CN112121786A - 一种氧化石墨烯掺杂改性四氧化二铋的压电催化和光催化联用催化剂及其制备方法和应用 - Google Patents
一种氧化石墨烯掺杂改性四氧化二铋的压电催化和光催化联用催化剂及其制备方法和应用 Download PDFInfo
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Abstract
本发明公开了一种氧化石墨烯掺杂改性四氧化二铋的压电催化和光催化联用催化剂,通过以下步骤制备而成:(1)在去离子水中加入二水合铋酸钠和氧化石墨粉末,并在293~303K的水浴温度下搅拌1~2h,得到分散均匀的悬浊液;(2)将得到的悬浊液加热至433±10K,进行水热合成反应5~24h;(3)步骤(2)得到的反应产物经过去离子水和无水乙醇多次离心洗涤至中性,然后在333~353K下烘干12~16h,完成。本发明在污水中磺胺甲基嘧啶的降解处理中,具有更高的催化效率。
Description
技术领域
本发明本发明属于水污染技术领域,具体涉及一种氧化石墨烯掺杂改性四氧化二铋(GO-Bi2O4)压电催化和光催化联用催化剂及其制备方法和应用。
背景技术
滥用抗生素给环境造成污染并给人类带来健康危害,耐药性抗生素的蔓延更是严峻的环境问题。磺胺甲基嘧啶(SM)是典型的磺胺类抗生素,广泛存在于污染水体中。传统的SM降解方法如吸附法、膜分离法等,这些方法对污染物降解不彻底,容易造成二次污染,成本高。为此,我们需要寻找水污染处理的高效途径。
在各种水污染处理方法中,利用光催化半导体材料和可再生太阳能降解污染物已被认为是一种很有前途的绿色环境修复技术。但很多光催化剂对太阳光的利用率比较低。尽管提出了许多方法来提高光催化降解活性,如对催化剂的能带隙进一步调优、形成复合半导体、离子掺杂、纳米形态操纵和在晶格中引入缺陷等等。如何在光催化系统中实现高效的电荷分离仍是一个具有挑战性的问题。当采用压电材料与其他光催化剂耦合时,压电材料附近的内建电场有助于电荷分离。压电催化和光催化联用的催化材料的电荷分离是通过偶极子极化产生的永久内建电场来实现的。通过光辐射和超声压电场联合作用抑制了光激发电荷载流子体复合,明显提升了催化效率。
铋基半导体材料具有良好的压电光催化性能,改性Bi2O4材料因其非中心对称结构使得催化性能得到大幅提升,氧化石墨烯(GO)是目前最有前景的光热剂之一,以此为基础,使用GO掺杂改性Bi2O4得到GO-Bi2O4压电催化和光催化耦合联用催化剂,该催化剂催化效率较未掺杂的Bi2O4催化剂有显著提高,应用于环境典型抗生素磺胺甲基嘧啶的降解效果理想。
发明内容
发明目的:本发明所要解决的技术问题是提供一种氧化石墨烯掺杂改性四氧化二铋(GO-Bi2O4)压电催化和光催化联用催化剂及其制备方法和应用,在污水中磺胺甲基嘧啶的降解处理中,具有更高的催化效率。
发明内容:为解决上述技术问题,本发明所采用的技术手段为:一种氧化石墨烯掺杂改性四氧化二铋的压电催化和光催化联用催化剂,通过以下步骤制备而成:
(1)在去离子水中加入二水合铋酸钠和氧化石墨粉末,并在293~303K的水浴温度下搅拌1~2h,得到分散均匀的悬浊液;
(2)将得到的悬浊液加热至433±10K,进行水热合成反应5~24h;
(3)步骤(2)得到的反应产物经过去离子水和无水乙醇多次离心洗涤至中性,然后在333~353K下烘干12~16h,完成。
作为优选方案,所述二水合铋酸钠和氧化石墨的添加质量比为(2~5):1。
本发明另一目的是提供一种上述催化剂用于降解污水中磺胺甲基嘧啶的应用。
本发明还提供了一种污水中磺胺甲基嘧啶的降解去除方法,在含磺胺甲基嘧啶的污水中,加入0.2~3g/L上述催化剂,并在氙灯光照和超声同时作用下,使磺胺甲基嘧啶降解0.5~2h。
作为优选方案,所述氙灯光照的功率为300~580mW/cm2。
作为优选方案,所述超声的功率为250~400W,超声频率为20~50KHz。有益效果:相比于现有技术,本发明具有以下优点:(1)本发明甄选氧化石墨烯(GO)和四氧化二铋(Bi2O4),以GO掺杂改性Bi2O4。其中Bi2O4的铋具有混合价态(Bi3+和Bi5+)比单一价态的Bi2O3具有更高的催化活性,改性Bi2O4具有更优的结构,使得制备的GO-Bi2O4催化剂性能与Bi2O4相比有明显提升。(2)本发明催化剂具有合成便利、环境友好、性能稳定、效率高等优点。
附图说明
图1为本发明实施例1制备的的GO-Bi2O4催化剂与其他对比例得到的Bi2O4催化剂的XRD对比图。
图2为本发明实施例1所制备的GO-Bi2O4催化剂和对比例1所制备的Bi2O4催化剂降解磺胺甲基嘧啶效果对比图。
图3为本发明实施例1所制备GO-Bi2O4催化剂在光催化、压电催化和压电/光联用三种条件下的磺胺甲基嘧啶降解曲线图。
具体实施方式
下面结合附图并以具体实施例,进一步阐明本发明。应理解这些实施例仅用于说明本发明而不用于限制本发明的范围,在阅读了本发明之后,本领域技术人员对本发明的各种等价形式的修改均落于本申请所附权利要求所限定的范围。
实施例1:GO-Bi2O4的制备及应用
(1)采用水热合成法制备GO-Bi2O4,将0.02g氧化石墨烯(GO)和0.56g二水合铋酸钠(NaBiO3·2H2O)加入到20mL超纯水中,置于搅拌器搅拌,使得材料完全分散。
(2)将上述悬浊液置于50mL内衬聚四氟乙烯的不锈钢高压反应釜中进行水热合成,反应温度433K,时间12h。
(3)将水热反应后的产物使用超纯水多次离心洗涤到中性,再用乙醇洗涤,然后将洗涤过后的产物置于328K烘箱中,干燥12h。
(4)以(3)得到的催化剂压电催化降解SM。取50mL初始浓度为30mg/L SM溶液于100mL烧杯中,GO-Bi2O4催化剂投加量为0.04g,使用氙灯光源(光功率密度:580mW/cm2)提供光照的同时进行超声(频率:40kHz,功率300W),温度为300K。反应时间为1h,使用HPLC检测SM浓度。
GO-Bi2O4在1h内对SM压电催化和光催化联用降解效率约为100%。
从图1的表征结果可以得出,相较于对比例1合成的Bi2O4催化剂,实施例1所制备GO-Bi2O4催化剂在XRD谱图中显现了氧化石墨烯(GO)的特征峰。
对比例1:Bi2O4的制备和应用
对于对比例1,以Bi2O4为催化剂,该催化剂采用水热法合成。将0.56g二水合铋酸钠粉末均匀分散20mL超纯水中,然后将悬浊液置于反应釜中433K反应12小时,再经洗涤、干燥、研磨过筛等制得。
将该催化剂应用于压电催化和光催化联用降解SM。由图2可知GO-Bi2O4催化剂用于压电催化和光催化联用降解SM比Bi2O4催化剂用于压电催化和光催化联用降解SM具有更好的降解效果。
对比例2:GO-Bi2O4压电催化降解SM
对于对比例2,按照实施例1中GO-Bi2O4的制备方法制得GO-Bi2O4。将该催化剂应用于压电催化降解SM。与实施例1相同的反应条件下,移除光源,并将反应器避光处理。GO-Bi2O4在1h内对SM压电催化降解效率约为40%。
对比例3:GO-Bi2O4光催化降解SM
对于对比例3,按照实施例1中GO-Bi2O4的制备方法制得GO-Bi2O4。将其用于光催化降解SM。与实施例1相同的反应条件下,移去超声装置。GO-Bi2O4在1h光催化降解SM效率约为90%。
由图3可见,GO-Bi2O4催化剂用于超声催化和光催化联用对污染物的降解效率明显优于单独的压电催化和单独的光催化技术。
最后应说明的是:以上实施例仅用以说明本发明的技术方案,而非对其限制;尽管参照前述实施例对本发明进行了详细的说明,本领域的普通技术人员应当理解:其依然可以对前述实施例所记载的技术方案进行修改,或者对其中部分技术特征进行等同替换;而这些修改或者替换,并不使相应技术方案的本质脱离本发明实施例技术方案的精神和范围。
Claims (6)
1.一种氧化石墨烯掺杂改性四氧化二铋的压电催化和光催化联用催化剂,其特征在于通过以下步骤制备而成:
(1)在去离子水中加入二水合铋酸钠和氧化石墨粉末,并在293~303K的水浴温度下搅拌1~2h,得到分散均匀的悬浊液;
(2)将得到的悬浊液加热至433±10K,进行水热合成反应5~24h;
(3)步骤(2)得到的反应产物经过去离子水和无水乙醇多次离心洗涤至中性,然后在333~353K下烘干12~16h,得到GO-Bi2O4催化剂。
2.根据权利要求1所述氧化石墨烯掺杂改性四氧化二铋的压电催化和光催化联用催化剂,其特征在于:所述GO-Bi2O4催化剂中Bi2O4和氧化石墨的质量比为(2~5):1。
3.权利要求1或2所述催化剂用于降解污水中磺胺甲基嘧啶的应用。
4.一种污水中磺胺甲基嘧啶的降解去除方法,其特征在于:在含磺胺甲基嘧啶的污水中,加入0.2~3g/L权利要求1或2所述催化剂,并在氙灯光照和超声同时作用下,使磺胺甲基嘧啶降解0.5~2h。
5.根据权利要求4所述污水中磺胺甲基嘧啶的降解去除方法,其特征在于:所述氙灯光照的功率为300~580mW/cm2。
6.根据权利要求4所述污水中磺胺甲基嘧啶的降解去除方法,其特征在于:所述超声的功率为250~400W,超声频率为20~50KHz。
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