CN112973738B - 一种磁性自组装MoS2@Fe3O4@Cu2O光催化剂的制备方法及其应用 - Google Patents
一种磁性自组装MoS2@Fe3O4@Cu2O光催化剂的制备方法及其应用 Download PDFInfo
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Abstract
本发明属于环境材料合成技术领域,具体涉及一种磁性自组装MoS2@Fe3O4@Cu2O光催化剂的合成方法;具体步骤:FeCl3·6H2O、NaAc溶于乙二醇中,搅拌后加入MoS2纳米片,搅拌后转移溶液至反应釜进行分级溶剂热反应,反应结束后样品冷却至室温,经离心收集,洗涤后干燥。再将MoS2@Fe3O4和CuSO4溶解在去离子水中搅拌,将NaBH4溶液添加到混合溶液中,搅拌后洗涤,真空干燥后得到样品即为磁性自组装MoS2@Fe3O4@Cu2O光催化剂。本发明的材料通过分级溶剂热法和磁性自组装技术的结合而制备,通过调控光催化剂的形貌及形成类Z型异质结以提高其光催化性能。
Description
技术领域
本发明属于环境材料合成技术领域,具体涉及一种磁性自组装MoS2@Fe3O4@Cu2O光催化剂的合成方法,及其高效光催化降解四环素的研究。
背景技术
目前,水环境污染问题日益严重,寻找一种合适的解决方案来有效和经济地处理水环境中的污染物是研究人员不断探索的主题之一。众所周知,水环境中存在最棘手的污染物是残留抗生素;四环素作为常见的抗生素,常用于人们的日常生活,特别是在水产养殖,滥用四环素不仅会造成大量的残留污染物排入环境,对环境尤其是水环境造成严重的污染,也会阻碍水处理的进展。考虑四环素对环境和人体的污染,研究能够去除并降解水中四环素的材料具有重要意义。
光催化技术由于其节能、环保和低成本等优点被认为是一种有效的环境保护解决方案。光降解方法将抗生素氧化成生物毒性较小且易生物降解的物质,甚至将它们转化为无害化合物。目前光催化领域设计的光催化剂种类繁多,但都涉及光催化效果差、光稳定性差、光响应区间短、光生电子空穴易复合等缺陷。
一方面,为了增强材料的光生电子空穴分离的效率,在合成光催化剂时选用分级溶剂热法以合成小粒径光催化剂,使电子更容易跃迁、分离,从而进一步提高材料的光降解能力。另一方面,为了简化材料的合成过程并有效降解四环素,引入了磁性自组装技术,磁性自组装技术是一种在磁性纳米材料合成过程中聚合金属无机物使其完成自组装的过程,利用磁性光催化剂的作用控制复合光催化剂的形貌,增强复合光催化剂的降解能力。
在过去的几年中,光催化剂作为处理水中污染物的研究受到了很多关注,然而光催化和磁性自组装技术的有效结合实现在复杂的水环境中处理多种污染物的研究还未见报道。因此,在复杂的水污染处理中,制备一种能够简单制备并降解水中四环素的材料具有广阔的前景和实用性。
发明内容
为了克服现有技术的不足,本发明提供一种磁性自组装MoS2@Fe3O4@Cu2O光催化剂,利用Fe3O4颗粒间的磁相互吸引作用将MoS2纳米片组装为花球状,即磁性自组装技术;在此基础上引入Cu2O,得到MoS2@Fe3O4@Cu2O花球,并通过花球中花瓣的空间限域效应将 Cu2O调控为小颗粒,并进一步形成类Z型异质结,使材料的降解率相对较高;将0.01g该磁性自组装光催化剂用于100mL 20mg/L的四环素溶液的光催化降解,在1h的模拟可见光照射下降解率达到了70%以上;此外,MoS2@Fe3O4@Cu2O的光催化效率分别是MoS2、 MoS2@Fe3O4和MoS2@Cu2O的3.5、1.75和2.5倍。
本发明提供一种磁性自组装MoS2@Fe3O4@Cu2O光催化剂的制备方法,按照下述步骤进行:
步骤1:2D-MoS2的合成:
硫代乙酰胺、钼酸钠和去离子水混合,磁力搅拌后,将所得无色混合溶液转移至高压反应釜中进行水热反应,反应结束冷却至室温后,得到黑色产物,用去离子水和乙醇洗涤数次;然后将黑色产物在真空冷冻干燥机中进行冻干处理,所得产物在室温下保存;
步骤2:MoS2@Fe3O4的合成:
将FeCl3·6H2O、NaAc溶于乙二醇中,进行第一次搅拌,然后加入MoS2纳米片,再进行第二次搅拌,得到混合溶液,转移到高压釜中进行分级溶剂热反应,反应后冷却至室温,所得产物经离心收集、去离子水和乙醇洗涤以及真空干燥后,得到MoS2@Fe3O4;
步骤3:磁性自组装MoS2@Fe3O4@Cu2O光催化剂的合成:
将步骤2合成的MoS2@Fe3O4和硫酸铜溶液(CuSO4)溶解在去离子水中,磁力搅拌后,再加入NaBH4溶液,磁力搅拌后收集产物,用去离子水和乙醇洗涤数次,然后经真空干燥得到样品,即为磁性自组装MoS2@Fe3O4@Cu2O光催化剂。
优选的,步骤1中,所述的硫代乙酰胺、钼酸钠和去离子水的用量比为0.45g:0.72g:80mL;所述的搅拌时间10min。
优选的,步骤1中,所述水热反应的反应温度为200℃,反应时间为24h;所述冻干处理的温度为-40℃,时间为24小时。
优选的,步骤2中,所述的FeCl3·6H2O、NaAc、乙二醇和MoS2纳米片的用量比为0.1g:0.36g:60mL:0.1g。
优选的,步骤2中,所述第一次搅拌的时间为10min;所述第二次搅拌的时间为3h。
优选的,步骤2中,所述分级溶剂热反应的条件为:先在100℃保持1h,然后升温至150℃保持2h,最终升温到190℃反应5h。
优选的,步骤2中,所述真空干燥的温度为60℃,时间为24小时。
优选的,步骤3中,所述MoS2@Fe3O4、CuSO4、去离子水和NaBH4溶液的用量比为0.5 g:1.0mL:20mL:5mL;所述CuSO4的浓度为0.5mol/L;所述NaBH4溶液的浓度为0.2mol/L。
优选的,步骤3中,所述搅拌的时间均为12h。
优选的,步骤3中,所述真空干燥的温度为60℃,时间为24小时。
有益效果:
(1)本发明制备的磁性自组装MoS2@Fe3O4@Cu2O光催化剂由于形成了类Z型异质结,使得所制备的磁性自组装MoS2@Fe3O4@Cu2O光催化剂具有较高的光催化活性,对四环素的降解率可达70%,MoS2@Fe3O4@Cu2O的光催化效率分别是MoS2、MoS2@Fe3O4和 MoS2@Cu2O的3.5、1.75和2.5倍。
(2)本发明制备的磁性自组装MoS2@Fe3O4@Cu2O光催化剂由于可在磁性材料制备的同时被合成,简化实验过程,为磁性光催化材料的简便制备提供了新的途径。
(3)本发明制备的磁性自组装MoS2@Fe3O4@Cu2O光催化剂,在制备过程中通过分级溶剂热法使Fe3O4形成均一的小颗粒,更利于电子跃迁、分离,从而提高光催化剂的光催化性能。
(4)本发明制备的磁性自组装MoS2@Fe3O4@Cu2O光催化剂,在Cu2O的引入过程中,利用Fe3O4小颗粒的磁相互吸引作用将MoS2纳米片组装成花球,并限制了Cu2O的大小,使得小颗粒Cu2O均一地生长,更利于电子的传输,提高光催化剂的光降解能力。
(5)本发明制备的磁性自组装MoS2@Fe3O4@Cu2O光催化剂可以降解四环素,目前利用磁性自组装技术合成光催化材料尚未有报道,所以本发明制备的材料具有独特性和创新性,而且具有操作简单、低成本、高利用率、针对性强、效果好的优势。
附图说明
图1为不同样品的XRD谱图。
图2为不同样品的SEM谱图(a、b和c)和TEM谱图(d、e、f);其中a、d为MoS2; b、e为MoS2@Fe3O4;c、f为磁性自组装MoS2@Fe3O4@Cu2O光催化剂。
图3为MoS2@Cu2O的SEM谱图。
图4为不同样品的磁化曲线;插图为磁性自组装MoS2@Fe3O4@Cu2O光催化剂溶于水后磁铁吸引下的状态图。
图5为不同样品对四环素的光降解考察图。
图6为磁性自组装MoS2@Fe3O4@Cu2O光催化剂稳定性考察图。
具体实施方式
下面结合具体实施实例对本发明做进一步说明。
四环素吸附活性评价:在DW-01型光化学反应仪中进行,将100mL 20mg/L的四环素溶液加入反应器中并测定其初始值,然后加入0.01g的磁性自组装MoS2@Fe3O4@Cu2O光催化剂,不开光源,设定温度为30℃,不开光照射,通空气(曝气量为2mL/min),打开磁力搅拌(转速为600rpm/min),间隔10min取样分析,通过紫外-可见分光光度计测定其浓度,并通过公式:Q=(C0-C)V/m算出其吸附容量Q,其中C0为四环素的初始浓度,C为达到吸附平衡时的四环素溶液的浓度,V为溶液的体积,m为加入的样品的质量。
光催化活性评价:在DW-01型光化学反应仪中进行,将100mL 20mg/L四环素溶液加入反应器中并测定其初始值,然后加入0.01g的磁性自组装MoS2@Fe3O4@Cu2O光催化剂,不开光源,设定温度为30℃,不开光照射,通空气(曝气量为2mL/min),打开磁力搅拌(转速为600rpm/min),达到吸附平衡后,再用模拟可见光照射(300w氙灯加紫外光滤光片),打开磁力搅拌(转速为600rpm/min)并开启曝气装置通入空气(流量为2mL/min),设定温度为30℃,光照过程中间隔10min取样分析,通过紫外-可见分光光度计测定其浓度,并通过公式:Dr=(C0-C)×100/C0算出其光降解率Dr,其中C0为达到吸附平衡时的四环素溶液的浓度,C为t时刻测定的四环素溶液的浓度,t为反应时间。
实施例1:
(1)2D-MoS2的合成:
将0.45g硫代乙酰胺、0.72g钼酸钠和80mL去离子水混合到200mL烧杯中,然后磁力搅拌10min。将得到的无色混合溶液转移到100ml聚四氟乙烯内衬不锈钢高压釜中,在200℃下反应24h,反应结束,溶液冷却至室温后,在3500rpm下离心5min,收集黑色产物,用去离子水和乙醇洗涤3次,最后,将合成黑产物在-40℃真空冷冻干燥机中干燥24h,所得产物在室温下保存;
(2)MoS2@Fe3O4的合成:
将0.1g FeCl3·6H2O、0.36g醋酸钠(NaAc)溶于60mL乙二醇中,搅拌10min,再加入0.1g MoS2纳米片,磁力搅拌3h,将所得溶液转移至100mL聚四氟乙烯内衬不锈钢高压釜中,在100℃保持1h,升温至150℃保持2h,最后升温至190℃反应5h,溶液冷却至室温。所得样品通过离心获得并用去离子水和乙醇洗涤,在60℃的真空干燥器中干燥24h,得到MoS2@Fe3O4;
(3)磁性自组装MoS2@Fe3O4@Cu2O光催化剂的合成:
将通过上述方法合成的0.5g MoS2@Fe3O4和1.0mL CuSO4(0.5mol/L)溶解在20mL去离子水中,然后磁搅拌12h;随后,将5.0mL新配制的NaBH4溶液(0.20mol/L,)添加到混合溶液中;再磁力搅拌12h后,收集产品,用去离子水和乙醇洗涤3次以上,然后在60℃的真空干燥器中干燥24h时,得到磁性自组装MoS2@Fe3O4@Cu2O光催化剂。
(4)MoS2@Cu2O的合成:与步骤(3)的方法一致,区别是将步骤(3)中加入的0.5gMoS2@Fe3O4替换为加入0.5g MoS2。
图1为不同样品的XRD谱图,从图中可以看出,MoS2纳米片的三个明显衍射峰(2θ值) 分别位于33.06°(101)、34.15°(012)和58.35°(110),与标准卡(JCPDS 8)一致。从MoS2@Fe3O4的XRD图谱可以观察到一些用四边形符号标记的峰(2θ=30.07°、37.05°、43.05°、56.93°、62.5°),与Fe3O4标准卡(JCPDS 77-1545)吻合良好。根据MoS2和Fe3O4的标准卡片,峰在35.42°(311)左右,几乎与MoS2纳米片的峰一致。进一步对比磁性自组装MoS2@Fe3O4@Cu2O光催化剂的XRD谱图可以发现,没有多余的峰增加或减少,综上所述,成功地合成了磁性自组装MoS2@Fe3O4@Cu2O光催化剂,且并没有改变原材料的晶型。
图2为不同样品的SEM谱图和TEM谱图,从图中可以看出:MoS2呈现2D片状结构,而Fe3O4和MoS2结合后,可以观察到3D花球,说明花球的形成与Fe3O4纳米粒子之间的相互吸引作用有关,Fe3O4可以作为MoS2和Fe3O4复合过程中的结构导向剂。通过分级溶剂热法合成的Fe3O4呈现均一的小颗粒,均一的Fe3O4纳米粒子更利于光催化剂中电子的跃迁、分离’,提高材料的光催化能力。通过TEM图可以看出磁性自组装MoS2@Fe3O4@Cu2O光催化剂形成了花球结构,并观察一些球形颗粒即为Cu2O。这些再次表明该磁性自组装 MoS2@Fe3O4@Cu2O光催化剂已被成功合成。
图3为MoS2@Cu2O的SEM谱图,从图中可以看出由于没有Fe3O4的磁性自组装作用,MoS2纳米片并未形成3D花球结构,因此得出Fe3O4是作为MoS2和Fe3O4复合过程中的结构导向剂。同时由于花状结构的空间限制,Cu2O的生长受到限制,与MoS2@Cu2O相比, MoS2@Fe3O4@Cu2O中的Cu2O的粒径更小且均一,更有利于光催化剂中电子的跃迁、分离,从而提高材料的光催化能力。
图4为MoS2和磁性自组装MoS2@Fe3O4@Cu2O光催化剂的磁化模式,由图中可以看出。MoS2@Fe3O4和磁性自组装MoS2@Fe3O4@Cu2O光催化剂的磁饱和值分别为4.01emu/g和0.5emu/g。尽管Cu2O的引入削弱了磁性自组装MoS2@Fe3O4@Cu2O光催化剂的磁性,但从小图可以清楚地观察到磁性自组装MoS2@Fe3O4@Cu2O光催化剂可以被磁体完全分离。说明磁性自组装MoS2@Fe3O4@Cu2O光催化剂的磁选性能良好。
图5为不同样品的四环素光降解曲线,从图中可以看出,磁性自组装MoS2@Fe3O4@Cu2O 光催化剂对四环素的降解活性最好,分别是MoS2、MoS2@Fe3O4和MoS2@Cu2O的3.5、1.75和2.5倍。其原因可能是:首先,在MoS2上负载Fe3O4,增加了MoS2的电子转移,从而提高了光催化活性。负载Cu2O仍能提高MoS2的电子转移效率,但效果不如Fe3O4。其次,在 MoS2@Fe3O4中引入Cu2O可以形成异质结,从而进一步提高磁性自组装MoS2@Fe3O4@Cu2O 光催化剂的光催化活性。
图6为磁性自组装MoS2@Fe3O4@Cu2O光催化剂的稳定性测试,经过5次循环后,磁性自组装MoS2@Fe3O4@Cu2O光催化剂的降解活性并非发生较大变化,表明材料的稳定性良好。
说明:以上实施例仅用以说明本发明而并非限制本发明所描述的技术方案;因此,尽管本说明书参照上述的各个实施例对本发明已进行了详细的说明,但是本领域的普通技术人员应当理解,仍然可以对本发明进行修改或等同替换;而一切不脱离本发明的精神和范围的技术方案及其改进,其均应涵盖在本发明的权利要求范围内。
Claims (9)
1.一种磁性自组装MoS2@Fe3O4@Cu2O光催化剂的制备方法,其特征在于,按照下述步骤进行:
步骤1:硫代乙酰胺、钼酸钠和去离子水混合,磁力搅拌后,将所得无色混合溶液转移至高压反应釜中进行水热反应,反应结束冷却至室温后,得到黑色产物,用去离子水和乙醇洗涤数次;然后将黑色产物在真空冷冻干燥机中进行冻干处理,所得产物在室温下保存;
步骤2:将FeCl3·6H2O、NaAc溶于乙二醇中,进行第一次搅拌,然后加入MoS2纳米片,再进行第二次搅拌,得到混合溶液,转移到高压釜中进行分级溶剂热反应,反应后冷却至室温,所得产物经离心收集、去离子水和乙醇洗涤以及真空干燥后,得到MoS2@Fe3O4;所述分级溶剂热反应的条件为:先在100 ℃保持1 h,然后升温至150 ℃保持2 h,最终升温到190 ℃反应5 h;
步骤3:将步骤2合成的MoS2@Fe3O4和CuSO4溶解在去离子水中,磁力搅拌后,再加入NaBH4溶液,磁力搅拌后收集产物,用去离子水和乙醇洗涤数次,然后经真空干燥得到样品,即为磁性自组装MoS2@Fe3O4@Cu2O光催化剂。
2. 根据权利要求1所述的一种磁性自组装MoS2@Fe3O4@Cu2O光催化剂的制备方法,其特征在于,步骤1中,所述的硫代乙酰胺、钼酸钠和去离子水的用量比为0.45 g:0.72 g:80mL;所述的搅拌时间10 min。
3. 根据权利要求1所述的一种磁性自组装MoS2@Fe3O4@Cu2O光催化剂的制备方法,其特征在于,步骤1中,所述水热反应的反应温度为200 ℃,反应时间为24 h;所述冻干处理的温度为-40℃,时间为24小时。
4. 根据权利要求1所述的一种磁性自组装MoS2@Fe3O4@Cu2O光催化剂的制备方法,其特征在于,步骤2中,所述的FeCl3·6H2O、NaAc、乙二醇和MoS2纳米片的用量比为0.1 g:0.36g:60 mL:0.1 g。
5. 根据权利要求1所述的一种磁性自组装MoS2@Fe3O4@Cu2O光催化剂的制备方法,其特征在于,步骤2中,所述第一次搅拌的时间为10 min;所述第二次搅拌的时间为3 h。
6.根据权利要求1所述的一种磁性自组装MoS2@Fe3O4@Cu2O光催化剂的制备方法,其特征在于,步骤2中,所述真空干燥的温度为60℃,时间为24小时。
7. 根据权利要求1所述的一种磁性自组装MoS2@Fe3O4@Cu2O光催化剂的制备方法,其特征在于,所述MoS2@Fe3O4、CuSO4、去离子水和NaBH4溶液的用量比为0.5 g:1.0 mL:20 mL:5mL;所述CuSO4的浓度为0.5 mol/L;所述NaBH4溶液的浓度为0.2 mol/L。
8. 根据权利要求1所述的一种磁性自组装MoS2@Fe3O4@Cu2O光催化剂的制备方法,其特征在于,步骤3中所述搅拌的时间均为12 h;所述真空干燥的温度为60℃,时间为24小时。
9.根据权利要求1~8任一所述的一种磁性自组装MoS2@Fe3O4@Cu2O光催化剂的制备方法制备的磁性自组装MoS2@Fe3O4@Cu2O光催化剂应用于光催化降解四环素。
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