CN113046857B - 一种可自更新活性防污涂层的海水提铀吸附剂及其制备方法 - Google Patents

一种可自更新活性防污涂层的海水提铀吸附剂及其制备方法 Download PDF

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CN113046857B
CN113046857B CN202110276080.3A CN202110276080A CN113046857B CN 113046857 B CN113046857 B CN 113046857B CN 202110276080 A CN202110276080 A CN 202110276080A CN 113046857 B CN113046857 B CN 113046857B
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吴锡龙
吴云娣
于智群
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Hainan University
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Abstract

本发明公开了一种可自更新活性防污涂层的海水提铀吸附剂的制备方法，包括以下步骤：利用聚丙烯腈和六水合硝酸锌制备六水合硝酸锌‑聚丙烯腈纺丝前体溶液；在一定条件下纺丝制备六水合硝酸锌‑聚丙烯腈纤维；取六水合硝酸锌‑聚丙烯腈纤维加入2‑甲基咪唑溶液中反应获得2‑甲基咪唑锌盐多孔配位聚合物‑聚丙烯复合纤维；利用单宁酸使复合纤维交联获得交联化的2‑甲基咪唑锌盐多孔配位聚合物‑六水合硝酸锌‑聚丙烯复合纤维；最后进行肟化反应获得偕胺肟化的用于海水提铀的纳米级复合纤维材料。通过本方法制备的海水提铀吸附剂，不仅可显著提高其提铀能力，且在循环提铀使用中具有持续自更新的防海洋生物污损能力，不收缩且结构稳定。

Description

一种可自更新活性防污涂层的海水提铀吸附剂及其制备方法
技术领域
本发明涉及新材料制备领域，尤其涉及一种可自更新活性防污涂层的海水提铀吸附剂及其制备方法。
背景技术
从海水中提取铀对于满足核能工业对铀资源日益增长的需求至关重要。但由于天然海水环境复杂，铀浓度低(3.3ppb，μg L-1)及海洋微生物污损严重等问题，导致提铀吸附剂未能广泛工业化应用。
金属有机框架纳米粒子掺杂的纤维材料作为提铀吸附剂之一，通常在用于海水提铀前经过改性处理如腈基肟化或碱液处理等，从而增加铀的吸附位点和改善纤维的亲水性从而促进铀的吸附。当纤维用于海水提铀时，由于海水循环流动对纤维的冲刷和纤维吸附铀后洗脱再生对纤维的破坏，改性和洗脱会同时引起纤维上金属有机框架纳米材料的大量脱落以及纤维不同程度的收缩或降解(与溶液种类、浓度、pH、处理时间、温度等因素有关)，影响纤维的表面形貌和结构强度，造成铀吸附效率和材料耐久性的严重下降。另外大量的海洋细菌会通过自身分泌的细胞外基质将菌体群落包裹其中，从而形成附着于吸附材料表面的有组织的细菌聚集体膜状物(微生物膜)，这为硅藻和大孢子提供营养和固定点，是引起海洋生物污损的重要因素之一，严重影响海水提铀材料的吸附效率。当前对于具有抗生物膜和抗藻粘附功能的纤维吸附剂材料研究较少，同时具有抗生物污损性能的海水提铀材料吸附效率普遍偏低。
发明内容
有鉴于此，本发明提供了一种可自更新活性防污涂层的海水提铀吸附剂的制备方法，解决现有技术存在的问题。
本发明采用一种可自更新活性防污涂层的海水提铀吸附剂的制备方法，包括以下步骤：
(1)利用聚丙烯腈和六水合硝酸锌制备六水合硝酸锌-聚丙烯腈纺丝前体溶液；
(2)在一定条件下纺丝制备六水合硝酸锌-聚丙烯腈纤维；
(3)取步骤(2)的六水合硝酸锌-聚丙烯腈纤维加入含2-甲基咪唑溶液中反应获得2-甲基咪唑锌盐多孔配位聚合物-聚丙烯腈复合纤维；
(4)利用单宁酸使步骤(3)的复合纤维交联获得交联化的2-甲基咪唑锌盐多孔配位聚合物-聚丙烯腈复合纤维；
(5)将交联化的2-甲基咪唑锌盐多孔配位聚合物-聚丙烯腈复合纤维进行肟化反应获得偕胺肟化复合纤维材料。
优选地，步骤(1)的六水合硝酸锌-聚丙烯腈纺丝前体溶液由1.6g聚丙烯腈和1.0g六水合硝酸锌缓慢溶解于10mL N，N-二甲基甲酰胺中，后在室温下搅拌3h制备而得。
优选地，步骤(2)的纺丝参数为：注射器采用30G针头，以20kPa的风压、1mL/h的速度推进溶液，在40℃温度下通过旋转辊筒以390rpm的转速接收纤维，纤维接收距离为30cm。
优选地，步骤(3)具体为18mg六水合硝酸锌-聚丙烯腈纤维加入5mL含有浓度为80mg/mL的2-甲基咪唑的甲醇溶液并于室温反应12h制备而得。
优选地，步骤(4)中，将18mg步骤(3)中的2-甲基咪唑锌盐多孔配位聚合物-聚丙烯腈复合纤维静置于5g/L的单宁酸溶液中并在室温下反应5h制备而得。
优选地，步骤(5)中肟化反应pH为6-7，反应时间为5-6h，反应温度为60-70℃，盐酸羟胺浓度为30-40g/L。
优选地，步骤(5)中肟化反应pH为6，反应温度为70℃，反应时间为5h，盐酸羟胺浓度为30g/L。
本发明另一方面提供一种可自更新活性防污涂层的海水提铀吸附剂。
采用本发明所提供的一种可自更新活性防污涂层的海水提铀吸附剂的方法，通过溶液气纺法制备原位生长金属有机框架纳米颗粒，以单宁酸(TA)交联后再肟化获得抗生物污损型纤维材料(in situ ZIF-8/TA/PAO)，一方面通过适当交联使本发明纤维材料在偕胺肟化过程中2-甲基咪唑锌盐多孔配位聚合物(ZIF-8)不脱落，同时在洗脱过程中单宁酸自动解离脱落而逐渐暴露出更多的ZIF-8，实现自更新能力，在经过5个吸附-解吸循环，经过洗脱再生的复合纤维吸附剂在含铀海水中仍然能够保持较高的吸附能力。
进一步地，本发明的可自更新活性防污涂层的海水提铀吸附剂不仅能产生活性氧，表现出优异的光催化活性，与藻类细胞相互作用导致亚细胞结构改变和/或藻类细胞死亡，且可释放锌离子使其能够吸附或穿过带负电荷的微生物膜，直接破坏参与细胞分裂的酶活性，抑制微生物生长或诱导其死亡，从而使本发明的海水提铀吸附剂具有良好的抗海洋生物污损活性。
附图说明
图1为实施例一及实施例四各步骤中间产物及最终产物的红外测试图；
图2为实施例一及实施例四各步骤中间产物及最终产物的电镜扫描图，其中a为聚丙烯腈PAN纤维；b为PAN-Zn纤维；c为原位生长后的PAN@ZIF-8纤维；d为单宁酸交联后的PAN@ZIF-8/TA纤维；e为未经过交联反应而是直接肟化的in situ ZIF-8/PAO纤维；f为经过交联再肟化制备的in situ ZIF-8/TA/PAO纤维；
图3为in situ ZIF-8/TA/PAO纤维经过5轮吸附和解吸过程中的电镜扫描图；
图4为in situ ZIF-8/TA/PAO纤维经过5轮吸附和解吸过程中的红外测试图；
图5为in situ ZIF-8/TA/PAO纤维经过5轮吸附和解吸过程中的X射线衍射图；
图6为PAO和in situ ZIF-8/TA/PAO纤维在天然海水中的提铀性能测试结果；
图7为PAO和in situ ZIF-8/TA/PAO纤维在天然海水提铀饱和后的电镜扫描图；
图8为PAO和in situ ZIF-8/TA/PAO纤维在天然海水提铀不同时间的电镜扫描图；
图9为不同用量的交联剂交联获得的in situ ZIF-8/TA/PAO纤维的扫描电镜图。
具体实施方式
以下对本发明的原理和特征进行描述，所举实施例只用于解释本发明，并非用于限定本发明的范围。
实施例一：一种可自更新活性防污涂层的海水提铀吸附剂的制备方法包括以下步骤：
(1)六水合硝酸锌-聚丙烯腈纺丝前体溶液的合成
在磁力搅拌下，将1.6g聚丙烯腈(PAN)和1.0g六水合硝酸锌(Zn(NO3)2·6H2O)缓慢溶解于10mL N，N-二甲基甲酰胺(DMF)中。在室温下搅拌3h，得到澄清的六水合硝酸锌-聚丙烯腈纺丝前体溶液。
(2)气纺六水合硝酸锌-聚丙烯腈(PAN@Zn2+)纤维的制备
将纺丝前体溶液注入注射器中制备PAN@Zn2+气纺纤维。纺丝参数设置如下：由配备有硅胶干燥管的空气压缩机提供干燥的压缩空气，加注有纺丝液的注射器采用30G针头，以20kPa的风压、1mL/h的推进速度推进溶液吹制纤维，在40℃温度下通过旋转辊筒以390rpm的转速接收纤维，纤维接收距离为30cm。
(3)原位生长金属有机框架即2-甲基咪唑锌盐-聚丙烯腈纤维(PAN@ZIF-8)的制备
取18mg步骤(2)中的六水合硝酸锌-聚丙烯腈纤维(PAN@Zn2+纤维)，加入5mL浓度为80mg/mL的2-甲基咪唑的甲醇溶液中室温反应12h，后洗涤干燥，获得原位生长金属有机框架-2-甲基咪唑锌盐多孔配位聚合物(ZIF-8)-聚丙烯腈的复合纤维PAN@ZIF-8。
(4)单宁酸交联带有ZIF-涂层的聚丙烯腈复合纤维PAN@ZIF-8/TA的制备
取18mg步骤(3)中的PAN@ZIF-8纤维静置于100mL 5g/L的单宁酸(TA)溶液中，并在室温下保持5h，后用水洗涤两次并干燥，得到交联后的PAN@ZIF-8/TA纤维(如式1所示)。
Figure GDA0003435484170000051
(5)PAN@ZIF-8/TA复合纤维偕胺肟化制备复合纤维in situ ZIF-8/TA/PAO
将18mg PAN@ZIF-8/TA纤维浸入30mL浓度为30g/L的盐酸羟胺溶液中，先用碳酸钠水溶液调节pH至6.0，后在70℃反应5h，最后洗涤干燥获得偕胺肟化的in situ ZIF-8/TA/PAO复合纤维材料(如式2)。
Figure GDA0003435484170000061
实施例二：实施例二和实施例一的区别在于：步骤(3)中2-甲基咪唑锌盐-聚丙烯腈纤维(PAN@ZIF-8)原位生长条件的不同，
根据XRD、ICP和BET的测试结果可知，实施例一制备的PAN@ZIF-8纤维ZIF-8中晶体长势最佳，比表面积最大。
实施例三：实施例三和实施例一的区别在于：步骤(4)中所加入交联剂的用量不同，交联程度对本发明复合纤维的影响结果如图9，其中实施例一的聚丙烯腈复合纤维PAN@ZIF-8/TA获得最佳纳米涂层，可确保ZIF-8活性涂层在交联和肟化过程不脱落的同时，在重复提铀过程中可实现自更新，从而达到可持续性的防污损能力。
实施例四：实施例四和实施例一的区别在于：步骤(5)中偕胺肟化反应条件的不同，其合成条件及结果如表1：
表1不同肟化反应条件对本发明复合纤维的影响
Figure GDA0003435484170000071
根据表1结果可知最佳肟化条件为pH(6)、肟化时间(5h)、肟化剂浓度为30g/l，制备的偕胺肟化的in situ ZIF-8/TA/PAO复合纤维材料肟化率100％，且在肟化反应中活性涂层无脱落。
实施例五：实施例四和实施例一的区别在于，未经过步骤(4)的单宁酸交联，直接肟化制备in situ ZIF-8/PAO纳米级复合纤维，如图2e所示，未经过交联反应而是直接肟化的in situ ZIF-8/PAO纤维表面和截面光滑，ZIF-8几乎完全脱落。
实施例六：对实施例一的一种可自更新活性防污涂层的海水提铀吸附剂进行表征及性能测试
(1)对实施例一的中间产物及in situ ZIF-8/PAO纳米级复合纤维进行红外表征
如图的通过红外测试结果可看出，实施例一中的in situ ZIF-8/PAO纳米级复合纤维的特征吸收峰有C＝N(1655cm-)，C-N(1345cm-)，N-0(950-)，聚丙烯晴的特征吸收峰消失，说明实施例一中的in situ ZIF-8/PAO纳米级复合纤维成功制备。
(2)对实施例一制备过程的中间产物及最终产物进行表面形貌观察，如图2可知，相对于聚丙烯腈PAN纤维表面光滑，PAN-Zn纤维表面更加粗糙，并且没有大块的黏结，说明Zn2+均匀的分布于纤维中，为ZIF-8颗粒的良好生长提供基底，而图2c为原位生长后的PAN@ZIF-8纤维表面和截面均布满ZIF-8晶体，说明ZIF-8在纤维中生长良好，图2d为单宁酸交联后的PAN@ZIF-8/TA纤维，从截面更清楚地看出形成交联层，说明纤维已成功交联，图2f表明经过交联再肟化制备的in situ ZIF-8/TA/PAO纤维表面仍布满ZIF-8，纤维尺寸为1-1.5μm。
实施例七：对实施例一的一种可自更新活性防污涂层的海水提铀吸附剂进行提铀性能测试
(1)将实施例一的in situ ZIF-8/TA/PAO纤维浸泡在1L铀浓度为8ppm(pH＝8)的模拟海水中吸附36h直至饱和，后在室温下将饱和的铀-吸收纤维浸泡在洗脱液中磁力搅拌35min，洗脱完成后，将纤维从洗脱液(500mL超纯水，5.7mL质量浓度为30％过氧化氢水溶液，53g碳酸氢钠粉末)中取出并浸入纯水中，并将水更换几次，直至pH约等于7，最后将纤维浸泡在加入铀的海水溶液中(32ppm)用于下一个循环。重复此吸附-洗脱过程五次。
将经过5轮吸附和解吸后的in situ ZIF-8/TA/PAO纤维进行SEM测试，如图3的电镜图表明，纤维在整个吸附和再生过程中保持了结构的完整；图4的FTIR表明随着洗脱次数的增加，纤维上单宁酸TA组分的减少而形成自更新涂层；图5的XRD结果表明，随着洗脱次数的增加，in situ ZIF-8/TA/PAO纤维逐渐表现出ZIF-8的晶型特征峰，说明ZIF-8逐渐暴露，达到自更新可重复利用的目的。
(2)将实施例一的in situ ZIF-8/TA/PAO纤维在50L循环流动天然海水中吸附25天后，PAO和in situ ZIF-8/TA/PAO纤维对铀的饱和吸附量分别达到8.92mg/g和11.17mg/g，如图6的结果表明in situ ZIF-8/TA/PAO复合纤维显著提高对铀酰离的吸附能力，在铀吸附50d后，PAO(i,ii,iii,iv)发生明显的收缩，并破裂成小块，而in situ ZIF-8/TA/PAO(v,vi,vii,viii)没有变形，且表面均匀分布大量的ZIF-8，表明它具有优越的保形性能如图7。
(3)将实施例一的in situ ZIF-8/TA/PAO纤维在50L循环流动天然海水中分别吸附10天、20天及30天并分别通过SEM观察形貌，如图8结果表明通过纤维在天然海水中进行不同吸附时间后，单纯PAO纤维被大量的海洋细菌和浮游生物覆盖，而in situ ZIF-8/TA/PAO纤维表面相对干净整洁，没有或只有很少的死细菌，暴露出更多的可利用吸附位点，有助于提高纤维对铀的吸附能力，即in situ ZIF-8/TA/PAO纤维具有良好的防生物污损能力。
综上所述，采用本发明所提供的一种可自更新活性防污涂层的海水提铀吸附剂的方法，通过溶液气纺法制备原位生长金属有机框架纳米颗粒，以单宁酸(TA)交联后再肟化获得抗生物污损型纤维材料(in situ ZIF-8/TA/PAO)，一方面使本发明纤维材料在偕胺肟化过程中ZIF-8不脱落，另一方面在洗脱过程中，TA自动解离脱落而逐渐暴露出更多的活性涂层ZIF-8，因此经过5个吸附-解吸循环，经过洗脱再生的复合纤维吸附剂在含铀海水中依然能够保持较高的吸附能力。
进一步地，本发明的in situ ZIF-8/TA/PAOZIF-8纤维材料产生活性氧(ROS)从而表现出优异的光催化活性，可与藻类细胞相互作用，导致亚细胞结构改变和/或藻类细胞死亡，且释放出来的锌离子(Zn2+)能够吸附或穿过带负电荷的微生物膜，直接破坏参与细胞分裂的酶活性，抑制微生物生长或诱导死亡，从而使in situ ZIF-8/TA/PAO复合纤维具有良好的抗生物污损活性。
以上所述仅为本发明的较佳实施例而已，并不用以限制本发明，凡在本发明的精神和原则之内，所做的任何修改、等同替换、改进等，均应包含在本发明保护的范围之内。

Claims (4)

1.一种可自更新活性防污涂层的海水提铀吸附剂的制备方法，其特征在于，包括以下步骤：
(1)利用聚丙烯腈和六水合硝酸锌制备六水合硝酸锌-聚丙烯腈纺丝前体溶液；
(2)在一定条件下纺丝制备六水合硝酸锌-聚丙烯腈纤维；
(3)取步骤(2)的六水合硝酸锌-聚丙烯腈纤维加入含2-甲基咪唑溶液中反应获得2-甲基咪唑锌盐多孔配位聚合物-聚丙烯腈复合纤维；
(4)利用单宁酸使步骤(3)的复合纤维交联获得交联化的2-甲基咪唑锌盐多孔配位聚合物-聚丙烯腈复合纤维；
(5)将交联化的2-甲基咪唑锌盐多孔配位聚合物-聚丙烯腈复合纤维进行肟化反应获得偕胺肟化复合纤维材料；
所述步骤(1)的六水合硝酸锌-聚丙烯腈纺丝前体溶液由1.6g聚丙烯腈和1.0g六水合硝酸锌缓慢溶解于10mL N，N-二甲基甲酰胺中，后在室温下搅拌3h制备而得；
所述步骤(3)具体为18mg六水合硝酸锌-聚丙烯腈纤维加入5mL含有浓度为80mg/mL的2-甲基咪唑的甲醇溶液并于室温反应12h制备而得；
所述步骤(4)中，将18mg步骤(3)中的2-甲基咪唑锌盐多孔配位聚合物-聚丙烯腈复合纤维静置于100mL 5g/L的单宁酸溶液中并在室温下反应5h制备而得；
所述步骤(5)中肟化反应pH为6-7，反应时间为5-6h，反应温度为60-70℃，盐酸羟胺浓度为30-40g/L。
2.根据权利要求1所述的一种可自更新活性防污涂层的海水提铀吸附剂的制备方法，其特征在于，所述步骤(2)的纺丝参数为：注射器采用30G针头，以20kPa的风压、1mL/h的速度推进溶液，在40℃温度下通过旋转辊筒以390rpm的转速接收纤维，纤维接收距离为30cm。
3.根据权利要求2所述的一种可自更新活性防污涂层的海水提铀吸附剂的制备方法，其特征在于，所述步骤(5)中肟化反应pH为6，反应温度为70℃，反应时间为5h，盐酸羟胺浓度为30g/L。
4.一种可自更新活性防污涂层的海水提铀吸附剂，由权利要求1-3任一项所述的方法制备而得。
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