CN108246306B - 一锅法合成具有可见光响应的光催化剂CuBi2O4/Bi2WO6纳米球及其应用 - Google Patents
一锅法合成具有可见光响应的光催化剂CuBi2O4/Bi2WO6纳米球及其应用 Download PDFInfo
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Abstract
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。具体涉及一锅法合成具有可见光响应的光催化剂CuBi2O4/Bi2WO6纳米球及其应用。本发明通过一锅法合成具有可见光响应的光催化剂CuBi2O4/Bi2WO6纳米球,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CuBi2O4/Bi2WO6纳米球的比表面积大,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CuBi2O4/Bi2WO6纳米球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,降低人们的能源利用。
半导体光催化氧化技术始于日本科学家Fujishima和Honda发现受光辐照的TiO2单晶电极可以将H2O分解,利用TiO2半导体光催化剂将光能转化为电能和化学能就成为半导体光催化领域的研究热点。然而,锐钛矿型TiO2的禁带宽度为3.2eV,其激发波长为387.5nm,属于太阳光中的紫外光范围。而对于太阳能,其主要能量集中于400~600nm的可见光范围,这大大减少了TiO2半导体光催化剂的效率,因此,开发出对可见光响应的新型的半导体材料是半导体光催化剂研究的重点内容之一。
在众多的新开发的半导体光催化剂中,研究者开发了钨酸盐化合物,发现该类催化剂具有较小的禁带宽度,能充分的利用太阳光,是一类有前景的光催化剂。但是随着研究的深入,大多数的钨酸盐化合物出现稳定性差,易光腐蚀,限制了其发展。
发明内容
本发明的目的在于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、不易腐蚀的可见光响应的光催化剂 CuBi2O4/Bi2WO6纳米球及制备方法和应用。本发明主要是通过改进催化剂成分及制备方法来实现上述目的。
CuBi2O4/Bi2WO6纳米球的制备方法为:
S1.将Bi(NO3)3·5H2O溶解于HNO3溶液中,与Cu(NO3)2·3H2O水溶液混合,并于反应釜中100-150℃反应10-15h,经洗涤、干燥得到CuBi2O4, Bi(NO3)3·5H2O与Cu(NO3)2·3H2O的摩尔比为2:1;
S2.将Bi(NO3)3·5H2O溶解于CH3COOH的水溶液中,与Na2WO4·2H2O 水溶液混合,Bi(NO3)3·5H2O与Na2WO4·2H2O的摩尔比为2:1,混合液pH 值为7,将S1获得的CuBi2O4与该混合液高压蒸汽加热,在150~250℃反应12-36h,冷却至室温;
S3.将S2所得产物离心、分离、清洗,放入烘干箱中烘干,然后研磨成粉,于马弗炉中350-450℃煅烧1-3h,得到CuBi2O4/Bi2WO6纳米球,其中CuBi2O4占Bi2WO61-5wt%。
所述步骤S1具体为:称取1.9402g Bi(NO3)3·5H2O溶解到20mL 1mol/L HNO3溶液中,待Bi(NO3)3溶解后为溶液A,称取0.4832g Cu(NO3)2·3H2O溶于20mL去离子水中为溶液B,搅拌下,将溶液B逐滴加入到溶液A中,进行磁力搅拌使其充分混合,在搅拌下,将60mL2.4mol/L的NaOH溶液逐滴滴入到混合溶液中,充分混合后将溶液放入聚四氟乙烯反应釜中,在120℃下反应12h后,用无水乙醇洗涤,然后在烘箱干燥,得到CuBi2O4。
所述步骤S2具体为:称取3.92g Bi(NO3)3·5H2O溶解于30mL 5mol/L 的CH3COOH的水溶液中,将1.33g Na2WO4·2H2O溶解在48mL去离子水中,室温时,将Na2WO4溶液逐滴加入到Bi(NO3)3溶液中,保持磁力搅拌 60min,继续搅拌,用氨水调节体系pH值为7,将1-5wt%的CuBi2O4加入上述混合溶液中,搅拌30min后,然后将混合溶液移入聚四氟反应釜中,高压蒸汽加热,保持在150~250℃反应12-36h,之后慢慢冷却到室温。
所述步骤S3具体为:将步骤S2产物在5000r/min的速度下离心30min 后从反应介质中分离出来,并用去离子水和乙醇清洗若干次,放入烘干箱中60℃烘干,待产物烘干之后,将其研磨成粉,并将粉末于马弗炉中以 10℃/min升温至在400℃煅烧2h,得到CuBi2O4/Bi2WO6纳米球。
本发明另一个目的请求保护采用上述方法制备的CuBi2O4/Bi2WO6纳米球。
本发明同时请求保护上述CuBi2O4/Bi2WO6纳米球在催化降解有机污染物中的应用。
CuBi2O4/Bi2WO6纳米球催化降解气相污染物的具体方法为:
将CuBi2O4/Bi2WO6纳米球放入反应器内,将惰性气体以流速20~100 mL/min通入反应器吹扫至系统稳定,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CuBi2O4/Bi2WO6纳米球固态表面吸附0.5~3h,然后开启氙灯进行光催化反应,4~6h后关闭氙灯。
CuBi2O4/Bi2WO6纳米球催化降解液相污染物的具体方法为:
将CuBi2O4/Bi2WO6纳米球与液相污染物按质量比10-50:1溶于置有污染物溶液中,超声分散30min,然后在黑暗中磁力搅拌30min,搅拌完毕先取2mL溶液在3000r/min下离心5min后测吸光度,然后以氙灯为光源进行照射,每20min取样一次进行离心,然后测吸光度,通过吸光度计算污染物的含量。
所述污染物包括丙酮、甲苯、乙苯、苯酚或甲醛。
本发明中通过一锅法合成具有可见光响应的光催化剂 CuBi2O4/Bi2WO6纳米球,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。
本发明与现有技术相比具有如下优点:
①CuBi2O4/Bi2WO6纳米球的比表面积大,吸附能力强;
②CuBi2O4/Bi2WO6纳米球与传统光催化剂二氧化钛相比,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;
③CuBi2O4/Bi2WO6纳米球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CuBi2O4/Bi2WO6纳米球放大到5μm的扫描电镜图。
图2为实施例1和实施例2中的CuBi2O4/Bi2WO6纳米球紫外-可见漫反射图。
图3为实施例1中的CuBi2O4/Bi2WO6纳米球与现有技术中的TiO2光催化降解丙酮降解图。
图4为实施例1中的CuBi2O4/Bi2WO6纳米球与TiO2光催化降解苯酚效果对比图。
具体实施方式
下面通过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、试剂等均可从商业渠道获得。
实施例1
称取1.9402g Bi(NO3)3·5H2O溶解到20m L 1mol/L HNO3溶液中,待 Bi(NO3)3溶解后为溶液A,称取0.4832g Cu(NO3)2·3H2O溶于20mL去离子水中为溶液B,搅拌下,将溶液B逐滴加入到溶液A中,进行磁力搅拌使其充分混合为溶液,在搅拌下,将60mL 2.4mol/L的NaOH溶液逐滴滴入到上述溶液中,充分混合后将溶液放入聚四氟乙烯反应釜中,在120℃下反应12h后,使用无水乙醇将产物进行若干次洗涤以后,在烘箱干燥,得到CuBi2O4;然后,制备CuBi2O4/Bi2WO6纳米球,其合成步骤如下:称取3.92g Bi(NO3)3·5H2O溶解于30mL 5mol/L的CH3COOH的水溶液中, 1.33gNa2WO4·2H2O溶解在48mL去离子水中,室温时,将Na2WO4溶液逐滴加入到Bi(NO3)3溶液中,保持磁力搅拌60min,继续搅拌,用氨水调节体系pH值为7,搅拌30min后,将0.085g的CuBi2O4加入上述溶液中,搅拌30min后,将溶液移入内衬聚四氟乙烯的反应釜中,在200℃反应22 h,之后慢慢冷却到室温。将产物在5000r/min的速度下离心30min后从反应介质中分离出来,并用去离子水和乙醇清洗若干次,放入烘干箱中 60℃烘干。待产物烘干之后,将其研磨成粉,并将粉末移入坩埚中,放进马弗炉中以10℃/min升温至在400℃煅烧2h,得到3%CuBi2O4/Bi2WO6纳米球,从图1上可以清楚显示CuBi2O4负载于Bi2WO6纳米球,从图2 上可以看出,在380-500nm可见光范围内3%CuBi2O4/Bi2WO6纳米球有较强的吸光率,而且产生红移。
实施例2
本实施例与实施例1的区别在于未加入CuBi2O4,制得纯Bi2WO6纳米球光催化剂。
实施例3
本实施例与实施例1的区别在于CuBi2O4添加量增加到0.1412g,在 150℃下反应36h,制得5%的CuBi2O4/Bi2WO6纳米球光催化剂。
实施例4
本实施例与实施例1的区别在于CuBi2O4量减少到0.0282g,在250℃下反应12h,制得1%的CuBi2O4/Bi2WO6纳米球光催化剂。
应用例1
购买商业光催化TiO2(P25,购买于赢创工业集团),未经过任何处理,直接用于光催化反应。
将实施例1中的0.2g CuBi2O4/Bi2WO6纳米球在玛瑙研钵中研磨至 20~60目,研磨后将CuBi2O4/Bi2WO6纳米球平铺在反应器内。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30 min,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CuBi2O4/Bi2WO6纳米球固态表面吸附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1μL,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,CuBi2O4/Bi2WO6纳米球作为催化剂时,经过4h降解,丙酮的去除率为97%,因此,在可见光条件下, CuBi2O4/Bi2WO6纳米球对气相污染物具有较强的催化氧化活性。
应用例2
购买商业光催化TiO2(P25,购买于赢创工业集团),未经过任何处理,直接用于光催化反应。
将实施例1中的0.04g CuBi2O4/Bi2WO6纳米球溶于置有80mL苯酚 (10mg/L)烧杯中,超声分散30min,然后在黑暗中磁力搅拌30min。搅拌完毕先取2mL溶液在3000r/min下离心5min后测吸光度。然后以氙灯为光源进行照射,每20min取样一次进行离心,然后测吸光度,通过吸光度计算苯酚的去除率。
实验结果见图4所示,在可见光条件下,CuBi2O4/Bi2WO6纳米球作为催化剂时,经过1h降解,苯酚去除率为98%,因此,CuBi2O4/Bi2WO6纳米球为光催化剂,在可见光条件下,对液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 (9)
1.具有可见光响应的光催化剂CuBi2O4/Bi2WO6纳米球的制备方法,其特征在于,包括以下步骤:
S1.将Bi(NO3)3·5H2O溶解于HNO3溶液中,与Cu(NO3)2·3H2O水溶液混合,并于反应釜中100-150℃反应10-15h,经洗涤、干燥得到CuBi2O4,Bi(NO3)3·5H2O与Cu(NO3)2·3H2O的摩尔比为2:1;
S2.将Bi(NO3)3·5H2O溶解于CH3COOH的水溶液中,与Na2WO4·2H2O水溶液混合,Bi(NO3)3·5H2O与Na2WO4·2H2O的摩尔比为2:1,混合液pH值为7,将S1获得的CuBi2O4与该混合液高压蒸汽加热,在150~250℃反应12-36h,冷却至室温;
S3.将S2所得产物离心、分离、清洗,放入烘干箱中烘干,然后研磨成粉,于马弗炉中350-450℃煅烧1-3h,得到CuBi2O4/Bi2WO6纳米球,其中CuBi2O4占Bi2WO61-5wt%。
2.根据权利要求1所述的方法,其特征在于,所述步骤S1具体为:称取1.9402g Bi(NO3)3·5H2O溶解到20mL 1mol/L HNO3溶液中,待Bi(NO3)3溶解后为溶液A,称取0.4832g Cu(NO3)2·3H2O溶于20mL去离子水中为溶液B,搅拌下,将溶液B逐滴加入到溶液A中,进行磁力搅拌使其充分混合,在搅拌下,将60mL 2.4mol/L的NaOH溶液逐滴滴入到混合溶液中,充分混合后将溶液放入聚四氟乙烯反应釜中,在120℃下反应12h后,用无水乙醇洗涤,然后在烘箱干燥,得到CuBi2O4。
3.根据权利要求1所述的方法,其特征在于,所述步骤S2具体为:称取3.92g Bi(NO3)3·5H2O溶解于30mL 5mol/L的CH3COOH的水溶液中,将1.33gNa2WO4·2H2O溶解在48mL去离子水中,室温时,将Na2WO4溶液逐滴加入到Bi(NO3)3溶液中,保持磁力搅拌60min,继续搅拌,用氨水调节体系pH值为7,将1-5wt%的CuBi2O4加入上述混合溶液中,搅拌30min后,然后将混合溶液移入聚四氟反应釜中,高压蒸汽加热,保持在150~250℃反应12-36h,之后慢慢冷却到室温。
4.根据权利要求1所述的方法,其特征在于,所述步骤S3具体为:将步骤S2产物在5000r/min的速度下离心30min后从反应介质中分离出来,并用去离子水和乙醇清洗若干次,放入烘干箱中60℃烘干,待产物烘干之后,将其研磨成粉,并将粉末于马弗炉中以10℃/min升温至在400℃煅烧2h,得到CuBi2O4/Bi2WO6纳米球。
5.一种如权利要求1-4任一项所述方法制备的CuBi2O4/Bi2WO6纳米球。
6.一种如权利要求1-4任一项所述方法制备的CuBi2O4/Bi2WO6纳米球在催化降解有机污染物中的应用。
7.根据权利要求6所述的应用,其特征在于,CuBi2O4/Bi2WO6纳米球催化降解气相污染物的具体方法为:
将CuBi2O4/Bi2WO6纳米球放入反应器内,将惰性气体以流速20~100mL/min通入反应器吹扫至系统稳定,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CuBi2O4/Bi2WO6纳米球固态表面吸附0.5~3h,然后开启氙灯进行光催化反应,4~6h后关闭氙灯。
8.根据权利要求6所述的应用,其特征在于,CuBi2O4/Bi2WO6纳米球催化降解液相污染物的具体方法为:
将CuBi2O4/Bi2WO6纳米球与液相污染物按质量比10-50:1溶于置有污染物溶液中,超声分散30min,然后在黑暗中磁力搅拌30min,搅拌完毕先取2mL溶液在3000r/min下离心5min后测吸光度,然后以氙灯为光源进行照射,每20min取样一次进行离心,然后测吸光度,通过吸光度计算污染物的含量。
9.根据权利要求6所述的应用,其特征在于,所述污染物包括丙酮、甲苯、乙苯、苯酚或甲醛。
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