CN107803196B - 一种合成具有可见光响应的光催化剂Zn2SnO4/Bi2WO6纳米片的制备方法 - Google Patents
一种合成具有可见光响应的光催化剂Zn2SnO4/Bi2WO6纳米片的制备方法 Download PDFInfo
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Abstract
一种合成具有可见光响应的光催化剂Zn2SnO4/Bi2WO6纳米片的制备方法,该方法先制备Zn2SnO4粉末,将Zn2SnO4粉末溶于Bi(NO3)3·5H2O与Na2WO4·2H2O混合溶液中,持续搅拌、超声处理后,进行离心、干燥,得到Zn2SnO4/Bi2WO6纳米片。本发明制备的Zn2SnO4/Bi2WO6纳米片比表面积大,吸附能力强;具有更好的可见光吸收性能,对光催化氧化降解有机污染物有很大的提高;而且本发明Zn2SnO4/Bi2WO6纳米片的制备方法比较简单,易于操作。
Description
技术领域
本发明涉及一种用于治理环境污染的半导体光催化剂及制备方法。
背景技术
能源危机和环境问题已是人类必须要面临的两个严峻问题,如何有效的控制和治理各种化学污染物对环境的污染是环境综合治理中的重点。近些年,作为高级氧化技术之一的半导体光催化氧化技术,正受到国内外学者的广泛研究,这种技术可以以太阳能作为能源来降解环境中的污染物,有效地利用太阳能,降低人们的能源消耗。
Bi2WO6作为一种新型可见光光催化剂,禁带宽度为2.7eV,因具有较好的可见光催化性能成为近几年研究的热点。然而,单一相的Bi2WO6除了具有低的量子效率外,还因对可见光利用率不高(约λ<450nm),限制了它在光催化方面的应用。为了加强Bi2WO6的光催化性能,非金属或金属离子掺杂成为提高其光催化性能的常用方法。然而,掺杂通常会在半导体内引起晶格缺陷而成为捕获光生电子的陷阱,导致部分光生电子不能到达催化剂表面,最终使催化效率提高的程度非常有限。
发明内容
为弥补现有技术的不足,本发明提供一种不仅具有可见光响应的、对有机污染物具有降解能力而且稳定性好、不易腐蚀的光催化剂Zn2SnO4/Bi2WO6纳米片及制备方法。
本发明是这样实现的,合成具有可见光响应的光催化剂Zn2SnO4/Bi2WO6纳米片的制备方法,包括如下步骤:
S1.将摩尔比为2:1的ZnCl2和SnCl4·5H2O溶解于乙醇水溶液中,边搅拌边逐滴加入NaOH溶液,持续搅拌,将得到的悬浊液移入到反应釜中,置于 150-250℃下加热12-36h,得到沉淀物Ⅰ,将沉淀物Ⅰ清洗、置于60℃下进行干燥,得到Zn2SnO4粉末;
S2.将Bi(NO3)3·5H2O溶解于CH3COOH水溶液中,得到溶液a;将 Na2WO4·2H2O溶解于去离子水中,得到溶液b,Bi(NO3)3·5H2O与Na2WO4·2H2O 摩尔比为2:1;在室温条件下,将溶液b逐滴加入溶液a中,搅拌、用氨水将混合溶液pH值调至7;将S1得到Zn2SnO4粉末加入到混合溶液中,Zn2SnO4占 Bi(NO3)3·5H2O的1~5mol%,持续搅拌后进行超声处理,然后移至反应釜内,在150-250℃下反应11-33h,冷却至室温,获得沉淀物Ⅱ,将沉淀物Ⅱ清洗、并在60℃下干燥,得到Zn2SnO4/Bi2WO6纳米片。
优选的,反应釜内衬为聚四氟乙烯。
本发明通过合成具有可见光响应的光催化剂Zn2SnO4/Bi2WO6纳米片,同时通过控制反应时间以及反应温度,形成大比表面积的球状形貌,使得制备的材料具有较大的比表面积,有利于污染物的吸附降解。
本发明另一个目的是请求保护采用本发明方法制备的Zn2SnO4/Bi2WO6纳米片催化降解液相污染物的方法,具体步骤如下:将Zn2SnO4/Bi2WO6纳米片放入反应器内,将惰性气体以流速20~100mL/min通入反应器吹扫至稳定,将气相污染物以流速1~10μL/h通入反应器10~60min后将进、出气口关闭,保持反应器密封,将反应器置于暗态使气相污染物在Zn2SnO4/Bi2WO6纳米片固态表面吸附0.5~3h,然后开启氙灯进行光催化反应,4~6h后关闭氙灯。所述气相污染物包括苯、甲苯、乙苯或丙酮。
本发明的通过合理的Zn2SnO4和Bi2WO6配比,调控工艺参数,将纳米片经溶剂热反应获得的微观结构为片状纳米级复合物Zn2SnO4/Bi2WO6。与现有技术相比,本发明具有以下优点:
1、本发明制备的Zn2SnO4/Bi2WO6纳米片的比表面积大,吸附能力强;
2、本发明制备的Zn2SnO4/Bi2WO6纳米片与单一相光催化剂钨酸盐相比,具有更好的可见光吸收性能,对光催化氧化降解有机污染物有很大的提高;
3、本发明提供的Zn2SnO4/Bi2WO6纳米片的制备方法比较简单,易于操作,适于工业生产。
附图说明
图1为实施例1中的Zn2SnO4/Bi2WO6纳米片放大倍数100000倍的扫描电镜图。
图2为实施例1和实施例2中的Zn2SnO4/Bi2WO6纳米片紫外-可见漫反射图。
图3为实施例1中的Zn2SnO4/Bi2WO6纳米片不同配比与Zn2SnO4、Bi2WO6光催化降解丙酮降解对比图。
具体实施方式
下面通过附图和具体实施例详述本发明,但不限制本发明的保护范围。如无特殊说明,本发明所采用的实验方法均为常规方法,所用实验器材、材料、试剂等均可从化学公司购买。应用例中涉及到光催化TiO2,型号P25,购买于赢创工业集团。
实施例1
(1)将2.5mmol ZnCl2和1.25mmol SnCl4·5H2O溶解于20mL去离子水和 20mL乙醇的混合液中,在搅拌条件下向其中逐滴加入10mL 1.0M NaOH溶液,持续搅拌约15min,将得到的悬浊液移入到100mL反应釜中,置于200℃下加热24h,得到沉淀物Ⅰ,将沉淀物Ⅰ分别用水和乙醇清洗三次后,置于60℃下进行干燥,得到Zn2SnO4粉末。
(2)制备Zn2SnO4/Bi2WO6纳米片,其合成步骤如下:将3.92g Bi(NO3)3·5H2O溶解于30mL 5.0M CH3COOH水溶液中,得到溶液a;1.33g Na2WO4·2H2O溶解于48mL去离子水中,得到溶液b;在室温条件下,溶液b 逐滴加入溶液a中,搅拌60min后,用氨水将pH值调至7,将0.0846g Zn2SnO4粉末加入到上述溶液,持续搅拌30min后,超声30min,然后将混合溶液移至120mL反应釜内,在200℃下反应22h,冷却至室温,获得沉淀物Ⅱ,将沉淀物Ⅱ用去离子水和无水乙醇反复清洗,并在60℃下干燥,得到 3%Zn2SnO4/Bi2WO6纳米片,Zn2SnO4占Bi2WO6质量的3wt%。从图1上可以清楚显示Zn2SnO4负载于Bi2WO6纳米片。
实施例2
将3.92g Bi(NO3)3·5H2O溶解于30mL 5.0M CH3COOH水溶液中,得到溶液a;1.33gNa2WO4·2H2O溶解于48mL去离子水中,得到溶液b;在室温条件下,溶液b逐滴加入溶液a中,搅拌60min后,用氨水将pH值调至7,然后将混合溶液移至120mL反应釜内,在200℃下反应22h,冷却至室温,获得沉淀物,将沉淀物用去离子水和无水乙醇反复清洗,并在60℃下干燥制得纯Bi2WO6纳米片光催化剂。
从图2上可以看出,在320-500nm可见光范围内Zn2SnO4/Bi2WO6纳米片和纯Bi2WO6纳米片均对可见光有响应,Zn2SnO4在紫外光范围内有响应,而且 Zn2SnO4/Bi2WO6纳米片相对于纯Zn2SnO4和纯Bi2WO6纳米片产生了一定的红移,说明可以利用更多的可见光。
实施例3
(1)将2.5mmol ZnCl2和1.25mmol SnCl4·5H2O溶解于20mL去离子水和 20mL乙醇的混合液中,在搅拌条件下向其中逐滴加入10mL 1.0M NaOH溶液,持续搅拌约15min,将得到的悬浊液移入到100mL反应釜中,置于150℃下加热36h,得到沉淀物Ⅰ,将沉淀物Ⅰ分别用水和乙醇清洗三次后,置于60℃下进行干燥,得到Zn2SnO4粉末。
(2)制备Zn2SnO4/Bi2WO6纳米片,其合成步骤如下:将3.92g Bi(NO3)3·5H2O溶解于30mL 5.0M CH3COOH水溶液中,得到溶液a;1.33g Na2WO4·2H2O溶解于48mL去离子水中,得到溶液b;在室温条件下,溶液b 逐滴加入溶液a中,搅拌60min后,用氨水将pH值调至7,将0.141g Zn2SnO4粉末加入到上述溶液,持续搅拌30min后,超声30min,然后将混合溶液移至120mL反应釜内,在150℃下反应33h,冷却至室温,获得沉淀物Ⅱ,将沉淀物Ⅱ用去离子水和无水乙醇反复清洗,并在60℃下干燥,得到5% Zn2SnO4/Bi2WO6纳米片。Zn2SnO4占Bi2WO6质量的5wt%。
实施例4
(1)将2.5mmol ZnCl2和1.25mmol SnCl4·5H2O溶解于20mL去离子水和 20mL乙醇的混合液中,在搅拌条件下向其中逐滴加入10mL 1.0M NaOH溶液,持续搅拌约15min,将得到的悬浊液移入到100mL反应釜中,置于250℃下加热12h,得到沉淀物Ⅰ,将沉淀物Ⅰ分别用水和乙醇清洗三次后,置于60℃下进行干燥,得到Zn2SnO4粉末。
(2)制备Zn2SnO4/Bi2WO6纳米片,其合成步骤如下:将3.92g Bi(NO3)3·5H2O溶解于30mL 5.0M CH3COOH水溶液中,得到溶液a;1.33g Na2WO4·2H2O溶解于48mL去离子水中,得到溶液b;在室温条件下,溶液b 逐滴加入溶液a中,搅拌60min后,用氨水将pH值调至7,将0.0.0282g Zn2SnO4粉末加入到上述溶液,持续搅拌30min后,超声30min,然后将混合溶液移至120mL反应釜内,在250℃下反应11h,冷却至室温,获得沉淀物Ⅱ,将沉淀物Ⅱ用去离子水和无水乙醇反复清洗,并在60℃下干燥,得到1% Zn2SnO4/Bi2WO6纳米片。Zn2SnO4占Bi2WO6质量的1wt%。
应用例1
按实施例1中的方法制备Zn2SnO4/Bi2WO6纳米片,将0.2g 3%Zn2SnO4/Bi2WO6纳米片在玛瑙研钵中研磨至20~60目,研磨后将 Zn2SnO4/Bi2WO6纳米片平铺在反应器内。用流速为70mL/min的氮气吹扫反应器,除去反应器中的杂质,至反应器处于稳定,将空气作为载气的丙酮通入到反应器中,流速为2μL/h,通入时间为30min,30min后将进、出气口关闭,保持反应器密封,将反应器置于暗态使气相的丙酮在Zn2SnO4/Bi2WO6纳米片固态表面吸附1h,开启氙灯进行光催化反应,反应过程中每隔30min在出气口取样1 μL,4h后关闭氙灯,丙酮浓度用Agilent 7890A气相色谱测定。
实验结果见图3所示,在可见光条件下,3%Zn2SnO4/Bi2WO6纳米片作为催化剂时,经过3h降解,丙酮的最高去除率为95.5%,因此,在可见光条件下, Zn2SnO4/Bi2WO6纳米片对气相污染物具有较强的催化氧化活性。
以上所述,仅为本发明创造较佳的具体实施方式,但本发明创造的保护范围并不局限于此,任何熟悉本技术领域的技术人员在本发明创造披露的技术范围内,根据本发明创造的技术方案及其发明构思加以等同替换或改变,都应涵盖在本发明创造的保护范围之内。
Claims (3)
1.一种具有可见光响应的光催化剂Zn2SnO4/Bi2WO6纳米片催化降解气相污染物的方法,其特征在于,
所述Zn2SnO4/Bi2WO6纳米片的制备方法包括如下步骤:
S1 .将摩尔比为2:1的ZnCl2和SnCl4·5H2O溶解于乙醇水溶液中,边搅拌边逐滴加入NaOH溶液,持续搅拌,将得到的悬浊液移入到反应釜中,置于150-250℃下加热12-36h,得到沉淀物Ⅰ,将沉淀物Ⅰ清洗、置于60℃下进行干燥,得到Zn2SnO4粉末;
S2 .将Bi(NO3)3·5H2O溶解于CH3COOH水溶液中,得到溶液a;将Na2WO4·2H2O溶解于去离子水中,得到溶液b,Bi(NO3)3·5H2O与Na2WO4·2H2O摩尔比为2:1;在室温条件下,将溶液b逐滴加入溶液a中,搅拌、用氨水将混合溶液pH值调至7;将S1得到Zn2SnO4粉末加入到混合溶液中,Zn2SnO4占Bi(NO3)3·5H2O的1~5mol%,持续搅拌后进行超声处理,然后移至反应釜内,在150-250℃下反应11-33h,冷却至室温,获得沉淀物Ⅱ,将沉淀物Ⅱ清洗、并在60℃下干燥,得到Zn2SnO4/Bi2WO6纳米片;
所述气相污染物为苯、甲苯、乙苯或丙酮。
2.根据权利要求1所述的方法,其特征在于,反应釜内衬为聚四氟乙烯。
3.根据权利要求1所述的方法,其特征在于,具体步骤如下:将Zn2SnO4/Bi2WO6纳米片放入反应器内,将惰性气体以流速20~100mL/min通入反应器吹扫至稳定,将气相污染物以流速1~10μL/h通入反应器10~60min后将进、出气口关闭,保持反应器密封,将反应器置于暗态使气相污染物在Zn2SnO4/Bi2WO6纳米片固态表面吸附0.5~3h,然后开启氙灯进行光催化反应,4~6h后关闭氙灯。
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