CN113731430B - 双Z型CuO/CuBi2O4/Bi2O3复合光催化剂及其制备方法和应用 - Google Patents
双Z型CuO/CuBi2O4/Bi2O3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/CuBi2O4/Bi2O3复合光催化剂及其制备方法和应用。将Cu(OH)2和Bi(OH)3分散于蒸馏水中,充分搅拌使混合溶液均匀后进行过滤,将过滤得到的沉淀混合物在50℃干燥12h,干燥后的粉末均匀研磨,放入马弗炉中于350~550℃,煅烧2~5h,得目标产物CuO/CuBi2O4/Bi2O3。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,基于不完全固相反应制备的双Z型CuO/CuBi2O4/Bi2O3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,具体涉及采用化学沉淀法和不完全固相反应法制备双Z型CuO/CuBi2O4/Bi2O3复合光催化剂及其在太阳光下催化降解抗生素废水的应用。
背景技术
抗生素是一类典型的持久性有机污染物,诺氟沙星(NFX)作为第三代喹诺酮类抗生素,是一种具有广谱性的抗生素药物,被广泛应用于对人和动物的疾病治疗。由于这类抗生素被大量使用且在人体和牲畜体内不能被完全吸收,导致残留物释放到水中,造成一系列环境污染问题。因此,自然环境中往往存在着大量的NFX残留物质。目前,环境保护与治理已引起世界各国的广泛关注。而传统的处理方法如微生物法、物理法和化学法往往具有处理效果不理想,处理成本高以及会对环境造成二次污染等问题。近年来,光催化氧化技术以其氧化还原能力较强、无二次污染、成本较低、并且重复利用后仍有很好的降解效果等特点成为处理废水中抗生素较好的选择。
目前在光催化氧化技术的研究中,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。CuBi2O4作为一种典型的p型半导体材料,拥有1.7eV左右的禁带宽度,由于具有窄带隙和良好的光催化性能而引起了人们的关注。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。铋基化合物以金属铋和其他铋的化合物为主要成分,具有特殊的层状结构和适当大小的禁带宽度,Bi2O3是最简单的铋系化合物,由于特殊的电子结构和优异的可见光响应性能,被认为是一种很有前景的可见光光催化剂。这三种半导体具有合适的带隙结构,并且具有良好的催化性能以及化学性质稳定性、成本低廉、制备工艺简单等特点,对抗生素废水和染料废水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
本发明的目的是通过Cu(OH)2与Bi(OH)3的不完全固相反应,通过控制煅烧温度与时间,使其一部分生成CuBi2O4,另一部分在高温条件下生成CuO与Bi2O3,进而使三者以近乎无界面的形式共存,构成双Z型CuO/CuBi2O4/Bi2O3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/CuBi2O4/Bi2O3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/CuBi2O4/Bi2O3复合光催化剂,制备方法包括如下步骤:将Cu(OH)2和Bi(OH)3分散于蒸馏水中,搅拌3~4h后进行过滤,将过滤所得沉淀在50℃干燥12h;干燥后的粉末均匀研磨后,放入马弗炉中于350~550℃,煅烧2~5h,得目标产物CuO/CuBi2O4/Bi2O3。
进一步的,上述的双Z型CuO/CuBi2O4/Bi2O3复合光催化剂,按摩尔比,Cu(OH)2:Bi(OH)3=1:1。
进一步的,上述的双Z型CuO/CuBi2O4/Bi2O3复合光催化剂,所述Cu(OH)2制备方法,包括如下步骤:将Cu(NO3)2·3H2O溶于去离子水中,搅拌使其溶解,然后逐滴滴加NaOH溶液,磁力搅拌后,静置,弃上清液,沉淀用蒸馏水洗涤至洗出液pH=7~8,离心,得Cu(OH)2。
进一步的,上述的双Z型CuO/CuBi2O4/Bi2O3复合光催化剂,所述Bi(OH)3制备方法,包括如下步骤:将Bi(NO3)3·5H2O溶于乙二醇中,搅拌使其溶解,然后逐滴滴加NaOH溶液,磁力搅拌后,静置,弃上清液,沉淀用蒸馏水洗涤至洗出液pH=7~8,离心,得Bi(OH)3。
本发明提供的双Z型CuO/CuBi2O4/Bi2O3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/CuBi2O4/Bi2O3复合光催化剂,在太阳光下照射3~4h。
进一步的,双Z型CuO/CuBi2O4/Bi2O3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。
更进一步的,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,通过不完全固相反应制备双Z型CuO/CuBi2O4/Bi2O3复合光催化剂,制备方法简单,并且能够使CuO、CuBi2O4、Bi2O3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/CuBi2O4/Bi2O3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的X射线衍射图。
图2是Bi2O3的X射线衍射图。
图3是CuBi2O4的X射线衍射图。
图4是CuO/CuBi2O4/Bi2O3的X射线衍射图。
图5是CuO/CuBi2O4/Bi2O3的扫描电子显微镜图。
图6是CuO/CuBi2O4/Bi2O3的透射电子显微镜图。
图7是CuO/CuBi2O4/Bi2O3紫外可见漫反射吸收光谱图。
图8是不同催化剂降解诺氟沙星溶液的紫外-可见光吸收图。
具体实施方式
实施例1
(一)双Z型CuO/CuBi2O4/Bi2O3复合光催化剂,制备方法如下:
1)通过化学沉淀法制备Cu(OH)2:首先,称量1.210g Cu(NO3)2·3H2O于烧杯中,向其中加入50mL去离子水,磁力搅拌30min使其全部溶解。其次,向烧杯中逐滴滴加10mL1.0mol/L NaOH溶液,磁力搅拌1.0h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=7~8,离心得到Cu(OH)2。
2)通过化学沉淀法制备Bi(OH)3:首先,称量2.425g Bi(NO3)3·5H2O于烧杯中,向其中加入100mL乙二醇,持续搅拌30min使其完全溶解。其次,向烧杯中逐滴滴加15mL1.0mol/LNaOH溶液,磁力搅拌1.0h后静置,待Bi(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=7~8,离心得到Bi(OH)3。
3)通过不完全固相反应制备CuO/CuBi2O4/Bi2O3复合光催化剂:将上述制备的Cu(OH)2和Bi(OH)3,按摩尔比1:1混合,分散于蒸馏水中,搅拌3.0h后过滤,将过滤得到的混合沉淀在50℃干燥12h。干燥后将粉末置于研钵中均匀研磨后放入坩埚。分别在350℃,450℃和550℃下煅烧3.0h,在450℃下分别煅烧2.0h、4.0h和5.0h。得到的产物分别标记为CuO/CuBi2O4/Bi2O3(350-3)、CuO/CuBi2O4/Bi2O3(450-3)、CuO/CuBi2O4/Bi2O3(550-3)、CuO/CuBi2O4/Bi2O3(450-2)、CuO/CuBi2O4/Bi2O3(450-4)、CuO/CuBi2O4/Bi2O3(450-5)。
(二)对比例
制备CuO纳米粒子:首先,称量1.210g Cu(NO3)2·3H2O于烧杯中,向其中加入50mL去离子水,磁力搅拌30min使其全部溶解。其次,向烧杯中逐滴滴加10mL 1.0mol/L NaOH溶液,磁力搅拌1.0h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=7~8,离心得到Cu(OH)2沉淀。将得到的沉淀在50℃干燥12h,干燥后进行均匀研磨,并放入坩埚中于马弗炉450℃煅烧4.0h,得到CuO纳米粒子。
制备Bi2O3纳米粒子:首先,称量2.425g Bi(NO3)3·5H2O于烧杯中,向其中加入100mL乙二醇,持续搅拌30min使其完全溶解。其次,向烧杯中逐滴滴加15mL 1.0mol/L NaOH溶液,磁力搅拌1.0h后静置,待Bi(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=7~8,离心得到Bi(OH)3沉淀。将得到的沉淀在50℃干燥12h,干燥后进行均匀研磨,并放入坩埚中于马弗炉450℃煅烧4.0h,得到Bi2O3纳米粒子。
制备CuBi2O4纳米粒子:首先,称量0.6050g Cu(NO3)2·3H2O溶于30mL去离子水中,搅拌使其溶解。向溶液中逐滴滴加5mL 1.0mol/L NaOH溶液,磁力搅拌1.0h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=7~8,离心得到Cu(OH)2沉淀。其次,称量2.425g Bi(NO3)3·5H2O溶于100mL乙二醇中,持续搅拌使其完全溶解后,向其中逐滴滴加15mL 1.0mol/L NaOH溶液,磁力搅拌1.0h后静置,待Bi(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=7~8,离心得到Bi(OH)3沉淀。最后,将得到的Cu(OH)2和Bi(OH)3沉淀分散于蒸馏水中,搅拌3.0h后过滤,将过滤得到的沉淀混合物在50℃干燥12h,干燥后的粉末均匀研磨后,放入坩埚于马弗炉700℃煅烧3.0h,得到CuBi2O4纳米粒子。
(三)催化剂的表征
图1是对比例制备的CuO纳米粒子的XRD图谱,如图1所示,CuO的特征峰与标准卡(JCPDS 80-1917)一致。该结果显示成功地制备了CuO。
图2是对比例制备的Bi2O3纳米粒子的XRD图谱,如图2所示,Bi2O3的特征峰可以被清晰地看到,并且与标准卡(JCPDS 71-2274)一一对应,这表明Bi2O3制备成功。
图3是对比例制备的CuBi2O4纳米粒子的XRD图谱,如图3所示,CuBi2O4的特征峰与标准卡(JCPDS 71-1774)相符合。该结果表明成功合成了CuBi2O4。
图4是双Z型CuO/CuBi2O4/Bi2O3(450-4)复合光催化剂的XRD图谱,如图4所示,属于CuO、CuBi2O4、Bi2O3三种物质的特征峰均可以被观察到,结果表明成功制备了CuO/CuBi2O4/Bi2O3(450-4)复合光催化剂。
图5是CuO/CuBi2O4/Bi2O3(450-4)的扫描电子显微镜图。由图5中可以看出,立体菱形状的CuO与表面呈光滑形态的短棒状Bi2O3及较大块状的CuBi2O4均可以被观察到,测试结果表明成功制备了CuO/CuBi2O4/Bi2O3复合光催化剂。
图6是CuO/CuBi2O4/Bi2O3(450-4)的透射电子显微镜图。从图6中可以清晰的看到三种不同方向的晶格条纹和宽度,经过比对分别属于CuO、Bi2O3及CuBi2O4纳米粒子,因此结果证明三种纳米粒子共存,CuO/CuBi2O4/Bi2O3复合光催化剂成功制备。
图7是CuO/CuBi2O4/Bi2O3(450-4)紫外可见漫反射吸收光谱图。如图7所示,所制备的CuO/CuBi2O4/Bi2O3复合光催化剂在200-800nm具有吸收波长,能够有效利用太阳光。
实施例2双Z型CuO/CuBi2O4/Bi2O3复合光催化剂在太阳光下降解抗生素中的应用
(一)催化剂煅烧温度对诺氟沙星降解率的影响
实验方法:分别称量0.03g CuO/CuBi2O4/Bi2O3(350-3)、CuO/CuBi2O4/Bi2O3(450-3)与CuO/CuBi2O4/Bi2O3(550-3)于3个加入30mL初始浓度为5mg/L的NFX溶液的石英管中,在太阳光下照射3h,离心取上清液,再将上清液进行过滤,然后在200-800nm波长范围内测定其吸光度。取274.9nm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。
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,在煅烧温度为450℃时所制备的复合光催化剂CuO/CuBi2O4/Bi2O3(450-3)降解NFX效果最好,在太阳光下照射3小时降解率可达63.91%,因此本发明所制备的双Z型CuO/CuBi2O4/Bi2O3复合光催化剂煅烧温度选择为450℃。
(二)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0.03g CuO/CuBi2O4/Bi2O3(450-2)、CuO/CuBi2O4/Bi2O3(450-3)、CuO/CuBi2O4/Bi2O3(450-4)及CuO/CuBi2O4/Bi2O3(450-5)于4个加入30mL初始浓度为5mg/L的NFX溶液的石英管中,在太阳光下照射3h,离心取上清液,再将上清液进行过滤,然后在200-800nm波长范围内测定其吸光度。取274.9nm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2所示。
表2催化剂煅烧时间对诺氟沙星降解率的影响
由表2可知,当煅烧温度为450℃,煅烧时间为4h时,所制备双Z型CuO/CuBi2O4/Bi2O3(450-4)复合光催化剂对NFX的降解率最高,降解率为74.52%。
(三)不同催化剂对诺氟沙星降解率的影响
分别称量0.03g CuO、Bi2O3、CuBi2O4及CuO/CuBi2O4/Bi2O3(450-4)于4个加入30mL初始浓度为5mg/L的NFX溶液的石英管中,在太阳光下照射3h,离心取上清液,再将上清液进行过滤,然后在200-800nm波长范围内测定其吸光度。取274.9nm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3和图8所示。
表3不同催化剂对诺氟沙星降解率的影响
由表3可见,相比3个单体,本发明所制备的双Z型CuO/CuBi2O4/Bi2O3复合光催化剂对NFX污染物的降解效果最好,降解率可达74.52%。
由图8中可以看出,在太阳光下,CuO、Bi2O3、CuBi2O4单体与CuO/CuBi2O4/Bi2O3(450-4)复合光催化剂对NFX均有降解作用,但双Z型CuO/CuBi2O4/Bi2O3(450-4)复合光催化剂对NFX溶液降解效果最明显。
(四)光照时间对诺氟沙星降解率的影响
分别称量4份0.03g CuO/CuBi2O4/Bi2O3(450-4)于4个加入30mL初始浓度为5mg/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,再将上清液进行过滤,然后在200-800nm波长范围内测定其吸光度。取274.9nm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4所示。
表4光照时间对诺氟沙星降解率的影响
由表4可知,NFX降解率随着光照时间的增加而增加,当照射240min时,NFX降解程度最大,降解率可达82.34%。
(五)催化剂不同投加量对诺氟沙星降解率的影响
量取30mL初始浓度为5mg/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/CuBi2O4/Bi2O3(450-4)复合光催化剂,在太阳光下照射3h,离心取上清液,再将上清液进行过滤,然后在200-800nm波长范围内测定其吸光度。取274.9nm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5所示。
降解率(%)=(1-C/C0)×100%(其中C0:原液的浓度;C:样品的浓度)。
表5催化剂不同投加量对诺氟沙星降解的影响
由表5可见,随着催化剂投加量的增加,NFX的降解率先增加后减小。当催化剂投加量为1.0g/L时,CuO/CuBi2O4/Bi2O3(450-4)复合光催化剂对NFX的降解率最高,为74.52%。
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 (7)
1. 双Z型CuO/CuBi2O4/Bi2O3复合光催化剂,其特征在于,制备方法包括如下步骤:将摩尔比为1:1的Cu(OH)2和Bi(OH)3分散于蒸馏水中,搅拌3~4 h后进行过滤,将过滤所得沉淀在50℃干燥12 h;干燥后的粉末均匀研磨后,放入马弗炉中于350~450℃,煅烧2~5 h,得目标产物CuO/CuBi2O4/Bi2O3。
2. 根据权利要求1所述的双Z型CuO/CuBi2O4/Bi2O3复合光催化剂,其特征在于,所述Cu(OH)2制备方法,包括如下步骤:将Cu(NO3)2·3H2O 溶于去离子水中,搅拌使其溶解,然后逐滴滴加NaOH溶液,磁力搅拌后,静置,弃上清液,沉淀用蒸馏水洗涤至洗出液pH=7~8,离心,得Cu(OH)2。
3. 根据权利要求1所述的双Z型CuO/CuBi2O4/Bi2O3复合光催化剂,其特征在于,所述Bi(OH)3制备方法,包括如下步骤:将Bi(NO3)3·5H2O 溶于乙二醇中,搅拌使其溶解,然后逐滴滴加NaOH溶液,磁力搅拌后,静置,弃上清液,沉淀用蒸馏水洗涤至洗出液pH=7~8,离心,得Bi(OH)3。
4.一种如权利要求1所述的双Z型CuO/CuBi2O4/Bi2O3复合光催化剂在太阳光下降解喹诺酮类抗生素中的应用。
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/CuBi2O4/Bi2O3复合光催化剂,在太阳光下照射3~4 h。
6. 根据权利要求5所述的应用,其特征在于,双Z型CuO/CuBi2O4/Bi2O3复合光催化剂的加入量为0.5~2.0 g/L。
7.根据权利要求4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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