CN112916021A - 一种Fe3O4@Cu2O-Au复合纳米材料及其制备方法、应用 - Google Patents
一种Fe3O4@Cu2O-Au复合纳米材料及其制备方法、应用 Download PDFInfo
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- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 title claims abstract description 123
- 239000002086 nanomaterial Substances 0.000 title claims abstract description 114
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- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 claims abstract description 41
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Abstract
本发明公开了一种Fe3O4@Cu2O‑Au复合纳米材料,纳米Cu2O包覆纳米Fe3O4形成Fe3O4@Cu2O复合纳米材料,纳米Au负载在Fe3O4@Cu2O复合纳米材料上。本发明还公开了上述Fe3O4@Cu2O‑Au复合纳米材料的制备方法和应用。本发明所述Fe3O4@Cu2O复合纳米材料的光催化活性可控,本发明通过简单的一步热分解方法制备Fe3O4@Cu2O复合纳米材料,其颗粒尺寸约为280nm,分散性好,在常温下表现出良好的超顺磁性,使用普通磁铁即可分离;并通过自组装方法,通过调控氯金酸的加入比例可控制备Fe3O4@Cu2O‑Au纳米光催化剂的技术。
Description
技术领域
本发明涉及纳米功能材料技术领域,尤其涉及一种Fe3O4@Cu2O-Au复合纳米材料及其制备方法、应用。
背景技术
近几年来社会经济不断发展,污水的大量排放严重地污染了河流、湖泊和海洋,造成了严重的污染,对生态环境的影响巨大。因此,污水治理成为了环境保护的首要任务。光催化降解技术是一种新兴的环境友好型绿色水处理技术,已被证实在降解环境污染物方面效果显著。Cu2O是具有2.0-2.2eV带隙的p型半导体,这使其成为在可见光照射下光催化降解有机污染物方面有前途的材料。然而,微米/纳米级的悬浮Cu2O粉末光催化剂难以从反应体系中分离和收集,这可能增加实际应用的成本并再次污染处理后的水。从可重复使用性的角度来看,将光催化剂与光催化系统分离是很重要的,而且避免半导体纳米颗粒的不利生物学影响也很重要。
目前,研究者们致力于开发各种方法来合成各种类型的可磁分离的光催化剂。近来,已经合成了各种类型的可磁分离的光催化剂,但是这些复合光催化剂中的磁性组份与半导体光催化剂组份之间的相互结合力较弱,而且在构建磁性复合光催化剂需要经过两步法或者多步法,制备工艺繁琐且成本较高。而采用一步法合成磁性复合光催化剂仍然是一个巨大的挑战。
此外,纯半导体光催化剂存在光生载流子复合率高的问题,导致光催化反应效率低。将贵金属(如Au等)沉积到半导体表面构建复合光催化材料是提高光催化剂的催化活性的一种办法。但是,Au纳米颗粒和Cu2O纳米颗粒的可控复合方法是一个亟待解决的难题。因此,开发一种组分可控的高效可回收型复合光催化剂和经济、绿色的制备方法,仍然是一个巨大的挑战。
发明内容
基于背景技术存在的技术问题,本发明提出了一种Fe3O4@Cu2O-Au复合纳米材料及其制备方法、应用,本发明针对现有的Fe3O4@Cu2O复合纳米材料中Fe3O4与Cu2O的结合力弱,需要多步反应制备、光催化性能不高等方面的不足,提供了一种通过简单的一步法反应制得Fe3O4和Cu2O结合紧密的Fe3O4@Cu2O复合纳米材料的制备方法,Fe3O4@Cu2O复合纳米材料的尺寸约为280nm,分散性好,在常温下表现出良好的超顺磁性,使用普通磁铁即可分离;同时对Au纳米颗粒负载量的有效调控,提高了Fe3O4@Cu2O-Au复合纳米光催化剂的光催化降解性能,实现了光催化剂的绿色回收;另外本发明简化了合成步骤,减少了操作难度,降低了生产成本。
本发明提出了一种Fe3O4@Cu2O-Au复合纳米材料,纳米Cu2O包覆纳米Fe3O4形成Fe3O4@Cu2O复合纳米材料,纳米Au负载在Fe3O4@Cu2O复合纳米材料上。
优选地,所述Fe3O4@Cu2O-Au复合纳米材料的粒径为300-400nm。
本发明还提出了上述Fe3O4@Cu2O-Au复合纳米材料的制备方法,包括如下步骤:
S1、在惰性气体氛围中,以乙酰丙酮铁、乙酰丙酮铜、还原剂和有机溶剂为原料,加热反应得到Fe3O4@Cu2O复合纳米材料;
S2、在还原剂作用下,Fe3O4@Cu2O复合纳米材料与氯金酸反应得到Fe3O4@Cu2O-Au复合纳米材料。
优选地,在S1中,加热反应的温度为260-280℃,时间为2-2.5h。
优选地,在S1中,加热反应的温度为260-270℃,时间为2h。
优选地,在S1中,加热反应的温度为265℃。
优选地,在S1中,还原剂为油胺,有机溶剂为二苯醚。
优选地,在S1中,有机溶剂和还原剂的体积比为1:0.9-1.1。
优选地,在S1中,有机溶剂和还原剂的体积比为1:1。
优选地,在S1中,乙酰丙酮铁和乙酰丙酮铜的重量比为1:0.4-0.6。
优选地,在S1中,乙酰丙酮铁和乙酰丙酮铜的重量比为1:0.5。
优选地,在S1中,乙酰丙酮铁和有机溶剂的质量体积比为47:1mg/mL。
上述S1中,惰性气体可以为氮气、氩气等。
优选地,在S2中,还原剂为硼氢化钠。
优选地,在S2中,Fe3O4@Cu2O复合纳米材料与氯金酸的重量比为1:1-30。
优选地,在S2中,Fe3O4@Cu2O复合纳米材料与还原剂的重量比为1:0.005-0.006。
优选地,在S2中,Fe3O4@Cu2O复合纳米材料与还原剂的重量比为1:0.006。
优选地,在S2中,反应温度为室温,时间为20-40min。
优选地,在S2中,将Fe3O4@Cu2O复合纳米材料在乙醇中分散均匀后,依次与聚乙烯吡咯烷酮、氯金酸水溶液、还原剂混匀,然后进行反应得到Fe3O4@Cu2O-Au复合纳米材料。
优选地,Fe3O4@Cu2O复合纳米材料与聚乙烯吡咯烷酮的重量比为1:1-1.2。
优选地,Fe3O4@Cu2O复合纳米材料与聚乙烯吡咯烷酮的重量比为1:1。
优选地,Fe3O4@Cu2O复合纳米材料与乙醇的质量体积比为1:1mg/mL。
上述水均为去离子水。
本发明还提出了上述Fe3O4@Cu2O-Au复合纳米材料作为光催化剂的应用。
优选地,作为光催化剂处理含孔雀石绿废水的应用。
有益效果:
1.本发明选用乙酰丙酮铁和乙酰丙酮铜为原料、二苯醚作为溶剂、油胺作为还原剂,在惰性气体保护下,进行简单的热分解法一步合成出粒径小于300nm的Fe3O4@Cu2O复合纳米材料,纳米Cu2O包覆纳米Fe3O4,这样操作不易引入杂质,增加磁性核Fe3O4和Cu2O纳米颗粒的纯度,且纳米Cu2O和纳米Fe3O4结合紧密,不易脱落。
2.然后以氯金酸为原料,利用原位还原法得到Fe3O4@Cu2O-Au复合纳米材料,使得Au纳米颗粒负载在Fe3O4@Cu2O复合纳米材料上;本发明可以良好地控制Au纳米颗粒沉积在Fe3O4@Cu2O复合纳米材料上,通过调节氯金酸的用量可以得到不同尺寸和形貌的Fe3O4@Cu2O-Au复合纳米材料;本发明操作简单,可控性强,重现性好,制得的Fe3O4@Cu2O-Au复合纳米材料的粒径分布均匀、分散性好、适合大规模生产。
3.Fe3O4纳米颗粒、Cu2O纳米颗粒和Au纳米颗粒复合,Cu2O纳米颗粒和Au纳米颗粒的协同光催化性质和磁性纳米颗粒的磁性质,使得本发明所述Fe3O4@Cu2O-Au复合纳米材料具有双重优点,既利于光催化剂从反应混合物中分离,又具有高催化降解性能。
附图说明
图1为实施例1中Fe3O4@Cu2O复合纳米材料、实施例1-5中Fe3O4@Cu2O-Au复合纳米材料的XRD谱图,其中,1-S1为实施例1中的Fe3O4@Cu2O复合纳米材料、1-S2至5-S2分别为实施例1-5中的Fe3O4@Cu2O-Au复合纳米材料。
图2为实施例1中Fe3O4@Cu2O复合纳米材料、实施例1-5中Fe3O4@Cu2O-Au复合纳米材料的SEM图像,其中,1-S1为实施例1中的Fe3O4@Cu2O复合纳米材料、1-S2至5-S2分别为实施例1-5中的Fe3O4@Cu2O-Au复合纳米材料。
图3为实施例1中Fe3O4@Cu2O复合纳米材料、实施例1-5中Fe3O4@Cu2O-Au复合纳米材料的磁滞回线图,其中,1-S1为实施例1中的Fe3O4@Cu2O复合纳米材料、1-S2至5-S2分别为实施例1-5中的Fe3O4@Cu2O-Au复合纳米材料。
图4为实施例1中Fe3O4@Cu2O复合纳米材料、实施例1-5中Fe3O4@Cu2O-Au复合纳米材料光催化降解孔雀石绿的降解率折线图,其中,1-S1为实施例1中的Fe3O4@Cu2O复合纳米材料、1-S2至5-S2分别为实施例1-5中的Fe3O4@Cu2O-Au复合纳米材料。
具体实施方式
下面,通过具体实施例对本发明的技术方案进行详细说明。
实施例1
一种Fe3O4@Cu2O-Au复合纳米材料的制备方法,包括如下步骤:
S1、将0.7g乙酰丙酮铁、0.28g乙酰丙酮铜加到15mL二苯醚中搅拌溶解,然后再加入15mL油胺,将混合溶液置于烧瓶中在265℃下回流加热2h,加热过程中持续向烧瓶中通入氩气,待冷却至室温后,收集沉淀,用无水乙醇洗涤沉淀得到Fe3O4@Cu2O复合纳米材料,将其存放在水中备用;
S2、取10mg Fe3O4@Cu2O复合纳米材料用无水乙醇清洗后,加入10mL乙醇中混匀;然后与10mg聚乙烯吡咯烷酮混合,搅拌20min后,缓慢加入1mL的浓度为10g/L的氯金酸水溶液搅拌10min,加入0.5mL浓度为3mmol/L硼氢化钠水溶液,继续搅拌30min,然后取沉淀用水超声清洗2次得到Fe3O4@Cu2O-Au复合纳米材料。
实施例2
S1、同实施例1中S1;
S2、加入5mL氯金酸水溶液,其他同实施例1中S2。
实施例3
S1、同实施例1中S1;
S2、加入10mL氯金酸水溶液,其他同实施例1中S2。
实施例4
S1、同实施例1中S1;
S2、加入20mL氯金酸水溶液,其他同实施例1中S2。
实施例5
S1、同实施例1中S1;
S2、加入30mL氯金酸水溶液,其他同实施例1中S2。
实施例6
一种Fe3O4@Cu2O-Au复合纳米材料的制备方法,包括如下步骤:
S1、将0.7g乙酰丙酮铁、0.35g乙酰丙酮铜加到15mL二苯醚中搅拌溶解,然后再加入13.5mL油胺,将混合溶液置于烧瓶中在260℃下回流加热2.5h,加热过程中持续向烧瓶中通入氩气,待冷却至室温后,收集沉淀,用无水乙醇洗涤沉淀得到Fe3O4@Cu2O复合纳米材料,将其存放在水中备用;
S2、取10mg Fe3O4@Cu2O复合纳米材料用无水乙醇清洗后,加入10mL乙醇中混匀;然后与11mg聚乙烯吡咯烷酮混合,搅拌30min后,缓慢加入20mL的浓度为10g/L的氯金酸水溶液搅拌15min,加入0.45mL浓度为3mmol/L硼氢化钠水溶液,继续搅拌20min,然后取沉淀用乙醇超声清洗2次得到Fe3O4@Cu2O-Au复合纳米材料。
实施例7
一种Fe3O4@Cu2O-Au复合纳米材料的制备方法,包括如下步骤:
S1、将0.7g乙酰丙酮铁、0.42g乙酰丙酮铜加到15mL二苯醚中搅拌溶解,然后再加入16.5mL油胺,将混合溶液置于烧瓶中在280℃下回流加热2h,加热过程中持续向烧瓶中通入氩气,待冷却至室温后,收集沉淀,用无水乙醇洗涤沉淀得到Fe3O4@Cu2O复合纳米材料,将其存放在水中备用;
S2、取10mg Fe3O4@Cu2O复合纳米材料用无水乙醇清洗后,加入10mL乙醇中混匀;然后与12mg聚乙烯吡咯烷酮混合,搅拌20min后,缓慢加入10mL的浓度为10g/L的氯金酸水溶液搅拌10min,加入0.5mL浓度为3mmol/L硼氢化钠水溶液,继续搅拌40min,然后取沉淀用水超声清洗2次得到Fe3O4@Cu2O-Au复合纳米材料。
实验1
取实施例1的S1制得的Fe3O4@Cu2O复合纳米材料,实施例1-5制得的Fe3O4@Cu2O-Au复合纳米材料,进行XRD检测、SEM扫描和磁性检测,结果如图1-3所示。
图1为实施例1中Fe3O4@Cu2O复合纳米材料、实施例1-5中Fe3O4@Cu2O-Au复合纳米材料的XRD谱图,其中,1-S1为实施例1中的Fe3O4@Cu2O复合纳米材料、1-S2至5-S2分别为实施例1-5中的Fe3O4@Cu2O-Au复合纳米材料。
图2为实施例1中Fe3O4@Cu2O复合纳米材料、实施例1-5中Fe3O4@Cu2O-Au复合纳米材料的SEM图像,其中,1-S1为实施例1中的Fe3O4@Cu2O复合纳米材料、1-S2至5-S2分别为实施例1-5中的Fe3O4@Cu2O-Au复合纳米材料。
图3为实施例1中Fe3O4@Cu2O复合纳米材料、实施例1-5中Fe3O4@Cu2O-Au复合纳米材料的磁滞回线图,其中,1-S1为实施例1中的Fe3O4@Cu2O复合纳米材料、1-S2至5-S2分别为实施例1-5中的Fe3O4@Cu2O-Au复合纳米材料。
由图1可以看出,Fe3O4@Cu2O复合纳米材料、Fe3O4@Cu2O-Au复合纳米材料中的Fe3O4、Cu2O和Au均为纯相,无任何杂质。
由图2可以看出,Cu2O包覆Fe3O4得到Fe3O4@Cu2O复合纳米材料,其粒径小于300nm,当氯金酸溶液的用量为1、5、10、20、30mL时,得到Fe3O4@Cu2O-Au复合纳米材料的颗粒尺寸分别约300、330、350、380、400nm。
由图3可以看出,Fe3O4@Cu2O复合纳米材料、Fe3O4@Cu2O-Au复合纳米材料均具有亚铁磁性,并且有较高的饱和磁化强度。
实验2
分别称取相同质量的实施例1的S1制得的Fe3O4@Cu2O复合纳米材料,实施例1-5制得的Fe3O4@Cu2O-Au复合纳米材料,然后分别加入100mL浓度为0.05mmol/L的孔雀石绿水溶液,再分别以100W氙灯可见光为光源照射,每20min取少量反应液利用紫外可见分光光度计测定其吸收度,检测光照2h的降解效果,并以不添加剂光催化剂,不进行光照处理的100mL浓度为0.05mmol/L的孔雀石绿水溶液作为无光照对比组,结果如图4所示。
图4为实施例1中Fe3O4@Cu2O复合纳米材料、实施例1-5中Fe3O4@Cu2O-Au复合纳米材料光催化降解孔雀石绿的降解率折线图,其中,1-S1为实施例1中的Fe3O4@Cu2O复合纳米材料、1-S2至5-S2分别为实施例1-5中的Fe3O4@Cu2O-Au复合纳米材料。
由图4可以看出,实施例1-5制得的Fe3O4@Cu2O-Au复合纳米材料均具有光催化降解性能,其中实施例4所制备得到的Fe3O4@Cu2O-Au复合纳米材料具有最高的催化降解效率。由此可见,有效地控制Au纳米颗粒负载量可以极大地帮助控制光催化剂的光催化活性。
以上所述,仅为本发明较佳的具体实施方式,但本发明的保护范围并不局限于此,任何熟悉本技术领域的技术人员在本发明揭露的技术范围内,根据本发明的技术方案及其发明构思加以等同替换或改变,都应涵盖在本发明的保护范围之内。
Claims (10)
1.一种Fe3O4@Cu2O-Au复合纳米材料,其特征在于,纳米Cu2O包覆纳米Fe3O4形成Fe3O4@Cu2O复合纳米材料,纳米Au负载在Fe3O4@Cu2O复合纳米材料上。
2.根据权利要求1所述Fe3O4@Cu2O-Au复合纳米材料,其特征在于,所述Fe3O4@Cu2O-Au复合纳米材料的粒径为300-400nm。
3.一种如权利要求1或2所述Fe3O4@Cu2O-Au复合纳米材料的制备方法,其特征在于,包括如下步骤:
S1、在惰性气体氛围中,以乙酰丙酮铁、乙酰丙酮铜、还原剂和有机溶剂为原料,加热反应得到Fe3O4@Cu2O复合纳米材料;
S2、在还原剂作用下,Fe3O4@Cu2O复合纳米材料与氯金酸反应得到Fe3O4@Cu2O-Au复合纳米材料。
4.根据权利要求3所述Fe3O4@Cu2O-Au复合纳米材料的制备方法,其特征在于,在S1中,加热反应的温度为260-280℃,时间为2-2.5h。
5.根据权利要求3或4所述Fe3O4@Cu2O-Au复合纳米材料的制备方法,其特征在于,在S1中,还原剂为油胺,有机溶剂为二苯醚;优选地,在S1中,有机溶剂和还原剂的体积比为1:0.9-1.1;优选地,在S1中,乙酰丙酮铁和乙酰丙酮铜的重量比为1:0.4-0.6。
6.根据权利要求3-5任一项所述Fe3O4@Cu2O-Au复合纳米材料的制备方法,其特征在于,在S2中,还原剂为硼氢化钠。
7.根据权利要求3-6任一项所述Fe3O4@Cu2O-Au复合纳米材料的制备方法,其特征在于,在S2中,Fe3O4@Cu2O复合纳米材料与氯金酸的重量比为1:1-30;优选地,在S2中,Fe3O4@Cu2O复合纳米材料与还原剂的重量比为1:0.005-0.006。
8.根据权利要求3-7任一项所述Fe3O4@Cu2O-Au复合纳米材料的制备方法,其特征在于,在S2中,反应温度为室温,时间为20-40min。
9.根据权利要求3-8任一项所述Fe3O4@Cu2O-Au复合纳米材料的制备方法,其特征在于,在S2中,将Fe3O4@Cu2O复合纳米材料在乙醇中分散均匀后,依次与聚乙烯吡咯烷酮、氯金酸水溶液、还原剂混匀,然后进行反应得到Fe3O4@Cu2O-Au复合纳米材料;优选地,Fe3O4@Cu2O复合纳米材料与聚乙烯吡咯烷酮的重量比为1:1-1.2。
10.一种如权利要求1或2所述Fe3O4@Cu2O-Au复合纳米材料作为光催化剂的应用;优选地,作为光催化剂处理含孔雀石绿废水的应用。
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