CN110156108B - 一种利用基于MIL-101(Cr3+)的金属有机骨架材料吸附水中有机染料的方法 - Google Patents
一种利用基于MIL-101(Cr3+)的金属有机骨架材料吸附水中有机染料的方法 Download PDFInfo
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Abstract
本发明公开了一种利用基于MIL‑101(Cr3+)的金属有机骨架材料吸附水中有机染料的方法。其中包括以下步骤:(1)将2‑甲基咪唑、Azobenzene‑4‑4’dicarboxylic acid、Cr(NO3)3·9H2O溶解于去离子水中,进行搅拌,在150℃‑180℃下采用水热法反应一定时间。(2)将反应产物反复洗涤提纯,再真空干燥,即可得到介孔‑微孔金属有机骨架材料。(3)将步骤(2)中得到介孔‑微孔金属有机骨架材料放入含有有机染料的水体中搅拌一定时间后,即完成吸附水体中的有机染料。该化合物可作为吸附剂,高效、快速的吸附亚甲基蓝等有机染料,对亚甲基蓝的去除率高达98.77%以上。
Description
技术领域
本发明涉及一种金属有机骨架材料,尤其涉及一种利用基于MIL-101(Cr3+)的金属有机骨架材料吸附水中有机染料的方法。
背景技术
随着我国纺织印染工业的迅猛发展,染料废水已成为了当今最主要的水污染源之一。在整个染料的生产过程中,硝化、横化、重氮化、还原氧化及盐析等流程中都有大量的染料废水产生。据估计,染料生产过程中大约有的有机原料和的无机原料进入水中,加上染料旳废水,致使染料废水成分非常复杂。染料废水中含有多种具有生物毒性及致癌性物质,同时还含有多种难降解的有害物质,其中有机污染物危害最为严重,而这些有色废水在环境中又会通过氧化、水解以及其它化学反应生成有毒的副产物。若直接排入水体,会严重影响水的透光性及水生生物的生长,且极易导致水体富营养化,破坏水体生态平衡。
染料废水具有以下特点:(1)染料废水中含有大量以苯、萘、醌等为基体的有机物,且大多含有极性基团,有色基团如(-NO、-N)以及苯胺、碱、酚类等,在浓度低于1ppm时有些染料就能使接受水体明显着色;(2)染料本身或中间体分子往往含有极性基团,这使他们的水溶性大大增强,致使流失量明显加大。因此染料废水中通常含有产品原料和副产物,如NaOH、NaCl、硫化物等无机盐和氨基化合物、苯胺、齡类、硝基物、卤化物等系列有机物,浓度高、毒性大;(3)染料废水多呈酸性,也有的呈碱性,一般含盐量都很大;(4)染料的种类日趋复杂,且抗光解、抗氧化、抗生物降解能力越来越强,染料废水用一般处理方法处理的难度越来越大。
目前,人们在减少污染以及去除环境中的污染物方面已经做了很多的努力,涌现出大量环境污染治理技术,如生物处理法、化学氧化法、高级氧化法、吸附法、膜分离法等。其中,吸附法一直以来备受人们青睐,它是利用多孔性的吸附剂将环境污染物富集转移到吸附剂表面,从而使污染物得以去除的一种方法,该方法具有成本相对较低、应用范围广、设计简单、操作运行简便、无二次污染且吸附剂易再生等优点。由于废水中染料分子的抗光解、抗氧化能力较强,因此,研究适用于液相吸附染料分子的吸附剂具有十分重要的意义。然后,到目前为止,很少有报道使用材料用作染料液相吸附剂的研究。最近,利用金属有机骨架材料(metal-organic frameworks,简称 MOFs)吸附去除环境污染物的研究受到人们的广泛关注。MOFs是指由金属离子或金属簇与有机配体,通过自组装形成的具有三维周期网格结构的有机-无机杂化新型多孔材料。MOFs具有超高的比表面积、较高且可调的孔隙率、结构组成多样性、开放的金属位点、化学可修饰等优点,在选择性吸附领域中展现出广阔的应用前景。
发明内容
基于上述问题,本发明目的在于提供一种新的制备方法,得到一种具有微孔结构且可有效吸附含有甲基橙、亚甲基蓝等有机染料的新型金属有机骨架材料。
针对以上问题,提供了如下技术方案:一种利用基于MIL-101(Cr3+)的金属有机骨架材料吸附水中有机染料的方法,包括以下步骤:
(1)将2-甲基咪唑溶于20ml的高纯水中,搅拌5-10min;将Azobenzene-4-4’dicarboxylic acid缓慢加入到2-甲基咪唑溶液中,继续搅拌20-40min;再将Cr(NO3)3·9H2O加入搅拌的混合溶液中,搅拌20-40min,溶液呈黑色浑浊状;其中中2-甲基咪唑、Azobenzene-4-4’dicarboxylic acid与Cr(NO3)3·9H2O的物质的量的比为1:2:2;
(2)将步骤(1)中的得到的混合溶液移至30ml聚四氟乙烯材质内衬的不锈钢反应釜中,并置于150℃-180℃烘箱中反应24-36h。将反应釜自然冷却至室温,将所得的沉淀离心分离,反复洗涤,真空干燥,即可得到一种基于MIL-101(Cr3+)型的介孔-微孔金属有机骨架材料;
(3)吸附水体中的有机染料:将步骤(2)中得到的基于MIL-101(Cr3+)型的介孔-微孔的金属有机骨架材料放入含有有机染料的水体中搅拌一定时间后,即完成吸附水体中的有机染料。
本发明进一步设置为:所述步骤(1)中的搅拌过程为常温下进行。
本发明进一步设置为:所述步骤(2)中烘箱的温度为170℃。
本发明进一步设置为:所述步骤(2)中在烘箱中反应的时间为24小时。
本发明进一步设置为:所述步骤(2)中所得沉淀离心分离后,用高纯水与无水乙醇多次洗涤,在80℃下真空干燥15h,获得所述一种基于MIL-101(Cr3+)型的介孔-微孔金属有机骨架材料。
本发明进一步设置为:所述步骤(2)中所得到的基于MIL-101(Cr3+)型的介孔-微孔金属有机骨架材料的BET比表面积为76.1679 m²/g。
如上所述,本发明提供了一种利用基于MIL-101(Cr3+)的金属有机骨架材料吸附水中有机染料的方法,所述基于MIL-101(Cr3+)型的介孔-微孔金属有机骨架材料制备过程简单具有一定的比表面积,具有微孔和介孔的特性,还具有良好的吸附性能,可用来作为吸附剂来吸附有机染料,尤其在有机染料中对亚甲基蓝的吸附效果明显,从而可用于污水处理,在环境化学中有着巨大的应用潜力和工业价值。
附图说明
图1为本发明实施例一制备得到的基于MIL-101(Cr3+)型的介孔-微孔金属有机骨架材料的热重曲线(TGA)图;
图2为本发明实施例一制备得到的基于MIL-101(Cr3+)型的介孔-微孔金属有机骨架材料的孔径分布曲线图;
图3为本发明实施例一制备得到的基于MIL-101(Cr3+)型的介孔-微孔金属有机骨架材料的氮气吸附曲线图;
图4为本发明实施例一制备得到的基于MIL-101(Cr3+)型的介孔-微孔金属有机骨架材料的扫描电子显微镜(SEM)图,标尺为40μm;
图5为为本发明实施例一制备得到的基于MIL-101(Cr3+)型的介孔-微孔金属有机骨架材料对亚甲基蓝溶液的吸附曲线图;
图6为为本发明实施例一制备得到的基于MIL-101(Cr3+)型的介孔-微孔金属有机骨架材料对罗丹明B溶液的吸附曲线图;
图7为为本发明实施例一制备得到的基于MIL-101(Cr3+)型的介孔-微孔金属有机骨架材料对甲基橙溶液的吸附曲线图;
图8为为本发明实施例一制备得到的基于MIL-101(Cr3+)型的介孔-微孔金属有机骨架材料对亚甲基蓝溶液、罗丹明B溶液、甲基橙溶液的去除率对比图。
具体实施方式
下面结合附图和实施例,对本发明的具体实施方式作进一步详细描述。以下实施例用于说明本发明,但不用来限制本发明的范围。
以下实施例中产品的检测条件为:
热重Thermogravimetric analysis (TGA) 是在氮气(N2)气氛下用 TA-Q600 热重分析仪在温州大学测定;气体吸附和Bet比表面积测试在上海麦克仪器分析服务中心测试;扫描电镜(SEM)在温州大学测定;液体紫外分光光度计(UV2450)在温州大学测定。
实施例一
基于MIL-101(Cr3+)型的介孔-微孔金属有机骨架材料的制备:
将(0.0821g,1mmol) 2-甲基咪唑溶于20ml的高纯水中,常温搅拌5min;将(0.5401g,2mmol) Azobenzene-4-4’dicarboxylic acid缓慢加入到2-甲基咪唑溶液中,常温继续搅拌25min;再将(0.8003g,2mmol)Cr(NO3)3·9H2O加入搅拌的混合溶液中,常温搅拌15min,溶液呈黑色浑浊状。将得到的混合溶液移至30ml聚四氟乙烯材质内衬的不锈钢反应釜中,并置于170℃烘箱中反应24h。将反应釜自然冷却至室温,将所得的沉淀离心分离,用无水乙醇洗涤3次,再用高纯水洗涤3次,80℃干燥15h,即可得到一种基于MIL-101(Cr3+)型的介孔-微孔金属有机骨架材料。
图1为基于MIL-101(Cr3+)型的介孔-微孔金属有机骨架材料的热重曲线。如图所示,从23℃到350℃样品的重量有轻微的失重,这主要是由于样品中溶剂分子的失去;从350℃到410℃样品的重量发生了快速的失重,这表明样品的结构快速坍塌;由于有机配体的碳化,410℃以上,样品的重量继续缓慢下降,表明C和N的氧化和形成的气体的释放。
图2为本实施例得到的MOF材料的孔径分布曲线图,从图中可以看出,孔径以介孔为主,存在部分微孔,主要分布在5nm2左右。
图3为本实施例得到的MOF材料的氮气吸附曲线图,样品的BET比表面积为76.1679m2/g,孔径以介孔为主,具有有微孔的特性,主要分布在5纳米左右。
图4为本实施例得到的MOF材料的扫描电子显微镜(SEM)图,标尺为40μm,从图中可以看出样品大小不均匀,呈不规则的块状。
实施例二
将(0.0821g,1mmol) 2-甲基咪唑溶于20ml的高纯水中,搅拌5min;将(0.5401g,2mmol) Azobenzene-4-4’dicarboxylic acid缓慢加入到2-甲基咪唑溶液中,继续搅拌25min;再将(0.8003g,2mmol)Cr(NO3)3·9H2O加入搅拌的混合溶液中,搅拌15min,溶液呈黑色浑浊状。将得到的混合溶液移至30ml聚四氟乙烯材质内衬的不锈钢反应釜中,并置于160℃烘箱中反应24h。
实施例三
将(0.0821g,1mmol) 2-甲基咪唑溶于20ml的高纯水中,搅拌5min;将(0.5401g,2mmol) Azobenzene-4-4’dicarboxylic acid缓慢加入到2-甲基咪唑溶液中,继续搅拌25min;再将(0.8003g,2mmol)Cr(NO3)3·9H2O加入搅拌的混合溶液中,搅拌15min,溶液呈黑色浑浊状。将得到的混合溶液移至30ml聚四氟乙烯材质内衬的不锈钢反应釜中,并置于150℃烘箱中反应24h。
实施例四
将(0.0821g,1mmol) 2-甲基咪唑溶于20ml的高纯水中,搅拌5min;将(0.5401g,2mmol) Azobenzene-4-4’dicarboxylic acid缓慢加入到2-甲基咪唑溶液中,继续搅拌25min;再将(0.8003g,2mmol)Cr(NO3)3·9H2O加入搅拌的混合溶液中,搅拌15min,溶液呈黑色浑浊状。将得到的混合溶液移至30ml聚四氟乙烯材质内衬的不锈钢反应釜中,并置于180℃烘箱中反应24h。
实施例五
将(0.0821g,1mmol)2-甲基咪唑溶于20ml的高纯水中,搅拌5min;将(0.5401g,2mmol) Azobenzene-4-4’dicarboxylic acid缓慢加入到2-甲基咪唑溶液中,继续搅拌25min;再将(0.8003g,2mmol)Cr(NO3)3·9H2O加入搅拌的混合溶液中,搅拌15min,溶液呈黑色浑浊状。将得到的混合溶液移至30ml聚四氟乙烯材质内衬的不锈钢反应釜中,并置于170℃烘箱中反应36h。
采用下述实验证明本发明效果:
基于MIL-101(Cr3+)型的介孔-微孔金属有机骨架材料对有机染料的吸附实验:
(1)配制浓度为15mg/L的亚甲基蓝溶液,分别量取40mL的亚甲基蓝溶液于锥形瓶中,称取30mg样品放置于亚甲基蓝溶液中,常温搅拌1440min,480min,360min,240min,120min,60min,30min,5min,过滤后取其清液测试紫外分光光度计。
(2)配制浓度为15mg/L的罗丹明B溶液,分别量取40mL的罗丹明B溶液于锥形瓶中,称取30mg样品放置于罗丹明B溶液中,常温搅拌1440min,480min,360min,240min,120min,60min,30min,5min,过滤后取其清液测试紫外分光光度计。
(3)配制浓度为15mg/L的甲基橙溶液,分别量取40mL的甲基橙溶液于锥形瓶中,称取30mg样品放置于甲基橙溶液中,常温搅拌1440min,480min,360min,240min,120min,60min,30min,5min,过滤后取其清液测试紫外分光光度计。
图5为本实施例得到的MOF材料对亚甲基蓝溶液的吸附曲线,原亚甲基蓝溶液的浓度为15mg/L,在搅拌5min后,吸光度已经降到了接近0.75,随着搅拌时间的增长,在搅拌60min后,吸光度更是降低到了接近0.03。从图中可以看出,样品对于亚甲基蓝溶液的吸附有着高效、快速吸附的效果。
图6为本实施例得到的MOF材料对罗丹明B溶液的吸附曲线,在搅拌5min后,罗丹明B溶液的吸光度降到了0.83左右,但随着时间的增加,罗丹明B溶液的吸光度并没有较大的减小。在搅拌480min后,罗丹明B溶液的吸光度接近0.5。从图中可以看出,样品对于罗丹明B溶液的吸附效果远没有对亚甲基蓝的吸附效果好。
图7为本实施例得到的MOF材料对甲基橙溶液的吸附曲线,在搅拌5min后,甲基橙溶液的吸光度降到了0.5左右,在搅拌720min后,吸光度接近0.2。从图中可以看出,样品吸附甲基橙的效果也没有吸附也甲基蓝的好。
图8为本实施例得到的MOF材料对三种有机染料的去除率的比较图,从图中可以看出,样品对亚甲基蓝有着快速、高效的吸附效果,其他两种有机染料的吸附效果并不是很好。
以上所述仅是本发明的优选实施方式,应当指出,对于本技术领域的普通技术人员来说,在不脱离本发明技术原理的前提下,还可以做出若干改进和变型,上述假设的这些改进和变型也应视为本发明的保护范围。
Claims (6)
1.一种利用基于MIL-101(Cr3+)的金属有机骨架材料吸附水中有机染料的方法,其特征在于:包括以下步骤:
(1)将2-甲基咪唑溶于20ml的高纯水中,搅拌5-10min;将Azobenzene-4-4’dicarboxylic acid缓慢加入到2-甲基咪唑溶液中,继续搅拌20-40min;再将Cr(NO3)3·9H2O加入搅拌的混合溶液中,搅拌20-40min,溶液呈黑色浑浊状;其中2-甲基咪唑、Azobenzene-4-4’dicarboxylic acid与Cr(NO3)3·9H2O的物质的量的比为1:2:2;
Azobenzene-4-4’dicarboxylic acid
(2)将步骤(1)中的得到的混合溶液移至30ml聚四氟乙烯材质内衬的不锈钢反应釜中,并置于150℃-180℃烘箱中反应24-36h;将反应釜自然冷却至室温,将所得的沉淀离心分离,反复洗涤,真空干燥,即可得到一种基于MIL-101(Cr3+)型的介孔-微孔金属有机骨架材料;
(3)吸附水体中的有机染料:将步骤(2)中得到的基于MIL-101(Cr3+)型的介孔-微孔的金属有机骨架材料放入含有有机染料的水体中搅拌一定时间后,即完成吸附水体中的有机染料。
2.根据权利要求1所述的一种利用基于MIL-101(Cr3+)的金属有机骨架材料吸附水中有机染料的方法,其特征在于:所述步骤(1)中的搅拌过程为常温下进行。
3.根据权利要求1所述的一种利用基于MIL-101(Cr3+)的金属有机骨架材料吸附水中有机染料的方法,其特征在于:所述步骤(2)中烘箱温度为170℃。
4.根据权利要求1所述的一种利用基于MIL-101(Cr3+)的金属有机骨架材料吸附水中有机染料的方法,其特征在于:所述步骤(2)中在烘箱中反应的时间为24小时。
5.根据权利要求1所述的一种利用基于MIL-101(Cr3+)的金属有机骨架材料吸附水中有机染料的方法,其特征在于:所述步骤(2)中所得沉淀离心分离后,用高纯水与无水乙醇多次洗涤,在80℃下真空干燥15h,获得所述一种基于MIL-101(Cr3+)型的介孔-微孔金属有机骨架材料。
6.根据权利要求1所述的一种利用基于MIL-101(Cr3+)的金属有机骨架材料吸附水中有机染料的方法,其特征在于:基于MIL-101(Cr3+)型的介孔-微孔金属有机骨架材料的BET比表面积为76.1679 m²/g。
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