CN106807400A - 一种复合铁酸铋光催化剂及其制备方法和应用 - Google Patents
一种复合铁酸铋光催化剂及其制备方法和应用 Download PDFInfo
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Abstract
本发明涉及一种复合铁酸铋光催化剂及其制备方法和应用。Ag/FeTiO3/BiFeO3制备方法包括如下步骤:将FeTiO3置于去离子水中,搅拌得悬浮液,于悬浮液中加入AgNO3,避光搅拌20‑30min;然后,在紫外灯照射下搅拌10‑20min,再加入BiFeO3,超声分散,离心分离,所得沉淀用去离子水清洗,干燥;最后,于400‑450℃马弗炉中煅烧20‑40min,得到目标产物。本发明对BiFeO3材料进行复合,在可见光作用下,高效光催化降解抗生素。
Description
技术领域
本发明属于光催化剂领域,具体涉及采用溶胶凝胶法制备复合铁酸铋光催化剂及其在可见光下催化降解水中抗生素的应用。
背景技术
水资源是人类、资源与环境三大系统的结合点,是一切生命活动的物质基础,在社会经济发展中有着举足轻重的地位。随着人类的发展和社会的进步,人们越来越深切地认识到水资源保护对经济社会发展的重要性。由于我国制药行业的快速稳步发展,制药行业已成为工业废水的排放大户。国内300多家企业生产占世界产量20%-30%的70多个品种的抗生素,废水排放量大,且目前大多直接排放,严重危害水体环境。目前国内外应用的治理技术不多且不成熟,已建成的以好氧工艺为主的工程,投资和处理成本高,废水实际处理率很低。因此,探索制药废水快速有效降解的新方法是相当必要的。
铁酸铋(BiFeO3)是一种在室温下同时具有铁电性和反铁磁性的单相多铁材料,具有较小的禁带宽度和多铁特性,它不仅可以使光能转化为化学能,而且可以实现光催化氧化水体和空气中的有机污染物。
BiFeO3能够吸收可见光,产生电子(e-)和空穴(h+),h+使有机污染物氧化,e-能与O2反应产生·O2-,最终生成·OH自由基,使有机污染物氧化分解。然而,BiFeO3作为光催化剂有两大缺陷:一是,BiFeO3禁带宽度为2.1eV,只能利用太阳光中部分可见光,太阳光利用率低。二是,电子(e-)和空穴(h+)容易复合,降低了催化剂的光催化效率。
发明内容
本发明的目的是为了扩大BiFeO3的可见光响应范围,减小电子和空穴的复合,从而提高BiFeO3对太阳能的利用率,提高其可见光催化活性,本发明对BiFeO3材料进行复合,提供一种在可见光作用下,光催化效果好的复合铁酸铋光催化剂。
本发明的另一目的是利用复合铁酸铋光催化剂催化降解水中抗生素。
本发明采用的技术方案是:一种复合铁酸铋光催化剂,所述的复合铁酸铋光催化剂为Ag/FeTiO3/BiFeO3,制备方法包括如下步骤:将FeTiO3置于去离子水中,搅拌得悬浮液,于悬浮液中加入AgNO3,避光搅拌20-30min;然后,在紫外灯照射下搅拌10-20min,再加入BiFeO3,超声分散,离心分离,所得沉淀用去离子水清洗,干燥;最后,于400-450℃马弗炉中煅烧20-40min,得到目标产物。
上述的一种复合铁酸铋光催化剂,所述的FeTiO3制备方法,包括如下步骤:将硝酸铁溶液滴入钛酸四丁酯溶液中,磁力搅拌,加入氢氧化钠溶液直到产生暗褐色沉淀,用去离子水清洗,干燥,在400-450℃马弗炉中煅烧4-5h,得到FeTiO3纳米颗粒。
上述的一种复合铁酸铋光催化剂,所述的BiFeO3制备方法,包括如下步骤:将五水合硝酸铋和九水合硝酸铁,溶解在乙二醇中,室温下,将该混合物磁力搅拌形成溶胶,溶胶在90℃烘箱干燥后,在450-500℃马弗炉中煅烧30-40min,冷却后,分别用蒸馏水和无水乙醇清洗,烘干,得到BiFeO3纳米颗粒。
上述的一种复合铁酸铋光催化剂,按质量比,FeTiO3:BiFeO3=1:0.5~2。
上述的一种复合铁酸铋光催化剂,所述的复合铁酸铋光催化剂中,按重量百分比,含Ag 1.0%~3.0%。
上述的复合铁酸铋光催化剂在可见光下降解抗生素中的应用。方法如下:于含有抗生素的溶液中,加入权利要求1所述的复合铁酸铋光催化剂,于可见光下照射30-50min。优选的,所述的抗生素为诺氟沙星。
本发明的有益效果是:本发明,为了有效利用可见光,利用BiFeO3价带产生的电荷,钛酸亚铁(FeTiO3)导带产生的自由基,将两个窄带半导体BiFeO3和FeTiO3进行复合,进行催化降解以提高可见光利用率。另外,为减少电子(e-)和空穴(h+)的复合,对复合催化剂进行贵金属掺杂改性,拓宽其光响应范围,使其吸收边红移,从而有效提高其可见光催化活性。一方面,贵金属纳米颗粒分散在复合催化剂的表面可以有效捕获光生电子,促进电子和空穴的分离,抑制光生电子-空穴的复合。另一方面,沉积在催化剂表面的贵金属颗粒可以通过表面等离子体共振效应而拓宽复合催化剂的可见光吸收。相比于其他贵金属Pt、Au和Rh等,Ag具有价廉易得的优点。
附图说明
图1是不同条件下诺氟沙星溶液的UV-vis光谱。
具体实施方式
一种复合铁酸铋光催化剂,制备方法包括如下步骤:
1)通过溶胶-凝胶法合成FeTiO3纳米颗:将硝酸铁溶液滴入钛酸四丁酯的乙醇溶液中,磁力搅拌,加入氢氧化钠溶液直到产生暗褐色沉淀,用去离子水清洗,干燥,在400℃马弗炉中煅烧4h,得到FeTiO3纳米颗粒。
2)通过溶胶-凝胶法合成BiFeO3纳米颗粒:将五水合硝酸铋和九水合硝酸铁,溶解在乙二醇中,室温下,将该混合物磁力搅拌30min形成溶胶,溶胶在90℃烘箱干燥后,在450℃马弗炉中煅烧30min,冷却后,分别用蒸馏水和无水乙醇清洗,烘干,得到BiFeO3纳米颗粒。
3)将FeTiO3置于去离子水中,搅拌得悬浮液,于悬浮液中加入AgNO3,避光搅拌20min;然后,在紫外灯照射下搅拌10min,再加入BiFeO3,超声分散5min,离心分离,所得沉淀用去离子水清洗,干燥;最后,于400℃马弗炉中煅烧30min,得到目标产物。优选的,按质量比,FeTiO3:BiFeO3=1:0.5~2。按重量百分比,含Ag 1.0%~3.0%。
实施例1
1)通过溶胶-凝胶法合成BiFeO3纳米颗粒:准确称取7.7611g五水合硝酸铋和6.4640g九水合硝酸铁,溶解在36mL乙二醇中。室温下,将该混合物磁力搅拌30min形成溶胶。溶胶在90℃烘箱干燥,在450℃马弗炉中煅烧30min。冷却后,分别用蒸馏水和无水乙醇清洗多次,烘干,得到BiFeO3纳米颗粒。
2)通过溶胶-凝胶法合成FeTiO3纳米颗粒:将10mL 1mol/L的硝酸铁溶液滴入10mL1mol/L钛酸四丁酯的乙醇溶液中,磁力搅拌3h。加入1mol/L氢氧化钠溶液直到产生暗褐色沉淀,用去离子水清洗,干燥。在400℃马弗炉中煅烧4h,得到FeTiO3纳米颗粒。
3)取1.0g上述制备的FeTiO3粉末置于20mL去离子水中,搅拌得混悬液,向悬浮液中加入0.04g AgNO3,避光搅拌20min。然后,在紫外灯照射下搅拌10min,再分别加入0.5g、1.0g、2.0g的BiFeO3粉末,超声5min。离心分离,所得沉淀用去离子水清洗,干燥。最后,在400℃马弗炉中煅烧30min,分别得到不同FeTiO3和BiFeO3质量比(1:0.5,1:1,1:2)的Ag负载量为2%的复合铁酸铋光催化剂。
实施例2
1)通过溶胶-凝胶法合成BiFeO3纳米颗粒:同实施例1。
2)通过溶胶-凝胶法合成FeTiO3纳米颗粒:同实施例1。
3)取1.0g上述制备的FeTiO3粉末置于20mL去离子水中,搅拌得混悬液,向悬浮液中分别加入0.02g、0.04g、0.06g的AgNO3,避光搅拌20min。然后,在紫外灯照射下搅拌10min,再加入1.0g的BiFeO3粉末,超声5min。离心分离,所得沉淀物用去离子水清洗,干燥。最后,在400℃马弗炉中煅烧30min,分别得到FeTiO3和BiFeO3质量比为1:1,不同Ag负载量(1%、2%、3%)的复合铁酸铋光催化剂。
实施例3复合铁酸铋光催化剂在光催化下降解诺氟沙星
可见光光催化降解:量取25mL 5mg/L的诺氟沙星溶液于石英管中,加入复合铁酸铋光催化剂25mg,在可见光下照射30-180min,离心,在200-800nm测定上清液紫外光谱。取273nm处的吸光度计算诺氟沙星的降解率。
降解率(%)=(C0–C)/C0×100%(其中C0:原液的浓度;C:样品的浓度)。
1、FeTiO3与BiFeO3的不同质量比对抗生素-诺氟沙星光降解的影响
复合铁酸铋光催化剂采用实施例1制备的产物,结果如表1。
表1 FeTiO3与BiFeO3比例对抗生素-诺氟沙星光降解的影响(Ag=2.0wt.%)
如表1所示,随着光照时间的延长,诺氟沙星的降解率逐渐增加,并且随着FeTiO3的用量增加,诺氟沙星的降解率也逐渐增大。在FeTiO3:BiFeO3=1:0.5,光照时间为180min时,降解率达到最高为100%。
2、不同Ag负载量对抗生素-诺氟沙星光降解的影响
复合铁酸铋光催化剂采用实施例2制备的产物,结果如表2。
表2 Ag负载量对抗生素-诺氟沙星光降解的影响(FeTiO3:BiFeO3=1:1)
如表2所示,随着光照时间的延长,诺氟沙星的降解率逐渐增加。并且随着Ag含量的增加,诺氟沙星的降解率也逐渐增大。在Ag=3.0wt.%,光照时间为180min时,降解率达到最高为100%。
3、对比试验
可见光光催化降解:量取25mL 5mg/L的诺氟沙星溶液于石英管中,加入复合铁酸铋光催化剂25mg(FeTiO3和BiFeO3质量比1:1,Ag负载量为2%),在可见光下照射90min,离心,在200-800nm测定上清液紫外光谱。取273nm处的吸光度计算诺氟沙星的降解率。改变催化条件,结果见表3和图1。
发明1:FeTiO3/BiFeO3+Visible-light;
发明2:Ag/FeTiO3/BiFeO3+Visible-light;
对比例1:单独Visible-light;
对比例2:单独FeTiO3/BiFeO3;
对比例3:单独Ag/FeTiO3/BiFeO3;
表3不同情况下诺氟沙星降解率的比较
由表3和图1可见,当单光照射,不加催化剂时,吸收峰只有微弱降低。说明单光时只有极小的降解率。此外,单独使用FeTiO3/BiFeO3和Ag/FeTiO3/BiFeO3时,诺氟沙星的去除率分别为5.93%和7.26%。然而,可见光与FeTiO3/BiFeO3和Ag/FeTiO3/BiFeO3结合时,吸收峰下降明显。这意味着,在可见光照射下,FeTiO3/BiFeO3和Ag/FeTiO3/BiFeO3都能吸收可见光,而使有机污染物降解。因此,在可见光和催化剂共同作用下,诺氟沙星溶液能够被降解。Ag/FeTiO3/BiFeO3结合可见光的降解效果高于FeTiO3/BiFeO3。
实施例4使用次数对抗生素-诺氟沙星光降解的影响
可见光光催化降解:量取25mL 5mg/L的诺氟沙星溶液于石英管中,加入复合铁酸铋光催化剂25mg(FeTiO3和BiFeO3质量比1:1,Ag负载量为2%),在可见光下照射90min,离心,在200-800nm测定上清液紫外光谱。取273nm处的吸光度计算诺氟沙星的降解率。改变催化剂的使用次数。结果见表4。
表4使用次数对可见光降解诺氟沙星的影响(90min)
从表3中可以看出,诺氟沙星的降解率较稳定。这表示在三次连续的循环试验中,Ag/FeTiO3/BiFeO3光催化体系展现了很好的光降解活性。因此在去除水中污染物时,催化剂可重复使用3次,该催化体系仍然具有较好的稳定性。
以上实施例中,抗生素采用的是诺氟沙星,但是并不限制本发明降解的抗生素为诺氟沙星,本发明的方法适用于降解任何抗生素,如四环素,磺胺等。
Claims (8)
1.一种复合铁酸铋光催化剂,其特征在于,所述的复合铁酸铋光催化剂为Ag/FeTiO3/BiFeO3,制备方法包括如下步骤:将FeTiO3置于去离子水中,搅拌得悬浮液,于悬浮液中加入AgNO3,避光搅拌20-30min;然后,在紫外灯照射下搅拌10-20min,再加入BiFeO3,超声分散,离心分离,所得沉淀用去离子水清洗,干燥;最后,于400-450℃马弗炉中煅烧20-40min,得到目标产物。
2.根据权利要求1所述的一种复合铁酸铋光催化剂,其特征在于,所述的FeTiO3制备方法,包括如下步骤:将硝酸铁溶液滴入钛酸四丁酯溶液中,磁力搅拌,加入氢氧化钠溶液直到产生暗褐色沉淀,用去离子水清洗,干燥,在400-450℃马弗炉中煅烧4-5h,得到FeTiO3纳米颗粒。
3.根据权利要求1所述的一种复合铁酸铋光催化剂,其特征在于,所述的BiFeO3制备方法,包括如下步骤:将五水合硝酸铋和九水合硝酸铁,溶解在乙二醇中,室温下,将该混合物磁力搅拌形成溶胶,溶胶在90℃烘箱干燥后,在450-500℃马弗炉中煅烧30-40min,冷却后,分别用蒸馏水和无水乙醇清洗,烘干,得到BiFeO3纳米颗粒。
4.根据权利要求1、2或3所述的一种复合铁酸铋光催化剂,其特征在于,按质量比,FeTiO3:BiFeO3=1:0.5~2。
5.根据权利要求1、2或3所述的一种复合铁酸铋光催化剂,其特征在于,所述的复合铁酸铋光催化剂中,按重量百分比,含Ag 1.0%~3.0%。
6.权利要求1所述的复合铁酸铋光催化剂在可见光下降解抗生素中的应用。
7.根据权利要求6所述的应用,其特征在于,方法如下:于含有抗生素的溶液中,加入权利要求1所述的复合铁酸铋光催化剂,于可见光下照射30-50min。
8.根据权利要求6所述的应用,其特征在于,所述的抗生素为诺氟沙星、四环素或磺胺。
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