CN113842887A - Co-MIL-53(Fe)-NH2/UIO-66-NH2复合材料及其制备和应用 - Google Patents
Co-MIL-53(Fe)-NH2/UIO-66-NH2复合材料及其制备和应用 Download PDFInfo
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Abstract
本发明属于纳米复合材料与环境材料制备及其降解环境污染物的技术领域，涉及一种Co‑MIL‑53(Fe)‑NH2/UIO‑66‑NH2复合材料及其制备和应用。通过原位法将八面体UiO‑66‑NH2和Co‑MIL‑53(Fe)‑NH2结合，成功制备了Co‑MIL‑53(Fe)‑NH2/UIO‑66‑NH2复合材料，用于吸附和可见光(λ≥420nm)下降解抗生素四环素，复合材料中Co‑MIL‑53(Fe)‑NH2与UiO‑66‑NH2质量比为7：3的具有最高效的吸附和光催化协同降解能力(Co‑MIL‑53(Fe)‑NH2为45％，UiO‑66‑NH2为53％)。
Description
技术领域：
本发明属于纳米复合材料与环境材料制备及其降解环境污染物的技术领域，涉及一种Co-MIL-53(Fe)-NH2/UIO-66-NH2复合材料及其制备和应用。
背景技术：
近年来，抗生素的广泛应用导致环境水体中抗生素的迅速增加，对人类健康构成巨大威胁。但由于其水溶性好、降解难度大，在许多水体中检测到不同浓度的TC。环境水体中TC的不断积累，不仅会污染环境，还会进入食物链，最终危害人类健康。因此，迫切需要研究降解TC的可能方法。
金属有机骨架(MOFs)是一系列具有高表面积和良好有序孔径的新型三维多孔材料。它们在吸附，催化和储气应用方面具有良好的潜力。值得我们关注的是一些特殊的MOFs类型(例如Fe-MOF，Ti(IV)-MOF，Zr-MOF，Zn-MOF)。它们在光照下具有良好的催化性能，这归因于它们的激发电子转移的准备。然而，MOFs产生激发电子和分离电荷的效率低导致光催化反应效率低。因此，通过将过渡金属引入MOFs中可能是一种提高量子效率的可行方法。例如孙等容团队合成了NH2-UIO-66(Zr/Ti)，证明了在MOFs中通过金属替代构建双金属基MOFs是提高光催化性能的有效途径。
发明内容：
本发明的目的在于提供一种Co-MIL-53(Fe)-NH2/UIO-66-NH2复合材料及其制备和应用，通过过渡金属钴掺杂的方式，制备了Co-MIL-53(Fe)-NH2/UIO-66-NH2双MOFs材料，其中UIO-66-NH2作为典型的Zr基MOFs材料，其可以有效促进光电载流子的分离和转移。而Co掺杂的Fe基MOFs由于元素Co的引入，通过Fe3+/Fe2+和Co3+/Co2+氧化还原过程进一步促进电荷转移。因此，通过Co-MIL-53(Fe)-NH2与UIO-66-NH2结合，构建直接Z型异质结，提高了催化剂光催化能力和吸附能力。所制得的光催化剂有利于光生载流子的输送过程，具有良好的可见光光催化活性，同时也具有大的比表面积。
为了实现本发明目的，采用了以下的技术方案：
Co-MIL-53(Fe)-NH2/UIO-66-NH2复合材料的制备方法，包括如下步骤：
(1)在DMF中加入设定量的Fe(NO3)3·9H2O、Co(NO3)2·6H2O和H2ATA，并超声处理直至完全溶解，得到混合溶液；
(2)向步骤(1)的混合溶液中加入设定量的UiO-66-NH2，内衬聚四氟乙烯的不锈钢反应釜中并加热至140℃±10℃并且至少保持6小时；
(4)冷却后，离心收集固体，并用甲醇和去离子水洗涤，所述Co-MIL-53(Fe)-NH2/UIO-66-NH2复合材料。
作为优选，真空干燥温度为85℃。
作为优选，在内衬聚四氟乙烯的不锈钢反应釜中反应温度控制在140±10℃，反应持续时间控制在6小时。若温度过低，会导致Co-MIL-53(Fe)-NH2结晶不完全和产量较低。若时间过短，会导致复合材料复合不完全和产量低。
作为优选，Co-MIL-53(Fe)-NH2与UIO-66-NH2的质量比为1:1-7:3。复合材料中Co-MIL-53(Fe)-NH2与UiO-66-NH2质量比为7：3的具有最高效的吸附和光催化协同降解能力。
与现有技术相比，本申请取得了如下有益效果：利用简单的原位法制备Co-MIL-53(Fe)-NH2/UIO-66-NH2复合材料，形貌为包裹结构，该材料具有吸附和光催化性能高，稳定性好等优点。本发明工艺简单，且所用原材料价廉易得，成本低，符合环境友好要求。由于该方法不需要高温、煅烧之类的前处理，从而减少了能耗和反应成本，便于批量生产。
附图说明：
图1为本发明实施例中的UiO-66-NH2，Co-MIL-53(Fe)-NH2和Co-MIL-53(Fe)-NH2/X％UIO-66-NH2复合材料的XRD图谱和三维荧光(PL)图谱。
图2为本发明实施例中的UiO-66-NH2，Co-MIL-53(Fe)-NH2和Co-MIL-53(Fe)-NH2/X％UIO-66-NH2复合材料的FT-IR图谱。
图3为本发明实施例中的UiO-66-NH2和Co-MIL-53(Fe)-NH2/X％UIO-66-NH2的SEM图像。
图4为本发明实施例中的Co-MIL-53(Fe)-NH2/X％UIO-66-NH2的XPS图谱。
图5为本发明实施例中的四环素的吸附降解图(0.02g催化剂；10mgPMS；50mL25mg/L TC)。
图6为本发明实施例中的Co-MIL-53(Fe)-NH2/X％UIO-66-NH2的TEM图谱。
具体实施方式：
本发明不局限于下列具体实施方式，本领域一般技术人员根据本发明公开的内容，可以采用其他多种具体实施方式实施本发明的，或者凡是采用本发明的设计结构和思路，做简单变化或更改的，都落入本发明的保护范围。需要说明的是，在不冲突的情况下，本发明中的实施例及实施例中的特征可以相互组合。
实施例：
UIO-66-NH2通过常规的溶剂热合成。具体按如下步骤进行：
A、向40ml DMF中加入0.81g H2ATA(2-氨基对苯二甲酸)和1.05g ZrCl4，超声完全溶解，加入17ml醋酸，搅拌30分钟至完全溶解；
B、将混合溶液转移到内衬聚四氟乙烯的不锈钢反应釜中，转移至烘箱保持120℃反应24h；
C、冷却至室温，乙醇和水洗涤，离心收集产物；
D、最后，将产物放在80℃的真空烘箱中干燥即可得到UIO-66-NH2复合材料
Co-MIL-53(Fe)-NH2/X％UIO-66-NH2也是通过溶剂热法合成。具体按以下步骤进行：
A、首先，将40.4mg的Fe(NO3)3·9H2O，87.3mg的Co(NO3)2·6H2O和18.1mg的H2ATA缓慢加入到10ml DMF溶液中，并超声处理直至完全溶解；
B、向步骤A溶液中加入不同量的UiO-66-NH2；
C、将混合溶液转移到内衬聚四氟乙烯的不锈钢反应釜中，转移至烘箱保持140℃±10℃反应6h；
D、冷却至室温，甲醇和水洗涤，离心收集产物；
E、最后，将产物放在80℃的真空烘箱中干燥即可得到Co-MIL-53(Fe)-NH2/X％UIO-66-NH2复合材料。
本发明Co-MIL-53(Fe)-NH2/UIO-66-NH2复合材料成功制备由X射线衍射(XRD)，三维荧光(PL)，傅里叶红外(FT-IR)，扫描电子显微镜(SEM)，能量色散X射线光谱(EDS)，X射线光电子能谱(XPS)和透射电子显微镜(TEM)来证明。XRD图谱中复合材料的衍射峰强度在2θ＝10-20°上升，说明了UIO-66-NH2上Co-MIL-53(Fe)-NH2含量的增加，证明复合材料的成功合成。FT-IR图中UIO-66-NH2，Co-MIL-53(Fe)-NH2与Co-MIL-53(Fe)-NH2/UIO-66-NH2复合材料的峰值能相对应，且Co-MIL-53(Fe)-NH2/UIO-66-NH2中出现Fe-O，Co-O和Zr-O的峰值，证明复合材料制备成功。SEM和TEM图谱证实了复合材料的结合。Co-MIL-53(Fe)-NH2的粒径约5-12nm，UiO-66-NH2的粒径为120～180nm。EDS和XPS图谱证实复合材料中存在C，O，N，Fe，Co和Zr元素，表明复合材料的成功合成。
本发明还提供了上述复合材料用在吸附和光降解领域，用于水中四环素的吸附和光降解。
吸附和光催化活性评价：在GHX-2型光化学反应仪(购自扬州大学科技城科技有限公司)中进行。将20mg催化剂，10mg PMS和50mL四环素(TC)(25mg/L)水溶液在50mL比色管中混合，加入光催化仪器反应器中。将该混合溶液在黑暗中磁力搅拌40分钟以达到吸附平衡，然后通过氙灯光照30分钟进行催化反应。每4分钟取3mL四环素溶液，立即通过离心分离3mL四环素溶液中的催化剂。使用紫外可见分光光度计(UV-3600，Shimadzu)测量吸光度，检测四环素的浓度变化，测量波长为357nm。对不同浓度的四环素溶液进行吸光度测定，绘制标准曲线。根据检测到的吸光度计算四环素的浓度，记为Ct。初始浓度25mg/L记为C0。
本发明所制备的Co-MIL-53(Fe)-NH2/UIO-66-NH2复合材料尤其是Co-MIL-53(Fe)-NH2/30％UIO-66-NH2在暗吸附40分钟后氙灯光照8分钟时对四环素的降解率可达88％。实验结果表明，通过物理混合的Co-MIL-53(Fe)-NH2/30％UIO-66-NH2在暗反应40分钟后氙灯光照8分钟时对四环素的降解率达到70％，远远低于复合材料Co-MIL-53(Fe)-NH2/30％UIO-66-NH2。
所述实施例为本发明的优选的实施方式，但本发明并不限于上述实施方式，在不背离本发明的实质内容的情况下，本领域技术人员能够做出的任何显而易见的改进、替换或变型均属于本发明的保护范围。
Claims (6)
1.一种Co-MIL-53(Fe)-NH2/UIO-66-NH2复合材料的制备方法，其特征在于：包括如下步骤：
(1)在DMF中加入设定量的Fe(NO3)3·9H2O、Co(NO3)2·6H2O和H2ATA，并超声处理直至完全溶解，得到混合溶液；
(2)向步骤(1)的混合溶液中加入设定量的UiO-66-NH2粉末，超声分散后置于内衬聚四氟乙烯的不锈钢反应釜中并加热至140℃±10℃并且至少保持6小时；
(3)冷却后，离心收集固体，并用甲醇和去离子水洗涤，真空干燥得所述Co-MIL-53(Fe)-NH2/UIO-66-NH2复合材料。
2.根据权利要求1所述的Co-MIL-53(Fe)-NH2/UIO-66-NH2复合材料的制备方法，其特征在于：步骤(3)中真空干燥温度为85℃。
3.根据权利要求1所述的Co-MIL-53(Fe)-NH2/UIO-66-NH2复合材料的制备方法，其特征在于：步骤(2)中Co-MIL-53(Fe)-NH2与UIO-66-NH2的质量比为1:1-7:3。
4.根据权利要求1所述的Co-MIL-53(Fe)-NH2/UIO-66-NH2复合材料的制备方法，其特征在于：复合材料中UIO-66-NH2的粒径为120～180nm，Co-MIL-53(Fe)-NH2的粒径为5～20nm。
5.如权利要求1至3中任一项所述的Co-MIL-53(Fe)-NH2/UIO-66-NH2复合材料的制备方法所制得的Co-MIL-53(Fe)-NH2/UIO-66-NH2复合材料。
6.如权利要求5所述的Co-MIL-53(Fe)-NH2/UIO-66-NH2复合材料的应用，其特征在于：用于水中四环素的吸附和光降解。
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