CN107649118B - 一种BiVO4负载混合晶相TiO2可见光复合光催化剂的制备方法 - Google Patents
一种BiVO4负载混合晶相TiO2可见光复合光催化剂的制备方法 Download PDFInfo
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Abstract
TiO2作为一种常见的半导体材料,量子效率较低、对可见光无响应等缺点严重制约了其在光催化领域的应用。本发明以钛酸异丙酯为原料,首先制备了无定型TiO2微米球,再通过绿色环保的水热过程制备了具有锐钛矿/板钛矿混合晶相的TiO2介孔球,该结构由纳米颗粒组成,通过纳米化过程降低电荷迁移过程中复合作用。其次通过简易的湿化学法将BiVO4纳米颗粒负载到TiO2介孔球上,得到的异质结构具有良好的可见光响应,对亚甲基蓝具有可见光降解作用。BiVO4/TiO2复合光催化剂以初级纳米颗粒自组装而成的微米级球状颗粒形式存在,易于从污水中回收,在工业废水处理中具有十分重要的实际意义。
Description
技术领域:
本发明涉及一种BiVO4负载TiO2介孔微米球结构光催化剂的制备方法,更具体的说,利用水热法制备含有锐钛矿/板钛矿混合晶相的TiO2花状纳米结构为载体,通过湿化学法将BiVO4纳米颗粒负载到TiO2,制备具有可见光响应的异质结纳米光催化剂。本技术属于纳米材料的制备领域。
背景技术:
近年来,随着社会经济的快速发展,环境污染问题日益凸显。国家对于工业废水排放的高标准,要求各企业尤其是中小型企业寻找一种高效、经济的污水处理方法。
半导体光催化技术是近几十年兴起的一种利用太阳能进行催化反应的高效技术,广泛应用到光解水制氢、光催化降解有机物等方面。1972年,Fujishima等人使用TiO2光电极将水进行了分解,自此掀起了光催化技术研究的热潮。二氧化钛作为一种半导体材料,由于其成本低廉、无毒无害、化学稳定性高的特点,受到了社会的广泛关注。然而,二氧化钛具有一些突出的缺点,使其在光催化领域的应用受到限制:
(1)二氧化钛的量子效率较低,光生电子-空穴的复合率高,将二氧化钛纳米化可以提高光生电荷的转移,但工业上对催化剂的回收产生了一定的困难;
(2)二氧化钛的禁带宽度为3.2eV,只能利用波长小于387nm的紫外光,而紫外光部分大约只占太阳光谱的4%,大大限制了对光能的利用。
为了解决上述问题,通常对TiO2材料进行改性处理。一方面通过自组装过程,使二氧化钛纳米化的基础上,构筑较为复杂的纳米管、纳米棒、3D纳米结构,这些结构由纳米尺寸的初级颗粒组成了尺寸较大的次级结构,有利于催化剂的沉降、回收。另一方面是通过离子掺杂、贵金属沉积、半导体复合等方式改性,其中半导体复合是较为有效的方式。钒酸铋作为一种窄带隙(2.4eV)半导体,但由于其具有较短的电子迁移长度,通常单独用作光催化剂时效果并不理想。可以用于与TiO2进行复合,增强光催化剂的光吸收范围,并通过异质结的构建达到增加电荷分离寿命的目的,提高光催化效率。目前关于BiVO4负载TiO2复合光催化剂的报道较少,且大多数研究集中在先制备BiVO4颗粒,再利用溶胶法将TiO2负载在BiVO4表面(Applied Catalysis B:Environmental 104(2011)30-36、Journal of Alloys andCompounds 688(2016)703-711);且制备的BiVO4负载TiO2多以分散的小颗粒形式存在(Chemical Engineering Journal 314(2017)443–452、Ceramics International 41(2015)5999–6004),不利于催化反应后的回收。值得一提的是,目前几乎没有BiVO4负载混合晶相的TiO2球可见光催化剂的相关报道。
发明内容:
本发明的目的是提供一种BiVO4负载混合晶相TiO2可见光催化剂的制备方法,以克服现有技术上的不足,该方案可以实现半导体复合以提高催化剂的催化活性,同时以纳米颗粒自组装而成的微米介孔球的形式存在,易于从液相中分离,不易造成二次污染,同时也有利于催化剂的回收利用。
为实现上述的目的,解决上述技术问题,利用以下的技术方案,一种BiVO4负载混合晶相TiO2可见光催化剂的制备方法,包含以下的步骤:
(1)选用钛酸异丙酯(TTIP)作原料,溶解于500mL乙醇中,加入一定量的浓度为0.1mol·L-1的KCl 溶液,引发水解反应,出现白色沉淀后停止搅拌,静置12-48h。离心、水洗、干燥,得到白色TiO2·nH2O 粉末;
(2)将0.6g(1)中粉末加入到含有60mL的0.1mol·L-1NaOH溶液水热釜内衬中,滴加0.9mL的质量分数为3%双氧水,在鼓风干燥箱中140-200℃反应2-20h。冷却到室温后,将产物离心、水洗、干燥,得到白色钛酸钠粉末;
(3)将1.0g钛酸钠粉末加入到250mL 0.1M稀盐酸中,充分搅拌1小时,静置1小时。将产物离心、水洗、干燥。得到的白色产物在马弗炉中400-500℃煅烧60-120min,得到白色TiO2介孔球粉末;
(4)将2.425g Bi(NO3)3·5H2O加入到100mL的0.4mol·L-1的稀硝酸溶液中,充分搅拌得到硝酸铋溶液。将0.585g的NH4VO3加入到100mL的80℃去离子水中,充分搅拌得到偏钒酸铵溶液,加入一定质量的步骤(3)中得到的TiO2介孔球,充分搅拌,并将上述钒酸铋溶液滴加到该溶液中。使用氨水调节体系的pH=4,将混合物置于90℃水浴中加热蒸发,最终得到亮黄色浆状产物。水洗、离心、干燥,得到亮黄色粉末;
(5)将步骤(4)中得到的粉末在马弗炉中煅烧,400-500℃煅烧60-120min,最终得到BiVO4负载混合晶相TiO2可见光催化剂。
本专利选用的BiVO4作为一种重要的窄带隙(约2.4eV)半导体材料,通常单独作为一种可见光催化剂使用,同时可以看作是一种优异的光敏化剂。将BiVO4与TiO2复合,可以显著拓宽TiO2的光谱相应范围。当入射光的能量不足以激发TiO2产生光生电子-空穴从而引发氧化还原反应时,BiVO4却可以被激发,提高了太阳能的利用率。其次,混合晶相的TiO2本身可以形成异质结构,进一步增强光生电荷的分离效果。最后,与其他形貌相比,复合光催化剂以纳米颗粒自组装而成的次级介孔微米球的形式存在,有利于催化剂使用后从污水中回收利用。
与现有技术相比,本发明的有益效果是:
(1)本发明利用湿化学法制备了BiVO4负载的TiO2介孔微米球结构,设备简便,成本较低。
(2)用窄带隙半导体BiVO4与TiO2复合,拓宽了光谱响应范围,提高了太阳能利用率。
(3)花状TiO2前驱体结构使得BiVO4的接触面积提高,形成良好的异质结构,增强抑制光生电子和空穴的复合;同时TiO2中锐钛矿/板钛矿混合晶相进一步增强分离效果。
(4)复合光催化剂以纳米颗粒自组装而成的次级介孔微米球的形式存在,易于从处理后的污水中回收利用,避免二次污染,是一种环境友好型光催化剂。
附图说明:
图1:混合晶相TiO2花状球前驱体的TEM图片
图2:实施例1中BiVO4/TiO2介孔微米球的TEM图片
图3:实施例1中BiVO4/TiO2介孔微米球的光谱响应
具体实施方式:
实施例1
向500mL乙醇中加入2mL 0.1mol·L-1的KCl溶液,搅拌10min。加入9mL TTIP,搅拌30分钟。静置24小时后,将白色浊液离心,并用乙醇、水洗,干燥。将0.6g的上述产物加入到60mL的0.1mol·L-1 NaOH溶液中,搅拌30分钟,然后加入0.9mL质量分数3%的过氧化氢溶液,搅拌2分钟,封装水热釜于鼓风干燥箱中180℃反应10h。取出水热釜后,冷却至室温,将产物水洗、干燥。将1.0g上述产物加入到250毫升0.1mol·L-1的稀盐酸中,持续搅拌1h,之后停止搅拌静置1h。之后倒掉上层清液,水洗、干燥产物,将产物于马弗炉中煅烧450℃2h。称取2.425g Bi(NO3)3加入到100mL 0.4mol·L-1的硝酸溶液中,搅拌30min,形成溶液A。称取0.585g的NH4VO3加入到100mL去离子水中,80℃水浴加热并搅拌均匀,加入3.994g TiO2,搅拌10min,形成悬浊液B。将溶液A缓慢滴加到悬浊液B中,搅拌30min。氨水调节溶液pH=4,90℃水浴得到亮黄色泥浆。水洗、干燥,于马弗炉中450℃煅烧2h。即可得到摩尔比为Bi:Ti=1:10的BiVO4负载的混合晶相TiO2介孔复合光催化剂。图2为BiVO4/TiO2介孔微米球的 TEM图片,图3为BiVO4/TiO2介孔微米球的光谱响应图。
实施例2
向500mL乙醇中加入2mL 0.1mol·L-1的KCl溶液,搅拌10min。加入9mL TTIP,搅拌30分钟。静置24小时后,将白色浊液离心,并用乙醇、水洗,干燥。将0.6g的上述产物加入到60mL的0.1mol·L-1 NaOH溶液中,搅拌30分钟,然后加入0.9mL质量分数3%的过氧化氢溶液,搅拌2分钟,封装水热釜于鼓风干燥箱中180℃反应10h。取出水热釜后,冷却至室温,将产物水洗、干燥。将1.0g上述产物加入到250毫升0.1mol·L-1的稀盐酸中,持续搅拌1h,之后停止搅拌静置1h。之后倒掉上层清液,水洗、干燥产物,将产物于马弗炉中煅烧450℃2h。称取2.425g Bi(NO3)3加入到100mL 0.4mol·L-1的硝酸溶液中,搅拌30min,形成溶液A。称取0.585g的NH4VO3加入到100mL去离子水中,80℃水浴加热并搅拌均匀,加入19.966g TiO2,搅拌10min,形成悬浊液B。将溶液A缓慢滴加到悬浊液B中,搅拌30min。氨水调节溶液pH=4,90℃水浴得到亮黄色泥浆。水洗、干燥,于马弗炉中450℃煅烧2h。即可得到摩尔比为Bi:Ti=1:50的BiVO4负载的混合晶相TiO2介孔复合光催化剂。
Claims (2)
1.一种BiVO4负载混合晶相TiO2可见光催化剂的制备方法,其特征在于,按以下步骤进行:
(1)选用钛酸异丙酯(TTIP)作原料,溶解于500mL乙醇中,加入一定量的浓度为0.1mol·L-1的KCl溶液,引发水解反应,出现白色沉淀后停止搅拌,静置12-48h;离心、水洗、干燥,得到白色TiO2·nH2O粉末;
(2)将600mg的TiO2·nH2O粉末加入到含有60mL的0.1mol·L-1NaOH溶液水热釜内衬中,滴加0.9mL的质量分数为3%双氧水,在鼓风干燥箱中140-200℃反应2-20h;冷却到室温后,将产物离心、水洗、干燥,得到白色钛酸钠粉末;
(3)将1.0g钛酸钠粉末加入到250mL 0.1M稀盐酸中,充分搅拌1小时,静置1小时;将产物离心、水洗、干燥;得到的白色产物在马弗炉中400-500℃煅烧120min,得到白色TiO2介孔球粉末;
(4)将2.425g Bi(NO3)3·5H2O加入到100mL的浓度0.4mol·L-1的稀硝酸溶液中,充分搅拌得到硝酸铋溶液;将0.585g的NH4VO3加入到100mL的80℃去离子水中,充分搅拌得到偏钒酸铵溶液,加入一定量的步骤(3)中得到的TiO2介孔球,充分搅拌,并将上述钒酸铋溶液滴加到该溶液中;使用氨水调节体系的pH=4,将混合物置于90℃水浴中加热蒸发,最终得到亮黄色浆状产物;水洗、离心、干燥,得到亮黄色粉末;
(5)将步骤(4)中得到的粉末在马弗炉中煅烧,400-500℃煅烧60-120min,最终得到BiVO4负载混合晶相TiO2可见光催化剂。
2.如权利要求1所述的BiVO4负载混合晶相TiO2可见光催化剂的制备方法,其特征在于,步骤(4)TiO2介孔球的加入量为0.399-19.968g。
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