CN108927183A - 一种异质结光催化剂、制备方法及其用途 - Google Patents
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- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/16—Phosphorus; Compounds thereof containing oxygen, i.e. acids, anhydrides and their derivates with N, S, B or halogens without carriers or on carriers based on C, Si, Al or Zr; also salts of Si, Al and Zr
- B01J27/18—Phosphorus; Compounds thereof containing oxygen, i.e. acids, anhydrides and their derivates with N, S, B or halogens without carriers or on carriers based on C, Si, Al or Zr; also salts of Si, Al and Zr with metals other than Al or Zr
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Abstract
本发明提供给了一种新的异质结光催化剂及其制备方法,所述催化剂是以BiIO4为内层,Ag3PO4为外层的复合结构;所述BiIO4与Ag3PO4的摩尔比为2‑10:100。制备方法工艺简单、易于控制、成本低廉,可制备高纯度的BiIO4/Ag3PO4异质结光催化剂。该催化剂用于光催化降解废水中苯酚。
Description
技术领域
本发明涉及材料化学领域,特别涉及一种异质结光催化剂、制备方法及其用途。
背景技术
随着现代工业的迅速发展,能源短缺和环境问题日益严重。因此,开发无污染的环保技术和清洁能源是我们面临的一项紧迫任务。自20世纪70年代TiO2被发现在紫外光照射下的光催化作用以来,半导体材料制成的光催化剂就被认为是解决环境问题的可靠解决方案之一。Ag3PO4具有很高的光致氧化降解有机染料(如罗丹明B,或亚甲基蓝等)的能力,而且量子产量可以达到90%。然而,由于Ag3PO4的导带(CB)的电势比氢的电势更正,Ag3PO4将不可避免地受到光腐蚀的影响,并且在没有电子受体的情况下表现出较低的光稳定性。Ag3PO4在独自参与可见光光催化降解苯酚废水反应时,在100分钟内的对废水中染料的降解率低于80%。
近年来,铋基材料例如BiPO4、BiVO4、Bi2WO6、BiOX(X=Cl、Br、I)作为光催化活性物质在有机污染物的降解中引起了大众的广泛关注。铋基光催化剂的分层结构存在于活性(Bi2O2)2+层和卤素原子层之间而有高效的光催化活性。在有机染料的降解过程中,发现了一种新型的含铋碘酸盐(BiIO4)材料,它是一种高效的光催化剂。在BiIO4的结构中,局部的极性碘离子(IO3)-存在于(Bi2O2)2+层之间,这将有利于电荷的转移。然而,BiIO4的带隙大只能被紫外光激发,这极大地限制了它的实际应用。BiIO4在独自参与可见光光催化降解苯酚废水反应时,在100分钟内的对废水中染料的降解率低于35%。
发明内容
为此,需要提供一种复合光催化剂及其制备方法,该催化剂对苯酚废水具有良好的催化活性。
为实现上述目的,发明人提供了一种异质结光催化剂,所述催化剂是以BiIO4为内层,Ag3PO4为外层的复合结构;所述BiIO4与Ag3PO4的摩尔比为2-10:100。
本发明将BiIO4与Ag3PO4进行复合,首次形成具有异质结结构的BiIO4/Ag3PO4光催化剂,通过将BiIO4与窄带隙的半导体Ag3PO4耦合形成异质结构来增强BiIO4可见光光催化活性;而与BiIO4的耦合会阻碍Ag3PO4中光生电子和空穴的复合,从而增强Ag3PO4的光催化活性。
进一步地,所述BiIO4的粒径为0.1-0.6μm,所述Ag3PO4的粒径为0.8-1.6μm。
发明人还提供了上述异质结光催化剂的制备方法,所述制备方法包括以下步骤:
BiIO4悬浮液配制:将粒径为0.1-0.6μm的BiIO4加入水中,超声分散均匀,形成BiIO4悬浮液;
BiIO4/Ag3PO4悬浮液配制:将BiIO4悬浮液中依次加入AgNO3溶液和Na2HPO4溶液,在20-30℃下混合均匀,得到BiIO4/Ag3PO4悬浮液;
分离、干燥:将BiIO4/Ag3PO4悬浮液进行固液分离,洗涤沉淀物,并对洗涤后沉淀物进行干燥,得到BiIO4/Ag3PO4成品;
所述BiIO4、AgNO3与Na2HPO4的摩尔比为2-10:300:100。
制备中,先加入AgNO3后再加入Na2HPO4形成的Ag3PO4沉淀形貌更好,质地更均匀。Ksp(Ag3PO4)=[Ag+]3[PO4],形成沉淀的过程银离子的贡献大于磷酸根离子。实验过程中先加入硝酸银使得溶液中含有大量银离子,加入磷酸氢钠可迅速形成均匀分散的沉淀。
进一步地,所述BiIO4/Ag3PO4悬浮液配制步骤中,,所述AgNO3溶液和Na2HPO4溶液的滴加速度为2ml/min,所述BiIO4悬浮液的配制量为50ml。
进一步地,所述制备方法中使用的配置用水为去离子水,所述AgNO3溶液和Na2HPO4溶液也采用离子水进行配置。采用去离子水可避免引入干扰杂质,影响催化剂的精密度。
进一步地,所述分离干燥步骤中,所述沉淀物依次用去离子水和乙醇进行洗涤。
进一步地,所述BiIO4为Bi(NO3)3·5H2O与I2O5通过水热法合成。
发明人进一步提供了异质结光催化剂用于光催化降解废水中苯酚的用途。
发明人提供了一种催化剂产品,所述产品中包括上述异质结光催化剂。
区别于现有技术,上述技术方案提供了一种新型的BiIO4/Ag3PO4异质结光催化剂,该催化剂的制备方法工艺简单、易于控制、成本低廉,可制备高纯度的BiIO4/Ag3PO4异质结光催化剂。本发明制备的BiIO4/Ag3PO4异质结光催化材料经过紫外可见漫反射的测试,其光响应向可见光区移动,其可见光催化活性比BiIO4和Ag3PO4均有显著提高;在光电流测试中与BiIO4和Ag3PO4相比起光电流更大,其特殊的异质结结构,加快了光生载流子的分离,减小了光生电子-空穴的复合几率,较好的提高了其可见光催化活性和稳定性,可进一步拓展其在挥发性有机废气光催化降解的应用。
附图说明
图1为实施例5制备的Ag3PO4扫描电镜图;
图2为实施例1制备的BiIO4的扫描电镜图;
图3为实施例2制备的BiIO4/Ag3PO4的扫描电镜图;
图4为实施例2制备的BiIO4/Ag3PO4的透射电镜图;
图5为实施例2制备的BiIO4/Ag3PO4的O-K、P-K、I-K、Bi-L、Ag-K和Ag-L的元素图谱;
图6为BiIO4、Ag3PO4和实施例2-4制备的BiIO4/Ag3PO4的X射线衍射图谱;
图7为BiIO4、Ag3PO4和实施例2-4中BiIO4/Ag3PO4的紫外漫反射光谱图;
图8为BiIO4,Ag3PO4和实施例2中BiIO4/Ag3PO4异质结光催化剂光电流响应图;
图9为BiIO4,Ag3PO4和实施例2-4的BiIO4/Ag3PO4异质结光催化剂样品降解效率图;
图10为BiIO4,Ag3PO4和和实施例2-4的BiIO4/Ag3PO4异质结光催化降解速率图。
具体实施方式
为详细说明技术方案的技术内容、构造特征、所实现目的及效果,以下结合具体实施例并配合附图详予说明。
实施例1:BiIO4的合成
将1.9402g Bi(NO3)3·5H2O加入到15mL去离子水中不断搅拌溶解,制备悬浊液;
将0.6676g I2O5添加到15ml去离子水中,并将烧杯被放置在超声波水浴中3分钟,制备澄清溶液。
将澄清溶液加入到上述悬浮液中,搅拌30分钟后在140℃的温度下反应24小时,反应完成后悬浊液自然冷却到室温之后进行固液分离,所得的沉淀物用去离子水和无水乙醇洗涤三次后在烘箱下干燥,得到0.1-0.6μm粒径的BiIO4粉末。
实施例2:5%BiIO4/Ag3PO4催化剂制备
BiIO4悬浮液配制:将粒径为0.1-0.6μm的0.1mmol BiIO4加入50mL去离子水中,超声波水浴10分钟分散均匀,形成BiIO4悬浮液;
BiIO4/Ag3PO4悬浮液配制:将BiIO4悬浮液中以2ml/min的速度滴加AgNO3溶液(6mmol AgNO3溶解于20mL去离子水配置),然后再以2ml/min的速度加入Na2HPO4溶液(2mmolNa2HPO4溶解于20mL去离子水配置),在25℃下搅拌6小时混合均匀,得到BiIO4/Ag3PO4悬浮液;
分离、干燥:将BiIO4/Ag3PO4悬浮液进行固液分离,用去离子水和乙醇洗涤沉淀物,并对洗涤后沉淀物在60℃的烘箱内进行12小时的干燥,得到BiIO4/Ag3PO4成品,
实施例2制备的BiIO4/Ag3PO4,BiIO4与Ag3PO4的摩尔比为5:100。
实施例3:2%BiIO4/Ag3PO4催化剂制备
BiIO4悬浮液配制:将粒径为0.1-0.6μm的0.1mmol BiIO4加入50mL去离子水中,超声波水浴10分钟分散均匀,形成BiIO4悬浮液;
BiIO4/Ag3PO4悬浮液配制:将BiIO4悬浮液中以2ml/min滴入AgNO3溶液(15mmolAgNO3溶解于20mL去离子水配置),然后再以2ml/min加入Na2HPO4溶液(5mmol Na2HPO4溶解于20mL去离子水配置),在20℃下搅拌6小时混合均匀,得到BiIO4/Ag3PO4悬浮液;
分离、干燥:将BiIO4/Ag3PO4悬浮液进行固液分离,用去离子水和乙醇洗涤沉淀物,并对洗涤后沉淀物进行干燥,得到BiIO4/Ag3PO4成品;
实施例3制备的BiIO4/Ag3PO4,BiIO4与Ag3PO4的摩尔比为2:100。
实施例4:10%BiIO4/Ag3PO4催化剂制备
BiIO4悬浮液配制:将粒径为0.1-0.6μm的0.2mmol BiIO4加入50mL去离子水中,超声波水浴10分钟分散均匀,形成BiIO4悬浮液;
BiIO4/Ag3PO4悬浮液配制:将BiIO4悬浮液中以2ml/min滴加AgNO3溶液(6mmolAgNO3溶解于20mL去离子水配置),然后再以2ml/min加入Na2HPO4溶液(2mmol Na2HPO4溶解于20mL去离子水配置),在30℃下搅拌6小时混合均匀,得到BiIO4/Ag3PO4悬浮液;
分离、干燥:将BiIO4/Ag3PO4悬浮液进行固液分离,用去离子水和乙醇洗涤沉淀物,并对洗涤后沉淀物进行干燥,得到BiIO4/Ag3PO4成品;
实施例4制备的BiIO4/Ag3PO4,BiIO4与Ag3PO4的摩尔比为10:100。
性能检测:
1、BiIO4/Ag3PO4扫描电镜和透射电镜检测:
将实施例1制备的BiIO4、Ag3PO4(AgNO3和Na2HPO4用化学沉淀法合成)和实施例2制备的5%BiIO4/Ag3PO4异质结的形貌大小和显微结构通过扫描电镜和透射电镜得以表征。
从图1可以看出,纯Ag3PO4是多面体纳米粒子,样品大小约为0.8-1.6微米。图2中可以看出BiIO4是具有均匀光滑表面的纳米薄片结构,长度和宽度约为0.1-0.6微米。图3和4分别展示了5%BiIO4/Ag3PO4异质结的扫描电镜和透射电镜图,可以发现Ag3PO4晶体粘附在了BiIO4纳米片上。
为进一步确定复合材料的元素组成,对5%BiIO4/Ag3PO4样品进行了化学元素分析。
图5分别展示了O-K、P-K、I-K、Bi-L、Ag-K和Ag-L的元素图谱,证明了Ag3PO4和BiIO4共存且Ag3PO4很好的分布在BiIO4的表面上。
以上检测结果表明实施例2成功地合成了BiIO4/Ag3PO4复合材料。
2、X射线衍射测试:
对BiIO4、Ag3PO4和不同比例的BiIO4/Ag3PO4进行X射线衍射,XRD图见图6。纯BiIO4的特征衍射峰正好对应着斜方晶型BiIO4(ICSD#262019)。对于纯Ag3PO4,当2θ为21.7°,29.7°,33.3°,36.5°,47.8°,52.6°,54.9°,57.2°,和71.8°的特征峰分别对应于(110)、(200)、(210)、(211)、(321)、(320)、(321)和(421)面,这与体心立方晶型Ag3PO4(JCPDSNo.06-0505)相吻合。与纯的BiIO4和Ag3PO4相比,可以看到,所有的BiIO4/Ag3PO4异质结有比较好的结晶度,而且特征衍射峰都与斜方晶型BiIO4和体心立方晶型Ag3PO4相对应。当复合材料中Ag3PO4的浓度降低时,BiIO4/Ag3PO4异质结的特征峰强度就会下降。同时,并没有发现其他杂质峰,表明了所制备的产品的具有高纯度。
3、紫外可见漫反射检测:
从图7中可以看出,宽带隙的纯BiIO4的吸收边在380纳米左右,而窄带隙的纯Ag3PO4的吸收边在530纳米左右。对于BiIO4/Ag3PO4异质结,他们在紫外-可见光区有相似的DRS光谱且有BiIO4和Ag3PO4的混合光学性质。随着在异质结中Ag3PO4的增加,吸收边逐渐地发生红移。
结果表明,在可见光照射下,BiIO4/Ag3PO4复合材料比单独的BiIO4和Ag3PO4具有更好的光催化性能。
4、光电流测试:
在可见光照射下,使用计时电流法对BiIO4,Ag3PO4和5%BiIO4/Ag3PO4行光电流测试,并且以10s的时间间隔对光电化学电池进行照射和避光处理,避光时电流低光照时电流高,而且所有的样品在每次的照射循环中都具有可重复的电流响应。一般来说,光电流越大,光电子-空穴对的分离效率就越好,光催化活性就越高。如图8所示,5%BiIO4/Ag3PO4异质结比纯BiIO4和Ag3PO4具有更高的光电流密度。光电流性能通常用于评估光生电子-空穴对的分离效率,因此光电流越高分离效率就越高,有利于光催化活性。
因此,进一步证明了,BiIO4/Ag3PO4复合材料比单独的BiIO4和Ag3PO4具有更好的光催化性能。
5、光催化活性系列测试:
根据在可见光照射下苯酚溶液的降解情况来研究样品的光催化活性。
测试方法:在本实验体系中,100mL苯酚水溶液(20mg/L)被用来模拟工业废水,300W的氙灯(1900mW/cm2)模拟可见光。首先,将0.1g光催化剂加入到100mL苯酚溶液中,在避光环境下连续搅拌30分钟,以达到一个吸附解离平衡。然后,将上述悬浮液置于300W的氙气灯下照射,每隔20分钟就从中吸取4mL的样品。离心之后用UV1902UV-vis分光光度计对其进行分析。苯酚的降解状态可以用C/C0来表示(即苯酚的浓度变化),其中C0是达到吸附平衡后光照前苯酚的初始浓度,C是代表在光照时某一时刻苯酚的浓度。
图9展示了BiIO4、Ag3PO4、2%BiIO4/Ag3PO4、5%BiIO4/Ag3PO4和10%BiIO4/Ag3PO4降解苯酚溶液时,苯酚溶液的浓度变化与降解时间的关系。很明显可以看出,5%BiIO4/Ag3PO4异质结表现出最佳的光催化活性。在可见光下照射100分钟后,苯酚溶液降解率达到98.1%,相应的BiIO4、Ag3PO4、2%BiIO4/Ag3PO4和10%BiIO4/Ag3PO4降解率分别为35.4%、79.5%、85.6%和86.8%。所有的BiIO4/Ag3PO4异质结都显示出比纯BiIO4和Ag3PO4拥有更好的光催化活性。结果表明,将BiIO4与Ag3PO4复合可以增强其光催化活性。为了研究催化剂对苯酚溶液的降解过程的化学动力学,根据Langmuir–Hinshelwood(L-H)动力学模型,提出了一种伪一阶模型:
ln(C0/C)=kt
其中当C0是苯酚溶液初始浓度时,C是在t时刻时苯酚溶液浓度,k是反应速率常数。
如图10所示,BiIO4、Ag3PO4、2%BiIO4/Ag3PO4、5%BiIO4/Ag3PO4和10%BiIO4/Ag3PO4的反应速率常数分别计算出为0.0042、0.0157、0.0194、0.0266和0.0202min-1。结果表明,5%BiIO4/Ag3PO4异质结在所有样品中具有最佳的光催化活性,
以上说明BiIO4/Ag3PO4异质结光催化剂的最佳BiIO4含量是5%且显著增强了光催化活性。
需要说明的是,在本文中,诸如第一和第二等之类的关系术语仅仅用来将一个实体或者操作与另一个实体或操作区分开来,而不一定要求或者暗示这些实体或操作之间存在任何这种实际的关系或者顺序。而且,术语“包括”、“包含”或者其任何其他变体意在涵盖非排他性的包含,从而使得包括一系列要素的过程、方法、物品或者终端设备不仅包括那些要素,而且还包括没有明确列出的其他要素,或者是还包括为这种过程、方法、物品或者终端设备所固有的要素。在没有更多限制的情况下,由语句“包括……”或“包含……”限定的要素,并不排除在包括所述要素的过程、方法、物品或者终端设备中还存在另外的要素。此外,在本文中,“大于”、“小于”、“超过”等理解为不包括本数;“以上”、“以下”、“以内”等理解为包括本数。
需要说明的是,尽管在本文中已经对上述各实施例进行了描述,但并非因此限制本发明的专利保护范围。因此,基于本发明的创新理念,对本文所述实施例进行的变更和修改,或利用本发明说明书及附图内容所作的等效结构或等效流程变换,直接或间接地将以上技术方案运用在其他相关的技术领域,均包括在本发明的专利保护范围之内。
Claims (10)
1.一种异质结光催化剂,其特征在于,所述催化剂是以BiIO4为内层,Ag3PO4为外层的复合结构;所述外层部分或全部覆盖所述内层,所述BiIO4与Ag3PO4的摩尔比为2-10:100。
2.根据权利要求1所述的异质结光催化剂,其特征在于,所述BiIO4的粒径为0.1-0.6μm,所述Ag3PO4的粒径为0.8-1.6μm。
3.权利要求1或2所述的异质结光催化剂的制备方法,其特征在于,所述制备方法包括以下步骤:
BiIO4悬浮液配制:将粒径为0.1-0.6μm的BiIO4加入水中,超声分散均匀,形成BiIO4悬浮液;
BiIO4/Ag3PO4悬浮液配制:将BiIO4悬浮液中依次加入AgNO3溶液和Na2HPO4溶液,在20-30℃下混合均匀,得到BiIO4/Ag3PO4悬浮液;
分离、干燥:将BiIO4/Ag3PO4悬浮液进行固液分离,洗涤沉淀物,并对洗涤后沉淀物进行干燥,得到BiIO4/Ag3PO4成品。
4.根据权利要求3所述的制备方法,其特征在于,所述BiIO4、AgNO3与Na2HPO4的摩尔比为2-10:300:100。
5.根据权利要求3所述的制备方法,其特征在于,所述BiIO4/Ag3PO4悬浮液配制步骤中,所述AgNO3溶液和Na2HPO4溶液的滴加速度为2ml/min;所述BiIO4悬浮液配制步骤中,BiIO4悬浮液的配制量为50ml。
6.根据权利要求3所述的制备方法,其特征在于,所述制备方法中使用的配置用水为去离子水,所述AgNO3溶液和Na2HPO4溶液也采用去离子水进行配置。
7.根据权利要求3所述的制备方法,其特征在于,所述分离干燥步骤中,所述沉淀物依次用去离子水和乙醇进行洗涤。
8.根据权利要求3所述的制备方法,其特征在于,所述BiIO4为Bi(NO3)3·5H2O与I2O5通过水热法合成。
9.权利要求1或2所述的异质结光催化剂用于光催化降解废水中苯酚。
10.一种催化剂产品,其特征在于,所述产品包括权利要求1或2所述的异质结光催化剂。
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