CN111871405A - 一种利用光协同压电催化高效降解染料废水的方法 - Google Patents
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Abstract
本发明公开了一种利用光协同压电催化高效降解染料废水的方法，在BaTiO3粉体表面包覆BiVO4纳米颗粒，BaTiO3粉体在振动环境下由于压电效应表面会产生力生电荷，BiVO4纳米颗粒在可见光下可以诱导出光生电荷；BaTiO3/BiVO4压电/半导体复合材料在协同可见光和超声振动作用下，会产生增强的催化活性，可加快染料废水的降解，在60min内降解效率高达98％。本发明在于可见光协同压电催化，在废水处理领域有广阔的应用前景，且制备工艺简单，适合工业化生产。
Description
技术领域
本发明涉及废水处理技术领域，具体涉及一种利用光协同压电催化高效降解染料废水的方法。
背景技术
当今人类社会飞速发展，随之而来的环境污染问题愈发严重，寻找解决这一问题的有效方法迫在眉睫。在水中存在着大量的有色有机化合物，例如从纺织物、印刷制品、食物或其他工业中排出的染料废水，都可能导致严重的环境污染问题。大多数染料因为其在水中溶解度大，化学性质稳定，导致实际废水处理工艺开发相对困难。迄今为止，各种物理、化学和生物处理方法已被人们用于去除工业废水中的有色有机化合物。利用物理技术对染料废水进行处理的方法，如活性炭吸附、过滤等，仅仅是指染料从液相转移到固相，容易造成二次污染。生物学方法因现代染料的稳定性生物体的毒性而不能应用于大多数类型的染料废水。化学法的主要缺点是催化材料只能使用一次，而不能循环使用。
纳米结构压电材料能够直接从微弱环境振动(如水流和声波)中获取机械能来生电，因此纳米结构压电材料可用于污水处理领域，通过原位压电化学反应过程来降解有害污染物。Xu等人通过水热辅助溶胶-凝胶制备Ba0.7Sr0.3TiO3纳米压电粉体,在298K-323K之间的水浴中进行热循环来研究其热释电催化性能(X.Xu,L.Xiao,Y.Jia,Z.Wu,F.Wang,Y.Wang,N.O.Haugen,H.Huang.Pyro-catalytic hydrogen evolution by Ba0.7Sr0.3TiO3nanoparticles:harvesting cold-hot alternation energy near room-temperature,Energy Environ.Sci.,2018,11:2198-2207.)。
BiVO4材料具有良好的可见光催化性能，Wetchakun等人采用均相沉淀法与水热法相结合的方法，成功制备了钒酸铋/二氧化铈纳米复合材料作为可见光催化剂，并进行了光催化剂的吸收范围和带隙能量对光催化性能影响的研究。其在可见光辐射下，以0.6:0.4mol/L的BiVO4/CeO2纳米复合材料对染料废水具有较高的光催化活性。(N.Wetchakun,S.Chaiwichain,B.Inceesungvorn,K.Pingmuang,S.Phanichphant,A.I.Minett,J.Chen.BiVO4/CeO2nanocomposites with high visible-light-induced photocatalyticactivity,ACS Appl.Mater.Interfaces,2012,7:3718–3723.)
本发明将BaTiO3粉体表面与BiVO4相复合，结合压电催化和光催化来提升催化降解染料废水的性能。一方面，通过控制反应水温，使BiVO4在BaTiO3表面沉积更为均匀，表现出优异的光催化性能；另一方面，表面覆盖BiVO4纳米颗粒可以阻碍BaTiO3在振动作用下生成正负电荷的复合，进一步增强其压电性能。两者结合，可提高对染料废水的降解率(50％～98％)。
发明内容
本发明所要解决的问题是：提供一种利用光协同压电催化高效降解染料废水的方法，通过在BaTiO3压电粉体表面复合BiVO4纳米颗粒，从而显著提高其催化降解染料废水效率。
本发明为解决上述问题所提供的技术方案为：一种利用光协同压电催化高效降解染料废水的方法，所述方法发包括以下步骤：
1)、称量一定量的BaTiO3粉体，粉体粒径200-500nm，x份Bi(NO3)3·5H2O和x份NH4VO3其中，x＝0.1，0.3，0.5，0.7；
2)、分别取称量好的Bi(NO3)3·5H2O溶于稀硝酸，NH4VO3溶于蒸馏水(Bi:V＝1:1)，用于合成BaTiO3/BiVO4复合材料；
3)、将BaTiO3倒入NH4VO3溶液中，持续超声搅拌；再将Bi(NO3)3溶液缓慢倒入混合液中，恒温反应，调节PH值至7-8，反应结束后过滤沉淀物烘干备用；
4)、将沉淀物煅烧，获得BaTiO3/BiVO4复合粉体；
5)、将复合粉体极化；
6)、协同可见光和超声振动催化，使用紫外分光光度计检测降解后的溶液并计算得到降解效率。
优选的，所述步骤3)中恒温温度为50℃-60℃。
优选的，所述步骤4)中沉淀物煅烧温度为350℃-500℃，煅烧保温时间为2h-24h。
优选的，所述步骤5)中复合粉体极化时间15min，极化电场为0.5kV～3kV。
优选的，所述步骤6)中在超声振动催化的同时，用氙灯模拟可见光对其进行辐照。
与现有技术相比，本发明的优点是：
(1)本发明提出了可见光协同压电催化提高催化降解有机污染物效率这一观点。
(2)本发明通过在压电BaTiO3粉体表面复合BiVO4纳米颗粒，构造一种压电/半导体异质结来增强催化性能。
(3)本发明通过将压电粉体进行极化，让纳米微畴沿一定的方向进行排列，在样品内部构建出内电场，有利于力生/光生电子空穴对的分离，进而提高催化效率。
综上所述，本发明制备工艺简便、经济合理，适合规模化工业生产，对于提高催化降解染料废水等方面具有重要的意义。
附图说明
此处所说明的附图用来提供对本发明的进一步理解，构成本发明的一部分，本发明的示意性实施例及其说明用于解释本发明，并不构成对本发明的不当限定。
图1为BaTiO3/BiVO4催化降解示意图。
图2为实施例1的BaTiO3/BiVO4催化剂的XRD。
图3为实施例1不同催化时间的紫外数据。
具体实施方式
以下将配合附图及实施例来详细说明本发明的实施方式，借此对本发明如何应用技术手段来解决技术问题并达成技术功效的实现过程能充分理解并据以实施。
实施例1：
1)称量1份BaTiO3粉体，粉体粒径300nm，0.5份Bi(NO3)3·5H2O和0.5份NH4VO3。
2)分别取Bi(NO3)3·5H2O溶于稀硝酸，NH4VO3溶于蒸馏水(Bi:V＝1:1)，用于合成BaTiO3/BiVO4复合材料。
3)将BaTiO3倒入NH4VO3溶液中，持续超声搅拌；再将Bi(NO3)3溶液缓慢倒入混合液中，60℃恒温反应，调节PH值至8，反应结束后过滤沉淀物烘干备用。
4)将沉淀物350℃煅烧24h，获得BaTiO3/BiVO4复合粉体。
5)将复合粉体极化，极化场强为2kV，极化时间为15min。
6)协同可见光和超声振动催化罗丹明B溶液，反应时间为60分钟，反应水温为30℃，获得高降解效率为98％。
实施例2：
1)称量1份BaTiO3粉体，粉体粒径200nm，0.3份Bi(NO3)3·5H2O和0.3份NH4VO3。
2)分别取Bi(NO3)3·5H2O溶于稀硝酸，NH4VO3溶于蒸馏水(Bi:V＝1:1)，用于合成BaTiO3/BiVO4复合材料。
3)将BaTiO3倒入NH4VO3溶液中，持续超声搅拌；再将Bi(NO3)3溶液缓慢倒入混合液中，50℃恒温反应，调节PH值至7，反应结束后过滤沉淀物烘干备用。
4)将沉淀物400℃煅烧12h，获得BaTiO3/BiVO4复合粉体。
5)将复合粉体极化，极化场强为0.5kV，极化时间为15min。
6)协同可见光和超声振动催化罗丹明B溶液，反应时间为60分钟，反应水温为20℃，获得降解效率为72％。
实施例3：
1)称量1份BaTiO3粉体，粉体粒径500nm，0.7份Bi(NO3)3·5H2O和0.7份NH4VO3。
2)分别取Bi(NO3)3·5H2O溶于稀硝酸，NH4VO3溶于蒸馏水(Bi:V＝1:1)，用于合成BaTiO3/BiVO4复合材料。
3)将BaTiO3倒入NH4VO3溶液中，持续超声搅拌；再将Bi(NO3)3溶液缓慢倒入混合液中，60℃恒温反应，调节PH值至7.5，反应结束后过滤沉淀物烘干备用。
4)将沉淀物400℃煅烧12h，获得BaTiO3/BiVO4复合粉体。
5)将复合粉体极化，极化场强为0.5kV，极化时间为15min。
6)协同可见光和超声振动催化罗丹明B溶液，反应时间为60分钟，反应水温为30℃，获得得到高降解率为85％。
以上仅就本发明的最佳实施例作了说明，但不能理解为是对权利要求的限制。本发明不仅局限于以上实施例，其具体结构允许有变化。凡在本发明独立权利要求的保护范围内所作的各种变化均在本发明保护范围内。
Claims (5)
1.一种利用光协同压电催化高效降解染料废水的方法，其特征在于：所述方法发包括以下步骤：
1)、称量一定量的BaTiO3粉体，粉体粒径200-500nm，x份Bi(NO3)3·5H2O和x份NH4VO3其中，x＝0.1，0.3，0.5，0.7；
2)、分别取称量好的Bi(NO3)3·5H2O溶于稀硝酸，NH4VO3溶于蒸馏水(Bi:V＝1:1)，用于合成BaTiO3/BiVO4复合材料；
3)、将BaTiO3倒入NH4VO3溶液中，持续超声搅拌；再将Bi(NO3)3溶液缓慢倒入混合液中，恒温反应，调节PH值至7-8，反应结束后过滤沉淀物烘干备用；
4)、将沉淀物煅烧，获得BaTiO3/BiVO4复合粉体；
5)、将复合粉体极化；
6)、协同可见光和超声振动催化，使用紫外分光光度计检测降解后的溶液并计算得到降解效率。
2.根据权利要求1所述的一种利用光协同压电催化高效降解染料废水的方法，其特征在于：所述步骤3)中恒温温度为50℃-60℃。
3.根据权利要求1所述的一种利用光协同压电催化高效降解染料废水的方法，其特征在于：所述步骤4)中沉淀物煅烧温度为350℃-500℃，煅烧保温时间为2h-24h。
4.根据权利要求1所述的一种利用光协同压电催化高效降解染料废水的方法，其特征在于：所述步骤5)中复合粉体极化时间15min，极化电场为0.5kV～3kV。
5.根据权利要求1所述的一种利用光协同压电催化高效降解染料废水的方法，其特征在于：所述步骤6)中在超声振动催化的同时，用氙灯模拟可见光对其进行辐照。
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