CN113070090A - 一种十二面体单原子铁类Fenton催化剂及其制备与应用 - Google Patents
一种十二面体单原子铁类Fenton催化剂及其制备与应用 Download PDFInfo
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Abstract
本发明公开了一种十二面体单原子铁类Fenton催化剂的制备方法及其应用。本发明是将乙酰丙酮铁、六水合硝酸锌、二甲基咪唑溶于甲醇,超声溶解并搅拌均匀,将得到的反应混合物转入反应釜中,通过溶剂热反应制备出由MOFs负载的铁基材料前驱体,然后在氩氛围下高温煅烧得到具有大比表面积的十二面体单原子铁催化剂,并将其应用于异相芬顿反应中,实现对磺胺类抗生素的高效降解。该催化剂具有好的循环使用性能、宽的pH适用范围(3~8),以及制备方法简单等特点,具有较高的应用价值,可用于抗生素废水的处理。
Description
技术领域
发明涉及一种纳米尺度的单原子铁催化剂及其制备方法和应用,该催化剂能通过活化过氧化氢实现对废水中磺胺类抗生素的高效去除,属于环境保护及处理的技术领域。
背景技术
水生环境中的抗生素残留物引起广泛关注,因为它们可能引起抗生素抗性细菌(ARB)和抗生素抗性基因(ARG),由于它们对水生生态系统和人类健康的危害,它们被认为是新型的水污染物。磺胺类由于价格低廉且性能稳定而属于世界范围内广泛使用的一类抗生素,而对磺胺类抗生素污染物的处理是现有水处理技术的一大挑战,去除效率低。与其他磺胺类抗生素相比,磺胺嘧啶在污水厂污染物中具有很高的检出频率(近100%)和高浓度(高达216ng/L)。除了相关细菌耐药性的传播外,磺胺嘧啶的广泛使用还可能带来相关的毒性风险。根据全球化学品统一分类和标签制度发布的标准,磺胺嘧啶被归类为剧毒有机污染物。因此,必须解决抗生素排入环境之前的污染问题,以控制ARB和ARG的传播途径。
目前用于处理污水中抗生素等有机污染物的方法较多,主要包括物理吸附、生化法、高级氧化法等。然而物理方法仅使抗生素污染物发生相的变化而无法使其分解变得无害;生化法需要很长时间,常用于处理低浓度的污染物且难以实现抗生素的降解。高级氧化技术通过产生氧化性极强的活性自由基,能够将机化合物大分子降解成为低毒或无毒的小分子物质,直至最终降解成为二氧化碳和水等无机物质。因此,目前高级氧化法被认为是去除水中有机物的最有效方法之一。铁基材料成本低廉,无毒,催化活性好,对于废水中的抗生素的去除具有明显的优势。
发明内容
本发明的目的是提供一种纳米尺度的十二面体单原子铁类Fenton催化剂及其制备方法,并将其应用于降解水中磺胺类抗生素。
本发明所提供的纳米尺度的十二面体单原子铁类Fenton催化剂,平均比表面积为600~800m2/g,平均孔径为2~3nm,十二面体结构的尺寸为300~600nm,是微孔介孔混合存在的结构。
本发明所要提供的纳米尺度的十二面体单原子铁类Fenton催化剂的制备方法,采用以下步骤:
(1)铁盐、锌盐、二甲基咪唑溶于甲醇中,超声,搅拌,得到棕红色溶液。
(2)将得到棕红色溶液转移到反应釜中,溶剂热反应3~5h,反应温度为100~150℃。
(3)冷却至室温后,将得到的棕红色沉淀收集起来,然后用N,N二甲基甲酰胺和甲醇清洗,真空干燥,得到由MOFs(金属有机骨架)负载的铁基材料前驱体。
(4)将得到的前驱体研磨成粉末之后放入管式炉中,在氩气氛围中,900-950℃高温煅烧2-4h,冷却即可得到纳米尺度的十二面体单原子铁类Fenton催化剂。
本发明上述所述的制备方法中,优选的,步骤(1)所述的铁盐为乙酰丙酮铁,锌盐为六水合硝酸锌。
本发明上述的制备方法中,优选的,步骤(1)的搅拌转速为500~900r/min,搅拌时间为0.5~2h;超声10~30min。
本发明上述所述的制备方法中,优选的,步骤(1)中铁盐、锌盐、二甲基咪唑的摩尔比为1:5-15:20-60,更优选为1:8-12:30-50,最优选为1:10:40。
本发明上述所述的制备方法中,优选的,超声,搅拌,离心均在室温下进行。
本发明上述所述的制备方法中,优选的,真空干燥温度为50~90℃,干燥时间为10~20h。
本发明所提供的纳米尺度的十二面体单原子铁类Fenton催化剂可在磺胺类抗生素降解中应用。进一步的,所述催化剂可应用于磺胺类抗生素的异相芬顿降解。所述磺胺类抗生素包括但不限于磺胺嘧啶、磺胺二甲嘧啶、磺胺甲恶唑、磺胺异恶唑、磺胺间甲氧嘧啶等等。
本发明所提供的纳米尺度的十二面体单原子铁类Fenton催化剂在对磺胺嘧啶的降解应用时,可采用下述方法步骤:
将纳米尺度的十二面体单原子铁类Fenton催化剂均匀分散在含有磺胺嘧啶的待处理水样中,加入过氧化氢作为氧化剂,降解时间为60~100min,过滤去除固体催化剂,得到处理后的水;优选的,所述待处理的水体pH值为3~7。
本发明的纳米尺度的十二面体单原子铁类Fenton催化剂可实现对磺胺类抗生素的高效降解。该催化剂具有好的循环使用性能、宽的pH适用范围(3~8),以及制备方法简单等特点,具有较高的应用价值,可用于磺胺类抗生素废水的处理。
附图说明
图1为本发明专利方法下制备出的一种纳米尺度的十二面体单原子铁催化剂的扫描电子显微镜(SEM)、透射电子显微镜(TEM)、环形暗场扫描电镜(HAADF)及元素分布图,用以更好地观察本专利方法下合成的催化剂的微观形貌,可看到材料中的孤立存在的Fe单原子。右下角比例尺:(a)500nm,(b)50nm,(c)2nm。
图2为本发明专利方法下制备的一种纳米尺度的十二面体单原子铁催化剂的BET吸脱附曲线和孔径分布曲线谱图,说明材料具有较大的比表面积,具有较好的吸附性能。
图3为本发明专利方法下制备的一种纳米尺度的十二面体单原子铁类Fenton催化剂的线性扫描伏安曲线,由曲线可确定材料的起始电位与半波电位,进而可以确定材料的氧化还原活性,从数据可知催化剂有较好的催化活性,说明本专利方法下所合成的催化剂能够催化降解有机污染物。
图4为本发明制备出的一种纳米尺度的十二面体单原子铁类Fenton催化剂降解磺胺嘧啶的浓度随时间变化图。图中Fe-ISAs@CN为按本专利方法合成制备的单原子催化剂;CN为相同方法但未加Fe源得到的对比材料。
具体实施方式
下面结合具体的实施方法对本发明做详细的阐述,但本发明的实质内容并不仅限于下述实施例所述。如无特别说明,所述方法均为常规方法,所述材料均能从公开商业途径获得,本领域内的技术人员应当知晓任何基于本发明实质内容的简单变换或替代均属于本发明所要求的保护范围。
下述实施例中,采用FEI-Quanta 200型扫描电子显微镜(SEM)、HR-TEM,TalosF200X型透射电子显微镜(TEM)及JEM-ARM200F型环形暗场扫描电镜(HAADF)表征催化剂的形貌;使用Micromeritics ASAP 2020M对催化剂进行氮气吸脱附比表面积分析及粒径与孔径分布分析;使用PINE型盘环电极装置(RDE)对样品进行分析;使用UV-2550型紫外-可见光分光光度计检测处理水样中的磺胺嘧啶的浓度。
实施例1
步骤1:乙酰丙酮铁、六水合硝酸锌、二甲基咪唑溶于60mL甲醇中,其中,二甲基咪唑的摩尔浓度为0.4mol/L;六水合硝酸锌的摩尔浓度为0.1mol/L;乙酰丙酮铁的摩尔浓度为0.01mol/L,超声15min,搅拌1h,得到棕红色溶液。
步骤2:将上述棕红色溶液转移到100mL反应釜中并放入烘箱中溶剂热反应4h,反应温度为120℃。
步骤3:将上述反应得到的溶液离心分离,并用甲醇和N,N二甲基甲酰胺各洗三次,真空60℃干燥12h,得到MOFs负载的前驱体材料。
步骤4:将得到的前驱体研磨成粉末之后放入管式炉中,在氩气气氛保护下,经过930℃的高温煅烧3h,随炉冷却即可得到纳米尺度的十二面体单原子铁催化剂Fe-ISAs@CN。
将上述纳米尺度的十二面体单原子铁催化剂经SEM、TEM、HAADF表征其形貌及元素分布,可以看出是十二面体纳米材料且各元素均匀分布(图1);采用Micromeritics ASAP2020M分析仪在氮气氛围测得催化剂比表面积为727.66m2/g,平均孔径为2.164nm。吸脱附曲线和孔径分布曲线如图2;通过RDE分析了材料的氧化还原活性,确定了在氧化还原过程中转移的电子为3.8(如图3)。
本实验得到的纳米尺度的十二面体单原子铁催化剂被应用于水中磺胺嘧啶的降解(Fe-ISAs@CN/H2O2):称取上述制备的纳米尺度的十二面体单原子铁催化剂5mg加入到50mL水样中,水样中的H2O2浓度10mM、磺胺嘧啶浓度为10mg/L。在25℃,pH=3条件下进行反应,在摇床中充分震荡,在特定的时间取样并使用滤头过滤,通过紫外-可见光分光光度计检测水溶液中磺胺嘧啶的含量(图4),反应时间为60min时,去除效率达到91%。将上述反应后溶液中的催化剂过滤后重复使用,其他条件不变,5次后磺胺嘧啶的去除率仍可达到82%。
图4中,-H2O2:以H2O2进行降解磺胺嘧啶的对比实验;-CN:以未加Fe源的材料作为催化剂降解磺胺嘧啶的对比实验;-Fe-ISAs@CN:以本发明得到的催化剂进行降解磺胺嘧啶的对比实验;-CN/H2O2:添加H2O2以未加Fe源的对比材料作为催化剂进行降解磺胺嘧啶的对比实验;-Fe-ISAs@CN/H2O2:添加H2O2且以本发明催化剂进行降解磺胺嘧啶的实验。
实施例2
步骤1:乙酰丙酮铁、六水合硝酸锌、二甲基咪唑溶于60mL甲醇中,其中,二甲基咪唑的摩尔浓度为0.4mol/L;六水合硝酸锌的摩尔浓度为0.1mol/L;乙酰丙酮铁的摩尔浓度为0.01mol/L,超声15min,搅拌1h,得到棕黄色溶液。
步骤2:将上述棕红色溶液转移到100mL反应釜中并放入烘箱中溶剂热反应4小时,反应温度为120℃。
步骤3:将上述反应得到的溶液离心分离,并用甲醇和N,N二甲基甲酰胺各洗三次,真空60℃干燥12h,得到MOFs负载的前驱体材料。
步骤4:将得到的前驱体研磨成粉末之后放入管式炉中,在氩气气氛保护下,经过900℃的高温煅烧3h,冷却即可得到纳米尺度的十二面体单原子铁催化剂。
本实验得到的纳米尺度的十二面体单原子铁催化剂被应用于水中磺胺甲恶唑的降解:称取上述制备的纳米尺度的十二面体单原子铁催化剂5mg加入到50mL水样中,水样中H2O2浓度10mM、磺胺甲恶唑浓度为10mg/L。在25℃,pH=6.5条件下进行反应,在摇床中充分震荡,在特定的时间取样并使用滤头过滤,通过紫外-可见光分光光度计检测水溶液中磺胺甲恶唑的含量,反应时间为60min时,去除效率达到80%。将上述反应后溶液中的催化剂过滤后重复使用,其他条件不变,5次后磺胺嘧啶的去除率仍可达到76%。
Claims (10)
1.一种十二面体单原子铁类Fenton催化剂,平均比表面积为600~800m2/g,平均孔径为2~3nm,十二面体结构的尺寸为300~600nm。
2.一种十二面体单原子铁类Fenton催化剂的制备方法,其特征在于,包括以下步骤:
(1)铁盐、锌盐、二甲基咪唑溶于甲醇中,超声,搅拌,得到棕红色溶液;
(2)将棕红色溶液转移到反应釜中,100~150℃下反应3~5h;
(3)冷却至室温后,将得到的棕红色沉淀用N,N二甲基甲酰胺和甲醇分别清洗,真空干燥,得到铁基材料前驱体;
(4)将得到的前驱体研磨成粉末之后放入管式炉中,在氩气氛围下,900-950℃的高温煅烧2-4h,得到纳米尺度的十二面体单原子铁催化剂。
3.根据权利要求2所述的制备方法,其特征在于,步骤(1)中的铁盐为乙酰丙酮铁,锌盐为六水合硝酸锌。
4.根据权利要求2所述的制备方法,其特征在于,步骤(1)中所述的铁盐、锌盐、二甲基咪唑的摩尔比为1:5-15:20-60。
5.根据权利要求4所述制备的方法,其特征在于,所述的铁盐、锌盐、二甲基咪唑的摩尔比为1:8-12:30-50。
6.根据权利要求2所述的制备方法,其特征在于,步骤(3)所述的真空干燥温度为50~90℃,干燥时间为10~20h。
7.权利要求1所述的或者由权利要求2~6任一项所述制备方法得到的纳米尺度的十二面体单原子铁催化剂在磺胺类抗生素降解中的应用。
8.根据权利要求7所述应用,其特征在于,所述催化剂在磺胺类抗生素的异相类芬顿降解中应用。
9.根据权利要求8所述应用,其特征在于,采用下述方法步骤:
将纳米尺度的十二面体单原子铁催化剂均匀分散在含磺胺嘧啶的待处理水样中,加入过氧化氢作为氧化剂,降解时间为60~100min,过滤去除固体催化剂,得到处理后的净化水。
10.根据权利要求9所述应用,其特征在于,所述待处理水体的pH值为3~7。
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