CN113578309A - 一种高效光催化剂Bi4Ti3O12的制备方法 - Google Patents
一种高效光催化剂Bi4Ti3O12的制备方法 Download PDFInfo
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Abstract
本发明属于功能材料领域,具体是涉及一种高效光催化剂Bi4Ti3O12的制备方法。以曲拉通X‑100为乳化剂、环己烷为溶剂、正己醇为助表面活性剂,混合后形成澄清透明的混合液,然后分成体积相等的三份,分别与钛酸四丁酯乙醇溶液、硝酸铋水溶液和氨水乙醇溶液混合配成微乳液B、C和D,在强力搅拌下,将C微乳液缓慢滴加进B混合形成微乳液E,再缓慢滴入D,经强烈搅拌形成前驱体;最后经过陈化、离心、清洗、干燥煅烧。该制备方法具有工艺简单,操作容易,颗粒大小可控、分散性好,粒径分布均匀,对设备要求低等优点。制备的钙钛矿型Bi4Ti3O12光催化剂,在可见光作用下,能够有效降解亚甲基蓝,具有极佳的光催化性能。
Description
技术领域
本发明属于功能材料领域,具体是涉及一种高效光催化剂Bi4Ti3O12的制备方法。
背景技术
1999年,有研究者首次将层状材料Bi12TiO20半导体材料作为一种新型的光催化剂开展了研宄。研究发现,作为Aurivillius型金属氧化物的一种,其晶体结构式可表示成(Bi2O2)2+(Bin-1TinO3n+1)2-,它是由三个钙钛矿型的(Bi2Ti3O10)2-基元和一个伪钙钛矿的层状(Bi2O2)2+构成,且具有很好的光催化制氢制氧的能力。
Bi4Ti3O12半导体材料具有较窄的禁带宽度(2.6~2.8eV),同时,由于该类半导体晶体具有层状结构,可以利用带正电的(Bi2O2)2+和带负电的(Bin-1TinO3n+1)2-的静电引力作用产生内部电场,这个层间的局部电势可以对光生载流子的分离与传输起到显著地促进作用,因而具有良好的光催化降解性能。此外研究也发现,目前所制备的Bi4Ti3O12光催化剂可靠性和稳定性较高,可以多次重复使用,且催化性能稳定。
大量的研究者研究表明,不同的制备工艺对光催化剂的形貌、尺寸和结构有重要影响,并直接影响到催化剂的光催化性能。因此,近年来研究者试图采用各种方法制备Bi4Ti3O12光催化剂,以期构筑更多的载体催化中心,提高光催化性能。目前,关于钛酸铋化合物的制备方法主要有高温固相法、水热法、溶胶-凝胶法、喷雾干燥法等。陶瓷学报(万萍,2019,40(6):805-809)采用固相法制备了稀土掺杂的Bi4Ti3O12材料,研究了煅烧温度对材料结构、形貌和发光性能的影响。物理化学学报(林雪,2013,29(2):411-417)采用水热法制备出不同形貌的Bi4Ti3O12粒子,研究表明,水热反应参数的设计对样品的形貌和光催化降解性能有着重要的影响。无机化学学报(高晓明,2017,33(3):455-462)采用水热法制备出球形Bi4Ti3O12粒子,研究表明其光催化降解酸性品红远优于亚甲基蓝、甲基橙等模拟污染物。宁夏工程技术(王立辉,2015,14(1):43-49)采用溶胶凝胶法制备Bi4Ti3O12粉体,并较详细研究了不同络合剂对粉体结构和光催化性能的影响。电子元件与材料(张青,2020,39(7):35-40)采用溶胶凝胶法制备La掺杂Bi4Ti3O12薄膜,研究了掺杂对材料光电性能的影响。功能材料(谭皎,2018,49(1):01216-01220)采用喷雾干燥法制备了Bi4Ti3O12中空微米球,研究发现,在紫外光照射下,2h内甲基橙模拟污染物降解率达到98.77%,光催化效果较佳。
微乳液是由表面活性剂、油相、水相及助溶剂等在适当比例下混合自发形成的热力学稳定体系,自上世纪40年代被提出以来,微乳液的应用领域已渗透到日用化工、材料科学、环境科学等领域。油包水型微乳液的水核被认为是合成纳米粒子的理想反应器,由于其可以对纳米粒子粒径和稳定性进行精确控制,因此为合成具有颗粒粒径大小可控和颗粒分散均匀的纳米粒子提供了良好的合成介质。目前,采用微乳液法制备Bi4Ti3O12光催化剂的研究不多,本研究采用微乳液法制备钙钛矿型Bi4Ti3O12光催化剂还未见报道。
发明内容
本发明要解决的技术问题为克服现有Bi4Ti3O12制备过程中具有的工艺操作复杂,颗粒大且颗粒分散性差的缺点,采用微乳液法制备出钙钛矿型Bi4Ti3O12光催化剂,该制备方法具有工艺简单,操作容易,颗粒大小可控、分散性好,粒径分布均匀,对设备要求低等优点。本方法制备的Bi4Ti3O12光催化剂在可见光下作用下具有较佳的光催化性能。
为了实现上述目的,本发明所采用的技术方案为:
一种高效光催化剂Bi4Ti3O12的制备方法,采用微乳液法制备,具体步骤如下:
步骤①、以曲拉通X-100为乳化剂、环己烷为溶剂、正己醇为助表面活性剂,将三者按一定的摩尔比混合后在磁力搅拌器下强烈搅拌,形成澄清透明的混合液A,并将此混合液分成体积相等的三份,记为A1、A2、A3;
步骤②、在强烈搅拌下,取混合液A1,将钛酸四丁酯乙醇溶液缓慢滴加入混合液中,形成澄清透明的黄色微乳液B;
步骤③、在强烈搅拌下,取混合液A2,将Bi(NO3)3·5H2O水溶液缓慢加入混合液中,形成无色澄清透明的微乳液C;
步骤④、在强烈搅拌下,取混合液A3,将氨水乙醇溶液缓慢加入混合液中,形成无色澄清透明的微乳液D;
步骤⑤、在强烈搅拌下,将微乳液C缓慢加入微乳液B中,形成澄清透明的黄色微乳液E;再缓慢滴加入D,经强烈搅拌形成Bi4Ti3O12前驱体;
步骤⑥、将Bi4Ti3O12前驱体经陈化、离心、清洗、干燥、煅烧从而形成钙钛矿型Bi4Ti3O12高效光催化剂。
作为本发明的优选技术方案,制备方法中:
步骤①的混合液A中曲拉通X-100、环己烷、正己醇之间的摩尔比为1∶10~20∶2~12,步骤②中混合液A1所含曲拉通X-100与钛酸四丁酯添加量的摩尔比为1∶0.06~0.30,步骤②添加钛酸四丁酯乙醇溶液中钛酸四丁酯与乙醇的体积比为1∶3~5,步骤③硝酸铋添加量与步骤②钛酸四丁酯添加量的摩尔比为4∶3,步骤④中氨水乙醇溶液中氨水与步骤③硝酸铋添加量的摩尔比为25~40∶1,步骤④添加氨水乙醇溶液中氨水与乙醇的体积比为1∶1~5。
步骤⑤中将C缓慢加入B中,用浓硝酸微调,使之形成澄清透明的黄色微乳液E。
步骤⑥中将Bi4Ti3O12前驱体在10~30℃下陈化12~36h,离心分离,并用纯水和无水乙醇反复清洗3~5遍,然后于烘箱中80~180℃干燥2~6h,再于马弗炉中450~700℃煅烧2~6h,从而形成钙钛矿型Bi4Ti3O12光催化剂。
本发明还提出了这种钙钛矿型Bi4Ti3O12光催化剂在光催化降解有机染料中的应用。
本发明的高效光催化剂Bi4Ti3O12的制备方法,相对于现有技术的有益效果表现在:
本发明采用微乳液法制备出了钙钛矿型Bi4Ti3O12高效光催化剂,该方法具有工艺简单,操作容易,颗粒大小可控、分散性好,粒径分布均匀,对设备要求低等优点。本发明制备出的钙钛矿型Bi4Ti3O12高效光催化剂,在可见光下作用下,能够有效降解亚甲基蓝,具有较佳的光催化性能。
附图说明
图1是本发明实施制备的钙钛矿型Bi4Ti3O12光催化剂的XRD图。
图2是本发明实施制备的钙钛矿型Bi4Ti3O12光催化剂的EDS图。
图3是本发明实施制备的钙钛矿型Bi4Ti3O12光催化剂的SEM图。
图4是本发明实施制备的钙钛矿型Bi4Ti3O12光催化剂在可见光下降解亚甲基蓝溶液的光催化降解图。
具体实施方式
下面结合附图对本发明的优选方式作进一步详细的描述。
实施例1
步骤①、取0.15mol曲拉通X-100为乳化剂、1.50mol环己烷为溶剂、0.60mol正己醇为助表面活性剂,在磁力搅拌器下强烈搅拌,形成澄清透明的混合液并将此混合液分成体积相等的三份,标记为A1、A2、A3。
步骤②、在强烈搅拌下,取混合液A1,再取钛酸四丁酯乙醇溶液(溶液中含0.0075mol钛酸四丁酯,钛酸四丁酯与曲拉通X-100的摩尔比为0.15∶1,钛酸四丁酯与乙醇的体积比为1∶4),将钛酸四丁酯乙醇溶液缓慢加入混合液A1中,形成澄清透明的黄色微乳液B。
步骤③、在强烈搅拌下,取混合液A2,再取含0.01mol Bi(NO3)3·5H2O的硝酸铋水溶液,将Bi(NO3)3·5H2O水溶液缓慢加入混合液A2中,形成无色澄清透明的微乳液C。
步骤④、强烈搅拌下,取混合液A3,再取氨水乙醇溶液(溶液中含0.3mol氨水,氨水与乙醇的体积比为1∶2),将氨水乙醇溶液缓慢加入混合液A3中,形成无色澄清透明的微乳液D。
步骤⑤、在强烈搅拌下,将微乳液C缓慢加入微乳液B中,并用浓硝酸微调,形成澄清透明的黄色微乳液E;再缓慢滴加入D,经强烈搅拌形成Bi4Ti3O12前驱体。
步骤⑥、将Bi4Ti3O12前驱体在20℃下陈化24h,离心分离,并用纯水和无水乙醇反复清洗3~5遍,然后于烘箱中120℃干燥3h,于马弗炉中500℃煅烧4.5h,从而形成钙钛矿型Bi4Ti3O12光催化剂。
从附图1的XRD图可以看出,所制备的样品为纯的钙钛矿型Bi4Ti3O12光催化剂,没有观察到其它杂质峰的存在;谱图中各个谱峰尖锐,说明样品晶化程度良好。
从附图2的EDS图可以看出,定量分析结果符合所制备的Bi4Ti3O12光催化剂各组分的摩尔比。
从附图3的SEM图可以看出,所制备的Bi4Ti3O12光催化剂呈类球体,球体直径约80nm,颗粒分散性好,粒径分布均匀。
从附图4的光催化降解图可以看出,所制备的Bi4Ti3O12光催化剂以亚甲基蓝为模拟污染物,经过110分钟,光催化降解率达到99.2%,表明光催化剂具有极佳的光催化活性。
因此,从XRD图、EDS图、SEM图和光催化降解图的分析结果中可以看出,通过微乳液法这种简单易控的方法,能方便的制备出颗粒较小、分散性较好,且粒径分布均匀的钙钛矿型Bi4Ti3O12光催化剂。在可见光作用下,所制备的Bi4Ti3O12光催化剂具有极佳的光催化性能。
实施例2
步骤①、取0.15mol曲拉通X-100为乳化剂、1.80mol环己烷为溶剂、0.90mol正己醇为助表面活性剂,在磁力搅拌器下强烈搅拌,形成澄清透明的混合液并将此混合液分成体积相等的三份,标记为A1、A2、A3。
步骤②、在强烈搅拌下,取混合液A1,再取钛酸四丁酯乙醇溶液(溶液中含0.006mol钛酸四丁酯,钛酸四丁酯与曲拉通X-100的摩尔比为0.12∶1,钛酸四丁酯与乙醇的体积比为1∶3),将钛酸四丁酯乙醇溶液缓慢加入混合液A1中,形成澄清透明的黄色微乳液B。
步骤③、在强烈搅拌下,取混合液A2,再取含0.008mol Bi(NO3)3·5H2O的硝酸铋水溶液,将Bi(NO3)3·5H2O水溶液缓慢加入混合液A2中,形成无色澄清透明的微乳液C。
步骤④、强烈搅拌下,取混合液A3,再取氨水乙醇溶液(溶液中含0.28mol氨水,氨水与乙醇的体积比为1∶3),将氨水乙醇溶液缓慢加入混合液A3中,形成无色澄清透明的微乳液D。
步骤⑤、在强烈搅拌下,将微乳液C缓慢加入微乳液B中,并用浓硝酸微调,形成澄清透明的黄色微乳液E;再缓慢滴加入D,经强烈搅拌形成Bi4Ti3O12前驱体。
步骤⑥、将Bi4Ti3O12前驱体在25℃下陈化30h,离心分离,并用纯水和无水乙醇反复清洗3~5遍,然后于烘箱中100℃干燥4h,于马弗炉中550℃煅烧3h,从而形成钙钛矿型Bi4Ti3O12光催化剂。
实施例3
步骤①、取0.15mol曲拉通X-100为乳化剂、2.70mol环己烷为溶剂、1.80mol正己醇为助表面活性剂,在磁力搅拌器下强烈搅拌,形成澄清透明的混合液并将此混合液分成体积相等的三份,标记为A1、A2、A3。
步骤②、在强烈搅拌下,取混合液A1,再取钛酸四丁酯乙醇溶液(溶液中含0.009mol钛酸四丁酯,钛酸四丁酯与曲拉通X-100的摩尔比为0.18∶1,钛酸四丁酯与乙醇的体积比为1∶5),将钛酸四丁酯乙醇溶液缓慢加入混合液A1中,形成澄清透明的黄色微乳液B。
步骤③、在强烈搅拌下,取混合液A2,再取含0.012mol Bi(NO3)3·5H2O的硝酸铋水溶液,将Bi(NO3)3·5H2O水溶液缓慢加入混合液A2中,形成无色澄清透明的微乳液C。
步骤④、强烈搅拌下,取混合液A3,再取氨水乙醇溶液(溶液中含0.45mol氨水,氨水与乙醇的体积比为1∶5),将氨水乙醇溶液缓慢加入混合液A3中,形成无色澄清透明的微乳液D。
步骤⑤、在强烈搅拌下,将微乳液C缓慢加入微乳液B中,并用浓硝酸微调,形成澄清透明的黄色微乳液E;再缓慢滴加入D,经强烈搅拌形成Bi4Ti3O12前驱体。
步骤⑥、将Bi4Ti3O12前驱体在20℃下陈化36h,离心分离,并用纯水和无水乙醇反复清洗3~5遍,然后于烘箱中180℃干燥2h,于马弗炉中600℃煅烧3h,从而形成钙钛矿型Bi4Ti3O12光催化剂。
上述各实施例只是为了说明本发明的技术构思及特点,其目的是在于让本领域内的普通技术人员能够了解本发明的内容并据以实施,并不能以此限制本发明的保护范围。凡是根据本发明内容的实质所作出的等效的变化或修饰,都应涵盖在本发明的保护范围内。
Claims (10)
1.一种高效光催化剂Bi4Ti3O12的制备方法,其特征在于,采用微乳液法制备,具体步骤如下:
步骤①、以曲拉通X-100为乳化剂、环己烷为溶剂、正己醇为助表面活性剂,将三者按一定的摩尔比混合后在磁力搅拌器下强烈搅拌,形成澄清透明的混合液A,并将此混合液分成体积相等的三份,记为A1、A2、A3;
步骤②、在强烈搅拌下,取混合液A1,将钛酸四丁酯乙醇溶液缓慢滴加入混合液中,形成澄清透明的黄色微乳液B;
步骤③、在强烈搅拌下,取混合液A2,将Bi(NO3)3·5H2O水溶液缓慢加入混合液中,形成无色澄清透明的微乳液C;
步骤④、在强烈搅拌下,取混合液A3,将氨水乙醇溶液缓慢加入混合液中,形成无色澄清透明的微乳液D;
步骤⑤、在强烈搅拌下,将微乳液C缓慢加入微乳液B中,形成澄清透明的黄色微乳液E;再缓慢滴加入D,经强烈搅拌形成Bi4Ti3O12前驱体;
步骤⑥、将Bi4Ti3O12前驱体经陈化、离心、清洗、干燥、煅烧从而形成钙钛矿型Bi4Ti3O12高效光催化剂。
2.如权利要求1所述的制备方法,其特征在于,步骤①的混合液A中曲拉通X-100、环己烷、正己醇之间的摩尔比为1∶10~20∶2~12。
3.如权利要求2所述的制备方法,其特征在于,步骤②中混合液A1所含曲拉通X-100与钛酸四丁酯添加量的摩尔比为1∶0.06~0.30。
4.如权利要求2所述的制备方法,其特征在于,步骤②添加钛酸四丁酯乙醇溶液中钛酸四丁酯与乙醇的体积比为1∶3~5。
5.如权利要求4所述的制备方法,其特征在于,步骤③硝酸铋添加量与步骤②钛酸四丁酯添加量的摩尔比为4∶3。
6.如权利要求5所述的制备方法,其特征在于,步骤④中氨水乙醇溶液中氨水与步骤③硝酸铋添加量的摩尔比为25~40∶1。
7.如权利要求1所述的制备方法,其特征在于,步骤④添加氨水乙醇溶液中氨水与乙醇的体积比为1∶1~5。
8.如权利要求1所述的制备方法,其特征在于,步骤⑤中将C缓慢加入B中,用浓硝酸微调,使之形成澄清透明的黄色微乳液E。
9.如权利要求1所述的制备方法,其特征在于,步骤⑥中将Bi4Ti3O12前驱体在10~30℃下陈化12~36h,离心分离,并用纯水和无水乙醇反复清洗3~5遍,然后于烘箱中80~180℃干燥2~6h,再于马弗炉中450~700℃煅烧2~6h,从而形成钙钛矿型Bi4Ti3O12光催化剂。
10.如权利要求1~9任一项所述方法制备的钙钛矿型Bi4Ti3O12光催化剂在光催化降解有机染料中的应用。
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