化剂选自。
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