CN116492995A - 一种1,3,5-苯三羧酸修饰的UIO-66(Zr)金属有机框架材料的制备方法及应用 - Google Patents
一种1,3,5-苯三羧酸修饰的UIO-66(Zr)金属有机框架材料的制备方法及应用 Download PDFInfo
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Abstract
本发明公开了一种1,3,5‑苯三羧酸(BTC)改性UIO‑66吸附剂的制备方法及应用。本发明的制备方法,包括以下步骤:将四氯化锆、对苯二甲酸于溶剂中溶解,搅拌均匀,并加入乙酸进行调节,得混合液;将混合液于120℃溶剂热反应24 h,固液分离、洗涤干燥,得UIO‑66吸附剂。取一定量的UIO‑66和BTC加入去离子水,充分混合后置于磁力搅拌器下回流24 h,然后用去离子水洗涤3次,将洗涤好的材料放入60℃烘箱干燥过夜,即得到UIO‑66‑BTC。本发明采用溶剂热法制备UIO‑66吸附剂,再进行BTC接枝改性,改性时可在磁力搅拌回流下一步完成,工艺流程简单,条件易行;较于原始UIO‑66,其可通过螯合、离子交换和静电相互作用,大大增强对水溶液中Pb(Ⅱ)和MB的吸附能力,以期广泛应用于工矿企业含Pb(Ⅱ)/MB废水的处理工序。
Description
技术领域
本发明涉及重金属和染料吸附材料领域,特别涉及一种1,3,5-苯三羧酸修饰的UIO-66(Zr)金属有机框架材料,可用于水体中铅离子(Pb)和亚甲基蓝(MB)的吸附和富集分离。
背景技术
水污染一直是人类发展过程中的一个棘手问题,由于污染源来源广泛,组成成分复杂,按照污染物的化学类别通常被分为无机废水和有机废水。但在实际水污染中,往往是无机和有机废水的混合,废水中的重金属离子和染料由于其生物毒性和不可逆性,被认为是危害生态环境和人类健康的重要因素。例如,当Pb(II)超过最大允许浓度(我国饮用水卫生标准GB 57492022, Pb(II)≤0.01 mg/L)时,Pb(II)不仅会损害内分泌器官,从而影响骨功能和调节骨矿物质代谢的能力,还会干扰骨细胞的功能。同样,当染料被排放到水中时,它们会使水染上颜色。染料的存在减少了阳光的穿透力,导致光合作用的减少,对水生生物有不利的影响。Pb(II)和MB是常见污染水域中比较典型的污染物,且重金属和染料污染是一个全球性的环境问题,特别是在发展中国家,由于工业和农业活动的增加以及废水和生活污水中的污染物不适释放造成的。因此,寻找一种方便、安全的处理含重金属离子和染料废水的方法已迫在眉睫。
研究人员在处理环境问题上投入了大量的精力,到目前为止,处理污染物的方法有很多。在这些方法中,吸附技术因其成本低、操作简单、去除率高而成为一种流行的方法。其中吸附剂种类繁多,包括膨润土、树脂、磁性材料、有机框架材料等。它几乎符合研究人员对污染物去除的不同期望。
金属-有机框架是由有机桥接配体与金属离子或金属离子簇通过配位自组装而成的具有三维网络结构的无机有机材料。由于其具有较高的比表面积和可调节的功能化孔隙结构,在废水处理中具有良好的应用前景。其中,UIO-66是最具代表性的Zr离子基金属有机框架,具有优异的热稳定性、优异的水稳定性和各种官能团修饰。带有特定官能团的UIO-66基吸附剂的后修饰,与原始UIO-66相比,这种改性的MOFs不仅具有类似于UIO-66的优异性能,而且具有更高的活性,因而,在寻找经济、高效、简单的UIO-66改性方法一直是研究的热点。
发明内容
本发明的目的是提供一种利用乙酸作为调节剂采用溶剂热法合成具有缺陷的UIO-66,并以1,3,5-苯三羧酸(BTC)对合成的UIO-66进行水热后修饰制备了具有高功能性与稳定性相权衡的UIO-66-BTC吸附剂,用于Pb(II)和MB去除,以解决传统吸附剂对重金属离子和染料吸附性能低、选择性差、可重复使用性以及稳定性弱等问题。制备UIO-66吸附材料并利用1,3,5-苯三羧酸聚合物对所得UIO-66材料进行表面修饰改性,一方面可以使用具有亲和力的官能团对特定离子进行去除,另一方面预设接枝化高功能-稳定接枝基团选择性,解决吸附剂吸附量低的问题。探索制备改性UIO吸附剂的新途径,在高效吸附重金属/染料的同时,保证最佳经济效益和环境效益。本发明主要利用BTC接枝到UIO吸附材料上,制备UIO-66-BTC吸附剂的方法,整个过程操作简单、能耗低、成本低,制备出来的改性UIO吸附材料对Pb(II)和MB具有良好的吸附性能,可作为一种很好的吸附剂。
具体步骤为:
(1)在超声波的作用下,将840 mg四氯化锆和648 mg对苯二甲酸分别溶解在30 mL和10 mL的DMF中。
(2)将步骤(1)中得到的两种溶液混合并加入13.6 mL的乙酸作为控制MOF晶体的尺寸和晶体中缺陷的数量调节剂,直到混合物搅拌均匀。
(3)将步骤(2)中得产物转移到100 mL不锈钢聚四氟乙烯内衬的反应釜中,在120℃下反应24 h,随炉冷却后,在4000 r/min下离心,进行溶剂分离。
(4)将步骤(3)中得到的样品使用DMF浸泡12 h,再用甲醇浸泡活化12 h,重复3次,纯化去除未反应的对苯二甲酸。
(5)将步骤(4)所得产物置于培养皿中,放在60 ℃的烘箱中烘12 h,得到白色粉末。
(6)将200 mg步骤(5)得到的白色粉末与1200 mg 1,3,5-苯三羧酸混合后,加入50mL去离子水,并超声振荡30 min后,在60 ℃的水浴中磁力搅拌下回流24 h。
(7)将步骤(6)所得混合产物自然冷却,过滤,采用去离子水洗涤三遍。
(8)将步骤(7)所得产物置于培养皿中,放在60 ℃的烘箱内干燥过夜,获得UIO-66-BTC吸附剂。
(9)上述制得的UIO-66-BTC吸附材料应用于对水溶液中Pb(Ⅱ)和MB的吸附去除。
本发明利用UIO-66吸附剂作为基底,为开发低成本、高比表面积、高吸附容量和高选择性的重金属吸附剂提供理论和实践基础;采用溶剂热法制备UIO-66吸附材料,再进行BTC接枝改性,工艺流程简单,条件易行;接枝BTC后的UIO-66吸附材料相较于原始UIO-66吸附材料,能够通过螯合、离子交换和静电相互作用,大大增强对水溶液中Pb(Ⅱ)和MB的吸附能力;所制备吸附剂可广泛应用于工矿企业含Pb(Ⅱ)/MB废水的处理工序。
附图说明
图1为本发明实施例制得的改性前后UIO-66吸附剂SEM对比图谱。
图2为本发明实施例制得的改性和吸附前后UIO-66吸附剂的FT-IR对比图谱。
图3为本发明实施例制得的改性和吸附前后UIO-66吸附剂的XPS对比图谱。
图4为本发明实施例制得的改性和吸附前后UIO-66吸附剂的XRD对比图谱。
具体实施方式
实施例:
(1)在超声波的作用下,将840 mg四氯化锆和648 mg对苯二甲酸分别溶解在30 mL和10 mL的DMF中。
(2)将步骤(1)中得到的两种溶液混合并加入13.6 mL的乙酸作为控制MOF晶体的尺寸和晶体中缺陷的数量调节剂,直到混合物搅拌均匀。
(3)将步骤(2)中得产物转移到100 mL不锈钢聚四氟乙烯内衬的反应釜中,在120℃下反应24 h,随炉冷却后,在4000 r/min下离心,进行溶剂分离。
(4)将步骤(3)中得到的样品使用DMF浸泡12 h,再用甲醇浸泡活化12 h,重复3次,纯化去除未反应的对苯二甲酸。
(5)将步骤(4)所得产物置于培养皿中,放在60 ℃的烘箱中烘12 h,得到白色粉末。
(6)将200 mg步骤(5)得到的白色粉末与1200 mg 1,3,5-苯三羧酸混合后,加入50mL去离子水,并超声振荡30 min后,在60 ℃的水浴中磁力搅拌下回流24 h。
(7)将步骤(6)所得混合产物自然冷却,过滤,采用去离子水洗涤三遍。
(8)将步骤(7)所得产物置于培养皿中,放在60 ℃的烘箱内干燥过夜,获得UIO-66-BTC吸附剂。
(9)上述制得的UIO-66-BTC吸附剂应用于对水溶液中Pb(Ⅱ)和MB的吸附去除。
(10)称取一定量本实施例制得的改性前后的UIO-66吸附剂于100 mL聚氯乙烯离心管内,采用50 mL移液管向离心管中加入50 mL、一定浓度、一定pH的Pb(Ⅱ)/MB溶液,置于恒温水浴振荡器内,在一定温度、200 r/min转速条件下振荡混合一定时间后,取出离心管,用10 mL不带针头的注射器抽取10 mL上清液,在注射器上装0.45 μm滤膜过滤,每组实验设置三个平行样,采用ICP-AES测量Pb(Ⅱ)的浓度,采用UV-9000s测量MB的浓度,实验结果取三组数据的平均值。
采用新型热场发射扫描电镜(SEM,SU5000,日本日立)分析1,3,5-苯三羧酸改性UIO-66吸附剂的表面形貌,结果见图1;采用傅里叶红外光谱分析仪(FTIR,470 FTIR,美国热电尼高力仪器公司)对所得产物样品进行表面官能团测试,结果见图2;采用X射线光电子能谱分析(XPS,ESCALAB250Xi,美国热电公司)用于分析样品表面的元素组成信息,结果见图3;采用X射线衍射分析(XRD, X'Pert PRO,荷兰帕纳科公司)对所得产物样品进行晶体结构测试,结果见图4。
Claims (2)
1.一种1,3,5-苯三羧酸改性UiO-66吸附剂的制备方法,其特征在于具体步骤为:
(1)在超声波的作用下,将840 mg四氯化锆和648 mg对苯二甲酸分别溶解在30 mL和10mL的DMF中;
(2)将步骤(1)中得到的两种溶液混合并加入13.6 mL的乙酸作为控制MOF晶体的尺寸和晶体中缺陷的数量调节剂,直到混合物搅拌均匀;
(3)将步骤(2)中得产物转移到100 mL不锈钢聚四氟乙烯内衬的反应釜中,在120 ℃下反应24 h;反应结束后待冷却至室温,将得到的混合物在4000 r/min下离心,进行溶剂分离;
(4)将步骤(3)中得到的样品使用DMF浸泡12 h,再用甲醇浸泡活化12 h,重复3次,纯化去除未反应的对苯二甲酸;
(5)将步骤(4)所得产物置于培养皿中,放在60 ℃的烘箱中烘12 h,获得白色粉末UiO-66;
(6)将200 mg步骤(5)得到的白色粉末与1200 mg 1,3,5-苯三羧酸混合后,加入50 mL去离子水,并超声振荡30 min后,在60 ℃的水浴中磁力搅拌下回流24 h;;
(7)将步骤(6)所得产物进行自然冷却,过滤,采用去离子水洗涤三遍;
(8)将步骤(7)所得产物置于培养皿中,放在60 ℃的烘箱内干燥过夜,获得1,3,5-苯三羧酸改性UiO-66吸附剂;
(9)上述制得的1,3,5-苯三羧酸改性UiO-66吸附剂应用于对水溶液中Pb(II)和MB的吸附去除。
2.一种根据权利要求1所述制备方法制备的吸附剂在工矿企业处理含Pb(Ⅱ)/MB废水中的应用。
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