CN117101618B - MOF衍生的LDHs/PEI修饰的壳聚糖基海水提铀微球及其制备方法 - Google Patents
MOF衍生的LDHs/PEI修饰的壳聚糖基海水提铀微球及其制备方法 Download PDFInfo
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Abstract
本发明涉及一种MOF衍生的LDHs/PEI修饰的壳聚糖基海水提铀微球及其制备方法。针对壳聚糖水凝胶在海水提铀产业化应用时所面临的吸附性能与水通量相互制约的问题,本发明设计了一种MOF衍生的LDHs/PEI修饰的壳聚糖基海水提铀微球,其中,PEI和壳聚糖通过戊二醛连接以形成分子孔,可以提高吸附性能和水通量;LDHs与聚合物复合,可以优化材料的孔隙结构,调整材料在实际使用时溶液的的渗透途径,进一步提高吸附性能和水通量。该材料吸附性能优异、水通量大,具有一定的实际应用价值。
Description
技术领域
本发明涉及海水提铀材料领域,具体涉及一种MOF衍生的LDHs/PEI修饰的壳聚糖基海水提铀微球及其制备方法。
背景技术
壳聚糖(CS)是一种天然多糖聚合物,具有成本低、来源广泛、可生物降解和可再生等优点。壳聚糖中丰富的羟基和氨基官能团提供了丰富的吸附位点,壳聚糖通过戊二醛进行交联改性后可以形成壳聚糖水凝胶,前期研究表明[Desalination, 2023, 546,116194.]:化学交联法制备的壳聚糖凝胶呈三维网状结构对碳酸铀酰离子具有良好的吸附性能,尤其对于低浓度(11.24 ~ 101.69ppb)溶液表现极佳的处理能力。然而,由于壳聚糖凝胶通量低、水流阻力大,因此使得吸附效率较低。众所周知,海水中铀的浓度只有约3ppb,材料中海水的通量是决定海水提铀效果的决定性因素,高通量是提高提取容量、加快吸附速率、降低生物污损、降低提取成本的前提和基础。因此,通量低已经成为严重制约壳聚糖水凝胶进一步的产业化应用的瓶颈问题。
然而,吸附性能和水通量相互影响,难以实现吸附性能和水通量的同步提升,提高水凝胶水通量具有如下技术难度:
技术难度1:壳聚糖内部通过戊二醛(GA)连接制备成水凝胶,尽管形成的网格较小,但易与碳酸铀酰离子或铀酰离子配位,采用长链二醛链接,尽管可以扩大网格,提高通量,但吸附性能将显著下降。
技术难度2:壳聚糖水凝胶中丰富的羟基官能团提供了丰富的吸附位点,但是羟基在材料表面易形成致密的水化层,使得水通量显著降低。
技术难度3:壳聚糖水凝胶为柔性材料,形成的分子孔道为柔性孔,在外力作用下容易变形。在柱分离提取过程中,壳聚糖水凝胶具有良好的填充效果,捷径较少,这也是壳聚糖水凝胶吸附性能好但通量差的重要原因。
综上所述,实现壳聚糖水凝胶吸附性能和水通量的同步提升,具有较大的技术难度。
发明内容
针对上述壳聚糖凝胶通量小,水流阻力大的实际问题,本申请提出如下发明构思:
(1)聚乙烯亚胺(PEI)和壳聚糖通过戊二醛连接以形成分子孔,可以提高吸附性能和水通量。
首先,聚乙烯亚胺支链上存在多个伯胺,可通过戊二醛连接,制备多种不同孔径的分子孔,以提高水通量;同时支链具有更好的空间伸展自由度,易于配位,提高其吸附性能;其次,聚乙烯亚胺具有大量的胺基,胺基不仅具有优异的配位能力,而且其形成氢键的能力远远低于羟基,在材料表面不易形成致密的水化层,可以提高水的通量,聚乙烯亚胺与壳聚糖的合成路线图如附图1所示。
(2)水滑石(LDHs)与聚合物复合,优化材料的孔隙结构,提高吸附性能和水通量。
首先,水滑石与聚合物复合,优化材料的孔隙结构,提高吸附性能和水通量。聚合物为柔性材料,形成的分子孔为柔性孔;复合后的空心水滑石纳米球起到支撑作用。尽管二者分别是有机和无机化合物,然而水滑石表面富含羟基,与聚乙烯亚胺和壳聚糖表面的羟基和胺基可以通过氢键相互作用,具有很好的兼容性,这导致孔隙结构丰富多样,孔隙间的连通性更好,有利于流体的渗透和通量的提高。
(3)水滑石与聚合物复合,优化材料的渗透途径,提高吸附性能和水通量。
首先,水滑石粉末无论以纳米微球还是以纳米颗粒存在时,都难以紧密结合,导致在柱吸附实验时,溶液会从吸附柱内的捷径流走,使吸附效率降低。通过使用聚合物填充水滑石微球或颗粒之间的孔隙,可以形成连续的传质通道,减小了孔隙间距离,优化渗透途径。提高了水滑石的渗透速率,避免溶液走捷径。其次,水滑石与聚合物复合,可以通过拓扑调控方式改变水滑石与聚合物复合所形成的材料的孔隙结构和分布情况,优化渗透途径,提高吸附性能和水通量。
(4)MOF衍生的LDHs/PEI修饰的壳聚糖基海水提铀微球,提高吸附性能和水通量。
与水凝胶相比,微球显而易见可以提升通量;然而提高吸附性能,这是由海水中铀的低浓度特点所决定的,即海水中通过吸附剂50亿个水分子才可能通过1个铀酰离子。尽管水凝胶可以充分填充,捷径少,但是阻力大,通量低,吸附铀的数量少。在本发明制备的微球内部,水滑石与聚合物复合,捷径少,吸附性能好。当吸附剂质量相同时,水凝胶可以看作是一个大球进行吸附,而本发明涉及的微球可以看作时很多小球同时吸附。由于海水中铀的浓度低,基本不存在小微球饱和超载现象,因此微球的吸附效率明显优于水凝胶,通过调整微球的粒径来提高吸附效率。
MOF衍生的LDHs/PEI修饰的壳聚糖基海水提铀微球的制备方法包括如下步骤:
步骤1:MOF制备:
将0.7083 g Co(NO3)2·6H2O溶于50 mL甲醇中,超声10 min,得到溶液A;将1.6212g 2-甲基咪唑溶于50 mL甲醇中,超声10 min,得到溶液B;将溶液B迅速倒入溶液A中,搅拌1h,25 ℃下静置24 h;离心收集固体并用甲醇清洗3次,60 ℃下干燥12 h,得到的固体粉末被命名为ZIF-67;
步骤2:空心LDHs纳米球的制备:
将0.16 g Ni(NO3)2·6H2O溶解在13 mL无水乙醇中,得到溶液C;0.04 g ZIF-67溶解在13 mL无水乙醇中,搅拌30 min,加入溶液C,搅拌24 h;离心收集固体,分别用去离子水和无水乙醇各清洗3次,60 ℃下干燥12 h,得到为MOF-衍生的空心LDHs纳米球,其形貌及结构如附图2所示;
步骤3:MOF衍生的LDHs/PEI修饰的壳聚糖基海水提铀微球制备:
在0.1-0.6 g PEI和0.6 g CS的混合溶液中加入空心LDHs纳米球,搅拌12 h,所述的PEI和CS的总质量与LDHs的质量比为12-3 : 1;溶液逐滴滴加到40% NaOH溶液中,不断搅拌,控制转速为100r/min,向上述溶液中加入2%的戊二醛溶液,搅拌10min,静置12h,使用去离子水冲洗微球至中性,得到的微球即为MOF衍生的LDHs/PEI修饰的壳聚糖基海水提铀微球。
MOF衍生的LDHs/PEI修饰的壳聚糖基海水提铀微球,包括聚合物和LDHs复合材料;所述的聚合物为聚乙烯亚胺和壳聚糖通过戊二醛连接而成的高分子聚合物;所述的LDHs为以MOF为前驱体衍生的空心LDHs纳米球;空心LDHs纳米球均匀分散在聚合物中;所述微球直径尺寸为500-2000μm。
有益效果:本发明制备的MOF衍生的LDHs/PEI修饰的壳聚糖基海水提铀微球可以使海水在其内部高效通过,显著提高吸附容量和通量。将LDHs分散到微球中,可以避免因LDHs易团聚而使其吸附性能下降的弊端,同时微球具有丰富的孔隙结构和传质通道,提高吸附效率。
附图说明
图1 壳聚糖与聚乙烯亚胺的合成路线图
图2 空心LDHs纳米球的(a)TEM图, (b)XRD图
图3 不同质量比的PEI-CS微球的(a-f) 表面SEM图,(g-l)表面局部放大后的SEM图,(m-r)横截面的SEM图, (s) FT-IR图, (t) XPS全谱, (u) XPS测试得到的材料中N元素的相对原子百分含量
图4 不同质量比的PEI-CS微球的铀吸附容量(pH=6, C0=150mg/L, m=20mg, V=50mL)
图5 (a-d) PEI和CS的总质量与LDHs的质量比分别为12:1、9:1、6:1、3:1时的SEM图
图6 不同质量比的MOF衍生的LDHs/PEI修饰的壳聚糖基海水提铀微球的铀吸附容量(pH=6, C0=150mg/L, m=20mg, V=50mL)
图7 直径为1000-1500μm的MOF衍生的LDHs/PEI修饰的壳聚糖基海水提铀微球的SEM图
图8 直径为500-1000μm的MOF衍生的LDHs/PEI修饰的壳聚糖基海水提铀微球的SEM图
图9 直径为1500-2000μm的MOF衍生的LDHs/PEI修饰的壳聚糖基海水提铀微球的SEM图
实施方式
下面结合具体实施例对本发明进行详细说明。以下实施例将有助于本领域的技术人员进一步理解本发明,但不以任何形式限制本发明。应当指出的是,对本领域的普通技术人员来说,在不脱离本发明构思的前提下,还可以做出若干变形和改进。这些都属于本发明的保护范围。
实施例
MOF衍生的LDHs/PEI修饰的壳聚糖基海水提铀微球的制备方法包括如下步骤:
步骤1:MOF制备:
将0.7083 g Co(NO3)2·6H2O溶于50 mL甲醇中,超声10 min,得到溶液A;将1.6212g 2-甲基咪唑溶于50 mL甲醇中,超声10 min,得到溶液B;将溶液B迅速倒入溶液A中,搅拌1h,25 ℃下静置24 h;离心收集固体并用甲醇清洗3次,60 ℃下干燥12 h,得到的固体粉末被命名为ZIF-67;
步骤2:空心LDHs纳米球的制备:
将0.16 g Ni(NO3)2·6H2O溶解在13 mL无水乙醇中,得到溶液C;0.04 g ZIF-67分别溶解在13 mL无水乙醇中,搅拌30 min,加入溶液C,搅拌24 h;离心收集固体,分别用去离子水和无水乙醇各清洗3次,60 ℃下干燥12 h,得到为MOF-衍生的空心LDHs纳米球,其形貌及结构如附图2所示;
步骤3:MOF衍生的LDHs/PEI修饰的壳聚糖基海水提铀微球制备:
在0.1-0.6 g PEI和0.6 g CS的混合溶液中加入空心LDHs纳米球,搅拌12 h,所述的PEI和CS的总质量与LDHs的质量比为12-3 : 1;溶液逐滴滴加到40% NaOH溶液中,不断搅拌,控制转速为100r/min,向上述溶液中加入2%的戊二醛溶液,搅拌10min,静置12h,使用去离子水冲洗微球至中性,得到的微球即为MOF衍生的LDHs/PEI修饰的壳聚糖基海水提铀微球。
MOF衍生的LDHs/PEI修饰的壳聚糖基海水提铀微球,包括聚合物和LDHs复合材料;所述的聚合物聚乙烯亚胺和壳聚糖通过戊二醛连接而成的高分子聚合物;所述的LDHs为以MOF前驱体衍生的空心LDHs纳米球;空心LDHs纳米球均匀分散在聚合物中;所述微球直径尺寸为150-2000μm。
实施例
本实施例与实施例1基本相似,不同之处在于:步骤3中PEI与CS的质量比为1 : 2。
技术说明:实验研究表明,在上述实验条件下制备的PEI-CS微球的孔隙结构丰富,并且吸附效果最好。
技术效果:依据本实施例中的制备方法所制备的PEI-CS微球的孔隙结构丰富,见附图3,水通量相对最高,并且吸附容量远高于其他质量比的PEI-CS微球,显著提高了材料的吸附性能,见附图4。
实施例
本实施例与实施例2基本相似,不同之处在于:步骤3中所述的PEI和CS的总质量与LDHs的质量比为6 : 1
技术说明:实验研究表明,在上述实验条件下制备的MOF衍生的LDHs/PEI修饰的壳聚糖基海水提铀微球孔隙结构规整,内部存在大量传质通道,有利于提高铀离子与微球内部活性位点的接触概率,可以显著提高吸附容量。
技术效果:依据本实施例中的制备方法所制备的MOF衍生的LDHs/PEI修饰的壳聚糖基海水提铀微球孔隙结构规整,内部存在大量传质通道,见附图5,同时展现了优异的铀吸附能力,见附图6。
实施例
本实施例与实施例3基本相似,不同之处在于:步骤3中使用1mL注射器将混合溶液逐滴滴加到40% NaOH溶液中制备成微球。
技术说明:实验研究表明,在上述实验条件下制备的MOF衍生的LDHs/PEI修饰的壳聚糖基海水提铀微球直径为1000-1500 μm,微球尺寸适中,同时具有优异的水通量和吸附性能,见附图7。
实施例
本实施例与实施例3基本相似,不同之处在于:步骤3中使用0.5 mL注射器将混合溶液逐滴滴加到40% NaOH溶液中制备成微球。
技术说明:实验研究表明,在上述实验条件下制备的MOF衍生的LDHs/PEI修饰的壳聚糖基海水提铀微球直径为500-1000 μm,微球尺寸较小,见附图8。具有优异的铀吸附性能,但水通量较差,适用于处理少量较高铀浓度的海水。
实施例
本实施例与实施例3基本相似,不同之处在于:步骤3中使用10 mL注射器将混合溶液逐滴滴加到40% NaOH溶液中制备成微球。
实验研究表明,在上述实验条件下制备的MOF衍生的LDHs/PEI修饰的壳聚糖基海水提铀微球直径为1500-2000μm,微球尺寸大,见附图9。具有较差的铀吸附性能,但水通量很高,适用于处理大量较低铀浓度的海水。
Claims (4)
1.MOF衍生的LDHs/PEI修饰的壳聚糖基海水提铀微球的制备方法:
步骤1:MOF制备:将0.7083g Co(NO3)2·6H2O溶于50mL甲醇中,超声10min,得到溶液A;将1.6212g 2-甲基咪唑溶于50mL甲醇中,超声10min,得到溶液B;将溶液B迅速倒入溶液A中,搅拌1h,25℃下静置24h;离心收集固体并用甲醇清洗3次,60 ℃下干燥12h,得到的固体粉末被命名为ZIF-67;
步骤2:空心LDHs纳米球的制备:将0.16g Ni(NO3)2·6H2O溶解在13mL无水乙醇中,得到溶液C;0.04g ZIF-67溶解在13mL无水乙醇中,搅拌30min,加入溶液C,搅拌24h;离心收集固体,用去离子水和无水乙醇各清洗3次,60℃下干燥12h,得到为MOF-衍生的空心LDHs纳米球;
步骤3:MOF衍生的LDHs/PEI修饰的壳聚糖基海水提铀微球制备:在0.1-0.6g PEI和0.6g CS的混合溶液中加入空心LDHs纳米球,搅拌12h,所述的PEI和CS的总质量与LDHs的质量比为12-3:1;溶液逐滴滴加到40%NaOH溶液中,不断搅拌,控制转速为100r/min,向上述溶液中加入2%的戊二醛溶液,搅拌10min,静置12h,使用去离子水冲洗微球至中性,得到的微球即为MOF衍生的LDHs/PEI修饰的壳聚糖基海水提铀微球。
2.如权利要求1所述MOF衍生的LDHs/PEI修饰的壳聚糖基海水提铀微球的制备方法,其特征在于所述的:步骤3中PEI与CS的质量分别为0.6g和0.3g。
3.如权利要求2所述MOF衍生的LDHs/PEI修饰的壳聚糖基海水提铀微球的制备方法,其特征在于所述的:步骤3中所述的PEI和CS的总质量与LDHs的质量比为6:1。
4.如权利要求1所述的MOF衍生的LDHs/PEI修饰的壳聚糖基海水提铀微球的制备方法所制备的微球,包括聚合物和LDHs复合材料;其特征在于所述的聚合物为聚乙烯亚胺和壳聚糖通过戊二醛连接而成的高分子聚合物;所述的LDHs为以MOF为前驱体衍生的空心LDHs纳米球;空心LDHs纳米球均匀分散在聚合物中;微球直径尺寸为500-2000μm。
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