CN109092334B - 一种可见光响应的BiOBr/CeVO4异质结的制备及其应用 - Google Patents
一种可见光响应的BiOBr/CeVO4异质结的制备及其应用 Download PDFInfo
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Abstract
本发明提供了一种可见光响应的BiOBr/CeVO4异质结的制备方法及其应用。具体制备方法为:将硝酸铈Ce(NO3)3·6H2O加入至有机溶剂中,磁力搅拌至溶解;将偏钒酸铵NH4VO3加入至蒸馏水中,磁力搅拌至溶解;上述溶液混合后,调节pH值,超声处理,得到CeVO4前驱体;将硝酸铋Bi(NO3)3·5H2O和KBr加入至蒸馏水中,磁力搅拌溶解后,调节pH值,室温超声处理,得BiOBr前驱体;将CeVO4前驱体和BiOBr前驱体倒入水热反应釜中,在100~200℃下反应2~10h;冷却室温后,样品经过离心、洗涤、干燥和焙烧,即得到BiOBr/CeVO4异质结。此催化剂在可见光照射下,实现目标污染物左氧氟沙星完全降解。该方法合成路线简单易控,形貌重现性好,适用于工业大批量生产的需求。
Description
技术领域
本发明涉及一种可见光响应的BiOBr/CeVO4异质结的制备方法及其应用,属于环境化工光催化水处理技术领域,特别涉及可见光处理抗生素污染废水。
背景技术
左氧氟沙星是第三代氟喹诺酮类广谱抗菌药,在低剂量添加时可以促进畜禽的生长,而高剂量使用时又可以用来治疗疾病,因此成为生产量和畜禽养殖业使用量较大的抗生素。然而,左氧氟沙星进入到动物体内后,绝大部分以原药或代谢产物进入水体,给水体严重的污染。因此,如何高效消除抗生素以提高水环境质量已引起许多国家的关注。抗生素废水成本复杂、CODCr浓度高、生物降解难、污染性强等特点,一直是废水处理中的难题。抗生素废水处理方法包括吸附法、膜分离法、光催化氧化法、电化学氧化法、超声波降解法等。其中,光催化氧化法以清洁的太阳能为能源,可以将污染物彻底降解,因此受到广泛关注。半导体是光催化剂的一个重要范畴,广泛应用在太阳能转化和环境净化方面,例如利用太阳能分解水制氢以及降解有机污染物。目前,研究和应用最为广泛的光催化剂是TiO2,但此催化剂只对约占4%太阳光中的紫外光有响应,而对约占43%可见光没有响应。为了更好的利用太阳能中的可见光,方法之一是研发出新型的具有可见光相应的光催化材料。
近年来,铋基光催化剂受到广泛关注,如BiVO4、BiOX(X=Cl、Br、I)、Bi2WO6和Bi2MoO6,其中BiOBr具有层状结构从而表现出优异的催化性能。然而,纯BiOBr光生电子空穴分离效率较低,导致其光催化抗生素效率较低。为了强化BiOBr的光催化活性,研究者已经做了大量的工作,如控制其粒子形貌、离子掺杂、贵金属修饰以及形成异质结。在这些方法中,异质结的形成可以有效地提高电子空穴的分离效率。因此,本专利通过将BiOBr与CeVO4半导体材料复合,制备异质结,降低BiOBr光生电子空穴复合率及提高其光催化活性。
发明内容
本发明的目的旨在提供一种简单、易于操作、催化活性高的BiOBr/CeVO4异质结的制备工艺。
本发明为实现此目的,本发明一方面提供一种CeVO4/BiVO4异质结,所述异质结的微观形貌是由部分BiOBr纳米粒子以覆盖的方式包裹在CeVO4微米球表面,所述 CeVO4微米球直径约为1μm,所述BiOBr纳米粒子呈现中间粗两端尖的形貌特征,长度约为0.3-0.9μm。
作为优选的技术方案,所述催化剂的禁带宽度为2.17eV,吸收边带为571nm,具有可见光响应。
另一方面本发明提供上述BiOBr/CeVO4异质结的制备方法,采用超声水热法,包括以下步骤:
步骤1、将硝酸铈Ce(NO3)3·6H2O加入至5-30ml有机溶剂中,磁力搅拌至溶解,得混合溶液A;
步骤2、将偏钒酸铵NH4VO3加入至5-30ml蒸馏水中,磁力搅拌至溶解,得混合溶液B;
步骤3、采用微量注射泵将混合溶液B以1-5ml/min的速度滴入混合溶液A中,调节溶液的pH值,室温超声处理,得产物C;
步骤4、将硝酸铋Bi(NO3)3·5H2O和等摩尔的KBr加入至5-30ml蒸馏水中,磁力搅拌至溶解后,调节溶液的pH值,室温超声处理,得产物D;
步骤5:将产物C和D加入到水热反应釜中,在一定反应温度下反应一定时间,得产物E;
步骤6:将产物E过滤,分别用蒸馏水和无水乙醇洗涤,然后在120℃下干燥12h,焙烧,即得所述的BiOBr/CeVO4异质结。
作为优选的技术方案,所述的步骤1中有机溶剂为无水乙醇、乙二醇、丙三醇或聚乙烯吡咯烷酮。
作为优选的技术方案,所述的步骤2中蒸馏水的温度为50~100℃;步骤1中的硝酸铈与步骤2中的偏钒酸铵的摩尔比为1:1~1:5。
作为优选的技术方案,所述的步骤3中pH为1~6,超声时间为30~120min。
作为优选的技术方案,所述的步骤4中pH值与步骤3中pH值一致,超声时间为 60~180min。步骤1中的硝酸铈与步骤4中的硝酸铋的摩尔比为10:1~5:1。
作为优选的技术方案,所述的步骤5中,反应温度为100~200℃,反应时间为2~10h。
作为优选的技术方案,所述的步骤6中焙烧温度为200~500℃,焙烧时间为1~5h。
再一方面本发明提供上述BiOBr/CeVO4异质结在可见光响应的光催化材料中的应用。
作为优选的技术方案,上述BiOBr/CeVO4异质结可用于光催化降解左氧氟沙星。
本发明的优点在于:
①合成出BiOBr纳米粒子和CeVO4微米球形貌的BiOBr/CeVO4异质结;
②合成的BiOBr/CeVO4异质结的禁带宽度为2.17eV,吸收边带为571nm,具有可见光响应;在可见光照射下,3h内可实现目标污染物左氧氟沙星完全降解;
③合成方法条件温和且易于操作,BiOBr/CeVO4形貌规则且重复性好,易于工业化生产。
附图说明
本发明附图3幅。
图1是本发明实施方案1制备的BiOBr/CeVO4异质结的SEM图。
图2是本发明实施方案1制备的BiOBr/CeVO4异质结的DRS图。
图3是本发明实施方案1制备的BiOBr/CeVO4异质结在可见光照射下降解左氧氟沙星的效率图。
具体实施方式
下述非限制性实施例可以使本领域的普通技术人员更全面地理解本发明,但不以任何方式限制本发明。
实施例1
BiOBr/CeVO4异质结的制备步骤为:
步骤1、将0.005mol硝酸铈Ce(NO3)3·6H2O加入至30ml乙二醇溶液中,磁力搅拌至溶解,得混合溶液A;
步骤2、将0.005mol偏钒酸铵NH4VO3加入到30ml的50℃蒸馏水中,磁力搅拌至溶解,得混合溶液B;
步骤3、采用微量注射泵将混合溶液B以5ml/min的速度滴入混合溶液A中,调节溶液的pH=1,室温超声30min,得产物C;
步骤4、将0.001mol硝酸铋Bi(NO3)3·5H2O和0.001mol的KBr加入至30ml蒸馏水中,磁力搅拌至溶解后,调节溶液的pH=1,室温超声60min,得产物D;
步骤5:将产物C和D加入到100ml水热反应釜中,在100℃反应温度下反应2h。
步骤6:步骤4结束后,过滤,分别用蒸馏水和无水乙醇洗涤,然后将产物在120℃下干燥12h,在200℃焙烧5h。
从图1可以看出所制备的BiOBr/CeVO4异质结,其微观形貌是由部分BiOBr纳米粒子以覆盖的方式包裹在CeVO4微米球表面,所述CeVO4微米球直径约为1μm,所述BiOBr纳米粒子呈现中间粗两端尖的形貌特征,长度约为0.3-0.9μm。
从图2可以看出所制备的BiOBr/CeVO4异质结的禁带宽度为2.17eV,吸收边带为571nm,具有可见光响应。
实施例2
BiOBr/CeVO4异质结的制备步骤为:
步骤1、将0.001mol硝酸铈Ce(NO3)3·6H2O加入至5ml丙三醇溶液中,磁力搅拌至溶解,得混合溶液A;
步骤2、将0.005mol偏钒酸铵NH4VO3加入到5ml的100℃蒸馏水中,磁力搅拌至溶解,得混合溶液B;
步骤3、采用微量注射泵将混合溶液B以1ml/min的速度滴入混合溶液A中,调节溶液的pH=6,室温超声120min,得产物C;
步骤4、将0.0001mol硝酸铋Bi(NO3)3·5H2O和0.0001mol的KBr加入至5ml的蒸馏水中,磁力搅拌至溶解后,调节溶液的pH=6,室温超声180min,得产物D;
步骤5:将产物C和D加入到100ml水热反应釜中,在200℃反应温度下反应10h。
步骤6:步骤4结束后,过滤,分别用蒸馏水和无水乙醇洗涤,然后将产物在120℃下干燥12h,在500℃焙烧1h。
实施例3
BiOBr/CeVO4异质结的制备步骤为:
步骤1、将0.005mol硝酸铈Ce(NO3)3·6H2O加入至20ml聚乙烯吡咯烷酮溶液中,磁力搅拌至溶解,得混合溶液A;
步骤2、将0.005mol偏钒酸铵NH4VO3加入到20ml的50℃蒸馏水中,磁力搅拌至溶解,得混合溶液B;
步骤3、采用微量注射泵将混合溶液B以5ml/min的速度滴入混合溶液A中,调节溶液的pH=4,室温超声60min,得产物C;
步骤4、将0.0005mol硝酸铋Bi(NO3)3·5H2O和0.0005mol的KBr加入至20ml的蒸馏水中,磁力搅拌至溶解后,调节溶液的pH=4,室温超声120min,得产物D;
步骤5:将产物C和D加入到100ml水热反应釜中,在150℃反应温度下反应4h。
步骤6:步骤4结束后,过滤,分别用蒸馏水和无水乙醇洗涤,然后将产物在120℃下干燥12h,在200℃焙烧5h。
应用例1
光催化降解左氧氟沙星的步骤为:
步骤1、将100mg的本发明实施方案1制备的BiOBr/CeVO4样品加入到200ml左氧氟沙星溶液(50mg/L)中,磁力搅拌1h。
步骤2、将上述反应溶液置于具有420nm滤光片的氙灯(300W)下进行光催化降解实验。
步骤3、每间隔1h,用移液管吸取1ml反应液,离心后的上清液并稀释,采用 UV1100分光光度计记录294nm吸收峰,检测左氧氟沙星浓度变化情况。
从图3可以看出,随着可见光照射时间的延长,左氧氟沙星降解效率逐渐提高, 3h后基本完全降解。
Claims (10)
1.一种可见光响应的BiOBr/CeVO4异质结,其特征在于:所述异质结的微观形貌是由部分BiOBr纳米粒子以覆盖的方式包裹在CeVO4微米球表面,所述CeVO4微米球直径约为1μm,所述BiOBr纳米粒子呈现中间粗两端尖的形貌特征,长度为0.3-0.9μm。
2.根据权利要求1所述的一种可见光响应的BiOBr/CeVO4异质结,其特征在于:所述异质结的禁带宽度为2.17eV,吸收边带为571nm,具有可见光响应。
3.权利要求1或2所述一种可见光响应的BiOBr/CeVO4异质结的制备方法,其特征在于采用超声水热法,包括以下步骤:
步骤1、将硝酸铈Ce(NO3)3·6H2O加入至5-30ml有机溶剂中,磁力搅拌至溶解,得混合溶液A;
步骤2、将偏钒酸铵NH4VO3加入至5-30ml蒸馏水中,磁力搅拌至溶解,得混合溶液B;
步骤3、采用微量注射泵将混合溶液B以1-5ml/min的速度滴入混合溶液A中,调节溶液的pH值,室温超声处理,得产物C;
步骤4、将硝酸铋Bi(NO3)3·5H2O和等摩尔的KBr加入至5-30ml蒸馏水中,磁力搅拌至溶解后,调节溶液的pH值,室温超声处理,得产物D;
步骤5:将产物C和D加入到水热反应釜中,在一定反应温度下反应一定时间,得产物E;
步骤6:将产物E过滤,分别用蒸馏水和无水乙醇洗涤,然后在120℃下干燥12h,焙烧,即得所述的BiOBr/CeVO4异质结。
4.根据权利要求3所述的一种可见光响应的BiOBr/CeVO4异质结的制备方法,其特征在于所述的步骤1中有机溶剂为无水乙醇、乙二醇、丙三醇或聚乙烯吡咯烷酮。
5.根据权利要求3所述的一种可见光响应的BiOBr/CeVO4异质结的制备方法,其特征在于所述的步骤2中蒸馏水的温度为50~100℃;步骤1中的硝酸铈与步骤2中的偏钒酸铵的摩尔比为1:1~1:5。
6.根据权利要求3所述的一种可见光响应的BiOBr/CeVO4异质结的制备方法,其特征在于所述的步骤3中pH为1~6,超声时间为30~120min。
7.根据权利要求3所述的一种可见光响应的BiOBr/CeVO4异质结的制备方法,其特征在于所述的步骤4中pH值与步骤3中pH值一致,超声时间为60~180min;步骤1中的硝酸铈与步骤4中的硝酸铋的摩尔比为10:1~5:1。
8.根据权利要求3所述的一种可见光响应的BiOBr/CeVO4异质结的制备方法,其特征在于所述的步骤5中反应温度为100~200℃,反应时间为2~10h。
9.根据权利要求3所述的一种可见光响应的BiOBr/CeVO4异质结的制备方法,其特征在于所述的步骤6中焙烧温度为200~500℃,焙烧时间为1~5h。
10.权利要求1所述一种可见光响应的BiOBr/CeVO4异质结在可见光响应的光催化材料中的应用,其特征在于可见光催化降解左氧氟沙星。
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