CN114797863A - 双Z型CuO/CuFe2O4/Fe2O3复合光催化剂及其制备方法和应用 - Google Patents
双Z型CuO/CuFe2O4/Fe2O3复合光催化剂及其制备方法和应用 Download PDFInfo
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Abstract
本发明涉及双Z型CuO/CuFe2O4/Fe2O3复合光催化剂及其制备方法和应用。将Cu(OH)2和Fe(OH)3共沉淀混合物,充分搅拌均匀后进行过滤,将过滤得到的沉淀混合物在60℃干燥12.0h,干燥后的粉末均匀研磨,放入马弗炉中于500~700℃,煅烧2.0~4.0h,得目标产物CuO/CuFe2O4/Fe2O3。本发明通过控制煅烧温度与煅烧时间,能够使三种纳米粒子共存,基于共沉淀‑不完全固相反应制备的双Z型CuO/CuFe2O4/Fe2O3复合光催化剂,在太阳光下可高效光催化降解水中有机污染物。
Description
技术领域
本发明属于光催化剂领域,具体涉及采用共沉淀法和不完全固相反应法制备双Z型CuO/CuFe2O4/Fe2O3复合光催化剂,并在太阳光照射下将其用于水中抗生素的降解。
背景技术
随着社会的进步和人类生活水平的提高,人们的环境保护意识和能源节约意识逐步增强,环境治理成为当前的工作重点。抗生素在世界各地应用广泛,因此不可避免地导致它们排放到水生环境中,成为新的环境污染物。诺氟沙星(NFX)是一种具有广谱性的抗生素药物,也是一种半衰期超长的难降解性有机污染物。由于其良好的稳定性和生物积累性,即使在低浓度的条件下,也会对生态和人类健康造成严重的、长期的危害。目前,有许多技术被用于水中抗生素的去除,有吸附法、膜过滤法、生物净化法、化学沉淀法及光催化氧化技术。在这些技术中,基于半导体的光催化技术因其高效、节能、低成本、环境友好等优点已被证明是解决不断增长的能源和环境问题的一个有前途的途径。
众所周知,传统的单一半导体光催化剂具有光生电子空穴对复合率高、太阳光捕获能力弱的缺点。因此,为了提高光催化剂的性能,设计出更高效的半导体光催化剂已经成为光催化技术发展的核心问题。目前众多方案中,由具有合适带隙结构的宽带隙半导体和窄带隙半导体复合所组成的三元双Z型光催化结构体系是提高光催化活性的有效途径之一。尖晶石结构的CuFe2O4禁带宽度为1.4eV,是一种可见光驱动的磁性光催化剂,因其化学稳定性、合成简单、成本低、毒性低、易于回收(完美的铁磁性)、优异的可见光吸收特性等优异优点而受到关注。CuO属于单斜晶系,是为数不多的金属氧化物型半导体。当其达到纳米级别时,广泛应用于传感器、电容器、光催化、超导材料、热导材料等领域。Fe2O3是一种n型半导体,禁带宽度约为2.3eV,是一种窄带半导体,可以吸收可见光,具有环境友好,成本低,有效利用率高,耐腐蚀性强等优点。这三种半导体具有合适的带隙结构,并且具有催化性能良好、化学性质稳定、成本低廉、制备工艺简单等特点,对染料以及抗生素等水中有机污染物都具有较强的降解能力,因此具有重要的研究价值。
发明内容
本发明的目的是采用Cu(OH)2和Fe(OH)3共沉淀混合物的不完全固相反应,通过控制煅烧温度和时间,使其在高温情况下一部分生成CuFe2O4,另一部分生成CuO和Fe2O3,进而使三者以近乎无界面的形式共存,构成双Z型CuO/CuFe2O4/Fe2O3复合光催化剂。复合体系的构建提高了体系的氧化还原能力,降低了光生电子和空穴的复合率,并且能充分利用太阳光,使光催化活性增强。
本发明的另一目的是利用双Z型CuO/CuFe2O4/Fe2O3复合光催化剂催化降解水中的抗生素。
本发明采用的技术方案是:双Z型CuO/CuFe2O4/Fe2O3复合光催化剂,采用共沉淀-不完全固相反应法制备,制备方法包括如下步骤:将Cu(OH)2和Fe(OH)3共沉淀混合物,在60℃干燥12.0h后,研磨,放入马弗炉中于500~700℃,煅烧2.0~4.0h,得到目标产物双Z型CuO/CuFe2O4/Fe2O3复合光催化剂。
进一步的,上述的双Z型CuO/CuFe2O4/Fe2O3复合光催化剂,按摩尔比,Cu2+:Fe3+=1.0:2.0。
进一步的,上述的双Z型CuO/CuFe2O4/Fe2O3复合光催化剂,所述Cu(OH)2和Fe(OH)3共沉淀混合物的制备方法,包括如下步骤:将Cu(NO3)2·3H2O和Fe(NO3)3·9H2O共同溶于去离子水中,搅拌溶解后,逐滴滴加NaOH溶液,磁力搅拌后,静置,弃上清液,沉淀用蒸馏水洗涤至pH=7.0~8.0,过滤,得到Cu(OH)2和Fe(OH)3共沉淀混合物。
本发明提供的双Z型CuO/CuFe2O4/Fe2O3复合光催化剂在太阳光下降解抗生素中的应用。
进一步的,方法如下:于含有抗生素的溶液中,加入双Z型CuO/CuFe2O4/Fe2O3复合光催化剂,在太阳光下照射3.0~4.0h。
进一步的,双Z型CuO/CuFe2O4/Fe2O3复合光催化剂的加入量为0.5~2.0g/L。
进一步的,所述抗生素为喹诺酮类抗生素。
进一步的,所述喹诺酮类抗生素为诺氟沙星(NFX)。
本发明的有益效果是:本发明通过共沉淀-不完全固相反应制备双Z型CuO/CuFe2O4/Fe2O3复合光催化剂,制备方法简单,并且能够使CuO、CuFe2O4、Fe2O3以近乎无界面的形式共存,提高了光生电子的传输效率。双Z型CuO/CuFe2O4/Fe2O3复合光催化剂的构建不仅能有效利用太阳光,而且还提高了体系的氧化还原能力和光生电子-空穴对(e--h+)的分离效率,进而提高了光催化活性。
附图说明
图1是CuO/CuFe2O4/Fe2O3(600℃,2h)复合光催化剂的X射线衍射图。
图2是CuO/CuFe2O4/Fe2O3(600℃,3h)复合光催化剂的X射线衍射图。
图3是CuO/CuFe2O4/Fe2O3(600℃,4h)复合光催化剂的X射线衍射图。
图4是CuO/CuFe2O4/Fe2O3(500℃,3h)复合光催化剂的X射线衍射图。
图5是CuO/CuFe2O4/Fe2O3(700℃,3h)复合光催化剂的X射线衍射图。
图6是不同条件下制备的CuO/CuFe2O4/Fe2O3复合光催化剂降解NFX溶液的紫外-可见光吸收图。
图7是光照时间对诺氟沙星降解率的影响
图8是催化剂不同投加量对诺氟沙星降解的影响
具体实施方法
实施例1
(一)双Z型CuO/CuFe2O4/Fe2O3复合光催化剂,制备方法如下:
1)通过化学共沉淀法制备Cu(OH)2和Fe(OH)3共沉淀混合物:
称量1.2081g Cu(NO3)2·3H2O和4.0402g Fe(NO3)3·9H2O(摩尔比Cu2+:Fe3+=1.0:2.0),加入到100.0mL去离子水中,磁力搅拌30.0min使其充分溶解。然后,向烧杯中逐滴滴加50.0mL 1.0mol/L NaOH溶液,使溶液中的Cu2+和Fe3+完全沉淀,磁力搅拌3.0h后,静置一段时间,弃去上清液,沉淀用蒸馏水洗涤至洗出液pH=7.0~8.0,过滤,将过滤所得沉淀在60℃干燥12.0h,充分研磨后,得到Cu(OH)2和Fe(OH)3共沉淀混合物。
2)通过不完全固相反应制备CuO/CuFe2O4/Fe2O3复合光催化剂:
将上述制备的Cu(OH)2和Fe(OH)3共沉淀混合物,放入坩埚。分别在500℃,600℃和700℃下煅烧3.0h,在600℃下分别煅烧2.0h和4.0h。得到的产物分别标记为CuO/CuFe2O4/Fe2O3(500℃,3h)、CuO/CuFe2O4/Fe2O3(600℃,3h)、CuO/CuFe2O4/Fe2O3(700℃,3h)、CuO/CuFe2O4/Fe2O3(600℃,2h)、CuO/CuFe2O4/Fe2O3(600℃,4h)。
(二)对比例
制备CuO纳米粒子:首先,称量4.8324g Cu(NO3)2·3H2O于烧杯中,向其中加入100.0mL去离子水,磁力搅拌30.0min使其全部溶解。其次,向烧杯中逐滴滴加50.0mL1.0mol/L NaOH溶液,磁力搅拌3.0h后静置,待Cu(OH)2沉淀完全后去除上清液。并将沉淀用去离子水洗涤,直至洗出液pH=7.0~8.0,离心得到Cu(OH)2沉淀。将得到的沉淀在60℃干燥12.0h,干燥后进行均匀研磨,并放入坩埚中于马弗炉600℃煅烧3.0h,得到CuO纳米粒子。
制备Fe2O3纳米粒子:首先,称量6.0603g Fe(NO3)3·9H2O于烧杯中,向其中加入100.0mL去离子水,持续搅拌30.0min使其完全溶解。其次,向烧杯中逐滴滴加55.0mL1.0mol/L NaOH溶液,磁力搅拌3.0h后静置,待Fe(OH)3沉淀完全后去除上清液。并将沉淀用去离子水洗涤,直至洗出液pH=7.0~8.0,过滤得到Fe(OH)3沉淀。将得到的沉淀在60℃干燥12.0h,干燥后进行均匀研磨,并放入坩埚中于马弗炉600℃煅烧3.0h,得到Fe2O3纳米粒子。
制备CuFe2O4纳米粒子:首先,称量2.4162g Cu(NO3)2·3H2O和8.0804gFe(NO3)3·9H2O共同溶于100.0mL去离子水中,搅拌使其溶解。向溶液中逐滴滴加90.0mL1.0mol/LNaOH溶液,磁力搅拌3.0h后静置,待Cu(OH)2和Fe(OH)3沉淀完全后去除上清液。并将沉淀用去离子水洗涤,直至洗出液pH=7.0~8.0,离心得到Cu(OH)2和Fe(OH)3共沉淀混合物。将混合物在60℃干燥12.0h,干燥后的粉末均匀研磨后,放入坩埚于马弗炉950℃煅烧3.0h,得到CuFe2O4纳米粒子。
(三)催化剂的表征
图1到图5是不同煅烧温度和时间下制备的CuO/CuFe2O4/Fe2O3复合光催化剂的XRD图谱。如图1-5所示,CuO的特征峰与标准卡(JCPDS 45-0937)一致,CuFe2O4的特征峰与标准卡(JCPDS 25-0283),Fe2O3的特征峰与标准卡(JCPDS 33-0664)。该结果显示成功地制备了CuO/CuFe2O4/Fe2O3复合光催化剂。
实施例2双Z型CuO/CuFe2O4/Fe2O3复合光催化剂在太阳光下降解抗生素中的应用(一)催化剂煅烧时间对诺氟沙星降解率的影响
实验方法:分别称量0.02g CuO/CuFe2O4/Fe2O3(600℃,2h)、CuO/CuFe2O4/Fe2O3(600℃,3h)与CuO/CuFe2O4/Fe2O3(600℃,4h),分别加入到放有20.0mL初始浓度为10.0mg/L的NFX溶液的石英管中,在太阳光下照射4.0h,离心取上清液,然后在200-800nm波长范围内测定其吸光度。取273.9nm处的吸光度值带入标准曲线公式中,计算NFX的降解率。结果如表1所示。
降解率(%)=(1-C/C0)×100%
其中,C0:原液中NFX的浓度;C:样品中NFX的浓度
表1催化剂煅烧温度对诺氟沙星降解率的影响
从表1中可以看出,在煅烧时间为3.0h时所制备的复合光催化剂CuO/CuFe2O4/Fe2O3(600℃,3h)降解NFX的效果最好,在太阳光下照射4.0h降解率可达71.5%,因此本发明所制备的双Z型CuO/CuFe2O4/Fe2O3复合光催化剂煅烧时间选择为3.0h。
(二)不同催化剂对诺氟沙星降解率的影响
分别称量0.02g CuO/CuFe2O4/Fe2O3(500℃,3h)、CuO/CuFe2O4/Fe2O3(600℃,3h)、CuO/CuFe2O4/Fe2O3(700℃,3h)、CuO/CuFe2O4/Fe2O3(600℃,2h)、CuO/CuFe2O4/Fe2O3(600℃,4h),分别加入到放有20.0mL初始浓度为10.0mg/L的NFX溶液的石英管中,在太阳光下照射3.0h,多次离心取上清液,然后在200-800nm波长范围内测定其吸光度。绘制紫外-可见光吸收图谱。结果如图6所示。
由图6中可以看出,在太阳光下加入催化剂对NFX的降解有很明显的作用。而CuO/CuFe2O4/Fe2O3(500℃,3h)、CuO/CuFe2O4/Fe2O3(600℃,3h)、CuO/CuFe2O4/Fe2O3(700℃,3h)、CuO/CuFe2O4/Fe2O3(600℃,2h)、CuO/CuFe2O4/Fe2O3(600℃,4h)5个复合光催化剂对NFX均有明显的降解作用,但双Z型CuO/CuFe2O4/Fe2O3(600℃,3h)复合光催化剂对NFX溶液降解效果最明显。
(三)光照时间对诺氟沙星降解率的影响
分别称量0.02g CuO/CuFe2O4/Fe2O3(600℃,3h)、CuO/CuFe2O4/Fe2O3(700℃,3h)、CuO/CuFe2O4/Fe2O3(600℃,2h)、CuO/CuFe2O4/Fe2O3(600℃,4h),分别加入到放有20.0mL初始浓度为10.0mg/L的NFX溶液的石英管中,在太阳光下照射不同时间,取样,离心取上清液,然后在200-800nm波长范围内测定其吸光度。取273.9nm处的吸光度值带入标准曲线公式中,计算NFX的降解率。结果如图7所示。
由图7可知,NFX降解率随着光照时间的增加而增加。其中,CuO/CuFe2O4/Fe2O3(600℃,3h)复合光催化剂对NFX降解程度最大,当光照时间为240.0min时,降解率可达71.5%。
(四)催化剂不同投加量对诺氟沙星降解率的影响
量取20.0mL初始浓度为10.0mg/L的诺氟沙星溶液分别置于4个石英管中,分别加入不同剂量的CuO/CuFe2O4/Fe2O3(600℃,3h)复合光催化剂,在太阳光下照射3.0h,离心取上清液,然后在200-800nm波长范围内测定其吸光度。取273.9nm处的吸光度值带入标准曲线公式中,计算NFX的降解率。结果如图8所示。
由图8可见,随着催化剂投加量的增加,NFX的降解率是不断增加的。当催化剂投加量为2.0g/L时,CuO/CuFe2O4/Fe2O3(600℃,3h)复合光催化剂对NFX的降解率最高,为75.3%。
以上实施例中,抗生素采用的是诺氟沙星,但是并不限制本发明降解的抗生素为诺氟沙星,本发明的方法适用于降解任何抗生素与染料废水等。
Claims (8)
1.双Z型CuO/CuFe2O4/Fe2O3复合光催化剂,其特征在于,采用共沉淀-不完全固相反应法制备,制备方法包括如下步骤:将Cu(OH)2和Fe(OH)3共沉淀混合物,在60℃干燥12.0h后,研磨,放入马弗炉中于500~700℃,煅烧2.0~4.0h,得到目标产物双Z型CuO/CuFe2O4/Fe2O3复合光催化剂。
2.根据权利要求1所述的双Z型CuO/CuFe2O4/Fe2O3复合光催化剂,其特征在于,按摩尔比,Cu2+:Fe3+=1.0:2.0。
3.根据权利要求1或2所述的双Z型CuO/CuFe2O4/Fe2O3复合光催化剂,其特征在于,所述Cu(OH)2和Fe(OH)3共沉淀混合物的制备方法,包括如下步骤:将Cu(NO3)2·3H2O和Fe(NO3)3·9H2O共同溶于去离子水中,搅拌溶解后,逐滴滴加NaOH溶液,磁力搅拌后,静置,弃上清液,沉淀用蒸馏水洗涤至pH=7.0~8.0,过滤,得到Cu(OH)2和Fe(OH)3共沉淀混合物。
4.权利要求1或2所述的双Z型CuO/CuFe2O4/Fe2O3复合光催化剂在太阳光下降解抗生素中的应用。
5.根据权利要求4所述的应用,其特征在于,方法如下:于含有抗生素的溶液中,加入双Z型CuO/CuFe2O4/Fe2O3复合光催化剂,在太阳光下照射3.0~4.0h。
6.根据权利要求5所述的应用,其特征在于,双Z型CuO/CuFe2O4/Fe2O3复合光催化剂的加入量为0.5~2.0g/L。
7.根据权利要求4-6任意一项所述的应用,其特征在于,所述抗生素为喹诺酮类抗生素。
8.根据权利要求7所述的应用,其特征在于,所述喹诺酮类抗生素为诺氟沙星。
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