CN112316969A - 一种N掺杂TiO2中空微球-BiOBr的光催化降解材料及制备方法 - Google Patents
一种N掺杂TiO2中空微球-BiOBr的光催化降解材料及制备方法 Download PDFInfo
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- 238000013033 photocatalytic degradation reaction Methods 0.000 title claims abstract description 34
- 239000000463 material Substances 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims description 7
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 65
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- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 claims abstract description 35
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- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 23
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- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims description 18
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- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
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- 239000010937 tungsten Substances 0.000 description 1
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Abstract
本发明涉及光催化降解技术领域,且公开了一种N掺杂TiO2中空微球‑BiOBr的光催化降解材料,以N掺杂多孔TiO2中空微球为基体,硝酸铋和溴化钠为原料,得到N掺杂TiO2中空微球负载花状纳米BiOBr复合材料,具有超高的比表面积,有利于暴露更多的光催化活性位点和吸附更多的甲基橙等有机污染物,N掺杂促进纳米多孔TiO2中空微球表面形成更多的氧空位,捕获光生电子,延缓光生电子‑空穴复合,BiOBr与TiO2形成p‑n型异质结,进一步促进光生电子‑空穴分离,同时使得复合材料的带隙变窄、吸收带边红移,提高了对可见光的吸收效率,使得N掺杂TiO2中空微球‑BiOBr的光催化降解材料具有优异的光催化降解甲基橙等有机污染物的性能。
Description
技术领域
本发明涉及光催化降解技术领域,具体为一种N掺杂TiO2中空微球 -BiOBr的光催化降解材料及制备方法。
背景技术
随着社会的发展,人们对于染料的应用越来越多,由此产生的含甲基橙等毒性大、难降解的有机污染物的废水也越来越多,常用的处理方法有光催化氧化法、生物法等,但是后者的效率很低,光催化技术具有降解效率高、成本低、绿色无污染等优点,有着广阔的应用前景,光催化降解材料TiO2、ZnO 等在可见光下具有很好的光催化活性,但是本身带隙较宽、光生电子-空穴易复合,制约了其应用,因此,需要对其作出改性。
TiO2是一种n型半导体,具有无毒、成本低、稳定性好等优点,对其进行改性,以改善其光催化效果,元素掺杂可以延缓其光生电子-空穴的复合速度,改善其光催化性能,且BiOBr是一种p型半导体,带隙宽度适中,且可见光催化活性和稳定性优异,因此,我们采用N掺杂TiO2中空微球-BiOBr的方式来解决上述问题。
(一)解决的技术问题
针对现有技术的不足,本发明提供了一种N掺杂TiO2中空微球-BiOBr的光催化降解材料及制备方法,解决了TiO2带隙较宽、光生电子-空穴易复合的问题。
(二)技术方案
为实现上述目的,本发明提供如下技术方案:一种N掺杂TiO2中空微球 -BiOBr的光催化降解材料,所述N掺杂TiO2中空微球-BiOBr的光催化降解材料制备方法如下:
(1)向反应瓶中加入无水乙醇、钛酸四丁酯,搅拌均匀,在搅拌下滴加进去离子水中,搅拌均匀,过滤,用无水乙醇洗涤干净,将洗涤产物置于反应釜中,加入无水乙醇、碳酸氢铵,其中钛酸四丁酯、碳酸氢铵的质量比为 60-75:100,搅拌均匀,置于烘箱中,在160-200℃下反应36-72h,冷却至室温,离心,用去离子水、无水乙醇洗涤干净并干燥,得到纳米多孔TiO2中空微球;
(2)向反应瓶中加入去离子水、尿素、纳米多孔TiO2中空微球,搅拌1-3 h,在60-80℃下水浴蒸干,置于马弗炉中,进行焙烧过程,冷却至室温,用稀硫酸、去离子水洗涤干净并干燥,得到N掺杂多孔TiO2中空微球;
(3)向反应瓶中加入乙二醇、硝酸铋,搅拌均匀,加入溴化钠的乙二醇溶液、N掺杂多孔TiO2中空微球,搅拌均匀,置于反应釜中,在160-180℃下反应4-8h,冷却至室温,用去离子水、无水乙醇洗涤干净并干燥,得到N 掺杂TiO2中空微球-BiOBr的光催化降解材料。
优选的,所述步骤(1)中烘箱包括主体,主体两侧的中间活动连接有固定轴,固定轴的中间活动连接有活动杆,活动杆的底部活动连接有连接杆,活动杆的左侧活动连接有齿轮一,连接杆的左侧活动连接有齿轮二,齿轮一的右侧活动连接有活动轴,活动轴的中间活动连接有载物槽,载物槽的中间活动连接有反应釜。
优选的,所述步骤(2)中尿素、纳米多孔TiO2中空微球的质量比为 30-45:100。
优选的,所述步骤(2)中焙烧过程为在320-380℃下焙烧2-4h。
优选的,所述步骤(3)中硝酸铋、溴化钠、N掺杂多孔TiO2中空微球的质量比为210-250:55-70:100。
(三)有益的技术效果
与现有技术相比,本发明具备以下有益的技术效果:
该一种N掺杂TiO2中空微球-BiOBr的光催化降解材料,钛酸四丁酯在乙醇的水溶液中水解生成二氧化钛溶胶,再以碳酸氢铵为空心模板剂,经过溶剂热反应,得到纳米多孔TiO2中空微球,其独特的多孔中空结构,具有丰富的孔隙结构,使得TiO2具有更高的比表面积,以纳米多孔TiO2中空微球为基体、尿素作为氮源,经过焙烧,得到N掺杂多孔TiO2中空微球,再以N掺杂多孔TiO2中空微球为基体、硝酸铋为铋源、溴化钠为溴源,经过水热反应,得到N掺杂TiO2中空微球负载花状纳米BiOBr复合材料,BiOBr独特的纳米花状形貌,具有超高的比表面积,有利于暴露更多的光催化活性位点和吸附更多的甲基橙等有机污染物。
该一种N掺杂TiO2中空微球-BiOBr的光催化降解材料,N掺杂降低了纳米多孔TiO2中空微球表面生成氧空位所需的能量,促进纳米多孔TiO2中空微球表面形成更多的氧空位,作为光生电子捕获陷阱捕获光生电子,有效延缓光生电子-空穴的复合,同时N掺杂纳米多孔TiO2中空微球进一步提高了比表面积,进一步暴露出更多的光催化活性位点,同时提高了氧气的吸附量,有利于形成更多的超氧自由基,p型半导体BiOBr与n型半导体TiO2形成p-n 型异质结结构,使TiO2的费米能级下降,BiOBr的费米能级升高,形成从 n-TiO2到p-BiOBr的内建电场,在内建电场的作用下,促进光生电子从BiOBr 的导带转移到TiO2的导带上,从而与氧气反应生成更多的超氧自由基,空穴从TiO2的价带转移到BiOBr的价带上,进一步促进光生电子-空穴的分离,减少了光生载流子的重组和复合,具有强氧化性的超氧自由基和空穴将甲基橙等有机污染物降解为小分子物质,且异质结结构使得复合材料的带隙变窄、吸收带边红移,提高了对可见光的吸收效率,使得N掺杂TiO2中空微球-BiOBr 的光催化降解材料具有优异的光催化降解性能。
附图说明
图1是烘箱正视结构示意图;
图2是齿轮正视结构示意图;
图3是齿轮后视结构示意图。
1、主体;2、固定轴;3、活动杆;4、连接杆;5、齿轮一;6、齿轮二; 7、活动轴;8、载物槽;9、反应釜。
具体实施方式
为实现上述目的,本发明提供如下具体实施方式和实施例:一种N掺杂 TiO2中空微球-BiOBr的光催化降解材料,N掺杂TiO2中空微球-BiOBr的光催化降解材料制备方法如下:
(1)向反应瓶中加入无水乙醇、钛酸四丁酯,搅拌均匀,在搅拌下滴加进去离子水中,搅拌均匀,过滤,用无水乙醇洗涤干净,将洗涤产物置于反应釜中,加入无水乙醇、碳酸氢铵,其中钛酸四丁酯、碳酸氢铵的质量比为 60-75:100,搅拌均匀,置于烘箱中,烘箱包括主体,主体两侧的中间活动连接有固定轴,固定轴的中间活动连接有活动杆,活动杆的底部活动连接有连接杆,活动杆的左侧活动连接有齿轮一,连接杆的左侧活动连接有齿轮二,齿轮一的右侧活动连接有活动轴,活动轴的中间活动连接有载物槽,载物槽的中间活动连接有反应釜,在160-200℃下反应36-72h,冷却至室温,离心,用去离子水、无水乙醇洗涤干净并干燥,得到纳米多孔TiO2中空微球;
(2)向反应瓶中加入去离子水、尿素、纳米多孔TiO2中空微球,二者的质量比为30-45:100,搅拌1-3h,在60-80℃下水浴蒸干,置于马弗炉中,进行焙烧过程,焙烧过程为在320-380℃下焙烧2-4h,冷却至室温,用稀硫酸、去离子水洗涤干净并干燥,得到N掺杂多孔TiO2中空微球;
(3)向反应瓶中加入乙二醇、硝酸铋,搅拌均匀,加入溴化钠的乙二醇溶液、N掺杂多孔TiO2中空微球,其中硝酸铋、溴化钠、N掺杂多孔TiO2中空微球的质量比为210-250:55-70:100,搅拌均匀,置于反应釜中,在160-180 ℃下反应4-8h,冷却至室温,用去离子水、无水乙醇洗涤干净并干燥,得到N 掺杂TiO2中空微球-BiOBr的光催化降解材料。
实施例1
(1)向反应瓶中加入无水乙醇、钛酸四丁酯,搅拌均匀,在搅拌下滴加进去离子水中,搅拌均匀,过滤,用无水乙醇洗涤干净,将洗涤产物置于反应釜中,加入无水乙醇、碳酸氢铵,其中钛酸四丁酯、碳酸氢铵的质量比为 60:100,搅拌均匀,置于烘箱中,烘箱包括主体,主体两侧的中间活动连接有固定轴,固定轴的中间活动连接有活动杆,活动杆的底部活动连接有连接杆,活动杆的左侧活动连接有齿轮一,连接杆的左侧活动连接有齿轮二,齿轮一的右侧活动连接有活动轴,活动轴的中间活动连接有载物槽,载物槽的中间活动连接有反应釜,在160℃下反应36h,冷却至室温,离心,用去离子水、无水乙醇洗涤干净并干燥,得到纳米多孔TiO2中空微球;
(2)向反应瓶中加入去离子水、尿素、纳米多孔TiO2中空微球,二者的质量比为30:100,搅拌1h,在60℃下水浴蒸干,置于马弗炉中,进行焙烧过程,焙烧过程为在320℃下焙烧2h,冷却至室温,用稀硫酸、去离子水洗涤干净并干燥,得到N掺杂多孔TiO2中空微球;
(3)向反应瓶中加入乙二醇、硝酸铋,搅拌均匀,加入溴化钠的乙二醇溶液、N掺杂多孔TiO2中空微球,其中硝酸铋、溴化钠、N掺杂多孔TiO2中空微球的质量比为210:55:100,搅拌均匀,置于反应釜中,在160℃下反应4 h,冷却至室温,用去离子水、无水乙醇洗涤干净并干燥,得到N掺杂TiO2中空微球-BiOBr的光催化降解材料。
实施例2
(1)向反应瓶中加入无水乙醇、钛酸四丁酯,搅拌均匀,在搅拌下滴加进去离子水中,搅拌均匀,过滤,用无水乙醇洗涤干净,将洗涤产物置于反应釜中,加入无水乙醇、碳酸氢铵,其中钛酸四丁酯、碳酸氢铵的质量比为 65:100,搅拌均匀,置于烘箱中,烘箱包括主体,主体两侧的中间活动连接有固定轴,固定轴的中间活动连接有活动杆,活动杆的底部活动连接有连接杆,活动杆的左侧活动连接有齿轮一,连接杆的左侧活动连接有齿轮二,齿轮一的右侧活动连接有活动轴,活动轴的中间活动连接有载物槽,载物槽的中间活动连接有反应釜,在170℃下反应48h,冷却至室温,离心,用去离子水、无水乙醇洗涤干净并干燥,得到纳米多孔TiO2中空微球;
(2)向反应瓶中加入去离子水、尿素、纳米多孔TiO2中空微球,二者的质量比为35:100,搅拌1.5h,在65℃下水浴蒸干,置于马弗炉中,进行焙烧过程,焙烧过程为在340℃下焙烧2.5h,冷却至室温,用稀硫酸、去离子水洗涤干净并干燥,得到N掺杂多孔TiO2中空微球;
(3)向反应瓶中加入乙二醇、硝酸铋,搅拌均匀,加入溴化钠的乙二醇溶液、N掺杂多孔TiO2中空微球,其中硝酸铋、溴化钠、N掺杂多孔TiO2中空微球的质量比为220:60:100,搅拌均匀,置于反应釜中,在165℃下反应5 h,冷却至室温,用去离子水、无水乙醇洗涤干净并干燥,得到N掺杂TiO2中空微球-BiOBr的光催化降解材料。
实施例3
(1)向反应瓶中加入无水乙醇、钛酸四丁酯,搅拌均匀,在搅拌下滴加进去离子水中,搅拌均匀,过滤,用无水乙醇洗涤干净,将洗涤产物置于反应釜中,加入无水乙醇、碳酸氢铵,其中钛酸四丁酯、碳酸氢铵的质量比为 70:100,搅拌均匀,置于烘箱中,烘箱包括主体,主体两侧的中间活动连接有固定轴,固定轴的中间活动连接有活动杆,活动杆的底部活动连接有连接杆,活动杆的左侧活动连接有齿轮一,连接杆的左侧活动连接有齿轮二,齿轮一的右侧活动连接有活动轴,活动轴的中间活动连接有载物槽,载物槽的中间活动连接有反应釜,在185℃下反应60h,冷却至室温,离心,用去离子水、无水乙醇洗涤干净并干燥,得到纳米多孔TiO2中空微球;
(2)向反应瓶中加入去离子水、尿素、纳米多孔TiO2中空微球,二者的质量比为40:100,搅拌2h,在70℃下水浴蒸干,置于马弗炉中,进行焙烧过程,焙烧过程为在360℃下焙烧3h,冷却至室温,用稀硫酸、去离子水洗涤干净并干燥,得到N掺杂多孔TiO2中空微球;
(3)向反应瓶中加入乙二醇、硝酸铋,搅拌均匀,加入溴化钠的乙二醇溶液、N掺杂多孔TiO2中空微球,其中硝酸铋、溴化钠、N掺杂多孔TiO2中空微球的质量比为235:65:100,搅拌均匀,置于反应釜中,在170℃下反应6 h,冷却至室温,用去离子水、无水乙醇洗涤干净并干燥,得到N掺杂TiO2中空微球-BiOBr的光催化降解材料。
实施例4
(1)向反应瓶中加入无水乙醇、钛酸四丁酯,搅拌均匀,在搅拌下滴加进去离子水中,搅拌均匀,过滤,用无水乙醇洗涤干净,将洗涤产物置于反应釜中,加入无水乙醇、碳酸氢铵,其中钛酸四丁酯、碳酸氢铵的质量比为 75:100,搅拌均匀,置于烘箱中,烘箱包括主体,主体两侧的中间活动连接有固定轴,固定轴的中间活动连接有活动杆,活动杆的底部活动连接有连接杆,活动杆的左侧活动连接有齿轮一,连接杆的左侧活动连接有齿轮二,齿轮一的右侧活动连接有活动轴,活动轴的中间活动连接有载物槽,载物槽的中间活动连接有反应釜,在200℃下反应72h,冷却至室温,离心,用去离子水、无水乙醇洗涤干净并干燥,得到纳米多孔TiO2中空微球;
(2)向反应瓶中加入去离子水、尿素、纳米多孔TiO2中空微球,二者的质量比为45:100,搅拌3h,在80℃下水浴蒸干,置于马弗炉中,进行焙烧过程,焙烧过程为在380℃下焙烧4h,冷却至室温,用稀硫酸、去离子水洗涤干净并干燥,得到N掺杂多孔TiO2中空微球;
(3)向反应瓶中加入乙二醇、硝酸铋,搅拌均匀,加入溴化钠的乙二醇溶液、N掺杂多孔TiO2中空微球,其中硝酸铋、溴化钠、N掺杂多孔TiO2中空微球的质量比为250:70:100,搅拌均匀,置于反应釜中,在180℃下反应8 h,冷却至室温,用去离子水、无水乙醇洗涤干净并干燥,得到N掺杂TiO2中空微球-BiOBr的光催化降解材料。
对比例1
(1)向反应瓶中加入无水乙醇、钛酸四丁酯,搅拌均匀,在搅拌下滴加进去离子水中,搅拌均匀,过滤,用无水乙醇洗涤干净,将洗涤产物置于反应釜中,加入无水乙醇、碳酸氢铵,其中钛酸四丁酯、碳酸氢铵的质量比为 45:100,搅拌均匀,置于烘箱中,烘箱包括主体,主体两侧的中间活动连接有固定轴,固定轴的中间活动连接有活动杆,活动杆的底部活动连接有连接杆,活动杆的左侧活动连接有齿轮一,连接杆的左侧活动连接有齿轮二,齿轮一的右侧活动连接有活动轴,活动轴的中间活动连接有载物槽,载物槽的中间活动连接有反应釜,在180℃下反应48h,冷却至室温,离心,用去离子水、无水乙醇洗涤干净并干燥,得到纳米多孔TiO2中空微球;
(2)向反应瓶中加入去离子水、尿素、纳米多孔TiO2中空微球,二者的质量比为25:100,搅拌2h,在70℃下水浴蒸干,置于马弗炉中,进行焙烧过程,焙烧过程为在350℃下焙烧3h,冷却至室温,用稀硫酸、去离子水洗涤干净并干燥,得到N掺杂多孔TiO2中空微球;
(3)向反应瓶中加入乙二醇、硝酸铋,搅拌均匀,加入溴化钠的乙二醇溶液、N掺杂多孔TiO2中空微球,其中硝酸铋、溴化钠、N掺杂多孔TiO2中空微球的质量比为200:50:100,搅拌均匀,置于反应釜中,在170℃下反应6 h,冷却至室温,用去离子水、无水乙醇洗涤干净并干燥,得到N掺杂TiO2中空微球-BiOBr的光催化降解材料。
向反应瓶中加入40mg/L的甲基橙溶液250mL,加入实施例和对比例中得到的N掺杂TiO2中空微球-BiOBr的光催化降解材料0.4g,遮光搅拌30 min,以500W卤钨灯作为可见光光源,光照2h,使用UV752型紫外可见分光光度计测试甲基橙的降解浓度,并计算光催化降解率,测试标准为GB/T 23762-2020。
Claims (5)
1.一种N掺杂TiO2中空微球-BiOBr的光催化降解材料,其特征在于:所述N掺杂TiO2中空微球-BiOBr的光催化降解材料制备方法如下:
(1)向无水乙醇中加入钛酸四丁酯,搅拌均匀,在搅拌下滴加进去离子水中,搅拌均匀,过滤,用无水乙醇洗涤干净,将洗涤产物置于反应釜中,加入无水乙醇、碳酸氢铵,其中钛酸四丁酯、碳酸氢铵的质量比为60-75:100,搅拌均匀,置于烘箱中,在160-200℃下反应36-72h,冷却,离心,洗涤并干燥,得到纳米多孔TiO2中空微球;
(2)向去离子水中加入尿素、纳米多孔TiO2中空微球,搅拌1-3h,在60-80℃下水浴蒸干,置于马弗炉中,进行焙烧过程,冷却,洗涤并干燥,得到N掺杂多孔TiO2中空微球;
(3)向乙二醇中加入硝酸铋,搅拌均匀,加入溴化钠的乙二醇溶液、N掺杂多孔TiO2中空微球,搅拌均匀,置于反应釜中,在160-180℃下反应4-8h,冷却洗涤并干燥,得到N掺杂TiO2中空微球-BiOBr的光催化降解材料。
2.根据权利要求1所述的一种N掺杂TiO2中空微球-BiOBr的光催化降解材料,其特征在于:所述步骤(1)中烘箱包括主体,主体两侧的中间活动连接有固定轴,固定轴的中间活动连接有活动杆,活动杆的底部活动连接有连接杆,活动杆的左侧活动连接有齿轮一,连接杆的左侧活动连接有齿轮二,齿轮一的右侧活动连接有活动轴,活动轴的中间活动连接有载物槽,载物槽的中间活动连接有反应釜。
3.根据权利要求1所述的一种N掺杂TiO2中空微球-BiOBr的光催化降解材料,其特征在于:所述步骤(2)中尿素、纳米多孔TiO2中空微球的质量比为30-45:100。
4.根据权利要求1所述的一种N掺杂TiO2中空微球-BiOBr的光催化降解材料,其特征在于:所述步骤(2)中焙烧过程为在320-380℃下焙烧2-4h。
5.根据权利要求1所述的一种N掺杂TiO2中空微球-BiOBr的光催化降解材料,其特征在于:所述步骤(3)中硝酸铋、溴化钠、N掺杂多孔TiO2中空微球的质量比为210-250:55-70:100。
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CN112973742A (zh) * | 2021-02-10 | 2021-06-18 | 哈尔滨工业大学 | 一种高效光解水制氢低维铋化物/还原二氧化钛复合材料及其制备方法 |
CN113856659A (zh) * | 2021-10-27 | 2021-12-31 | 合肥工业大学 | 一种BiOCl纳米片修饰N掺杂TiO2纳米管阵列的制备方法 |
CN116832837A (zh) * | 2023-03-21 | 2023-10-03 | 武汉理工大学 | 一种花球状TiO2/BiOBr核壳结构异质结材料及其制备方法、应用 |
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Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN112973742A (zh) * | 2021-02-10 | 2021-06-18 | 哈尔滨工业大学 | 一种高效光解水制氢低维铋化物/还原二氧化钛复合材料及其制备方法 |
CN113856659A (zh) * | 2021-10-27 | 2021-12-31 | 合肥工业大学 | 一种BiOCl纳米片修饰N掺杂TiO2纳米管阵列的制备方法 |
CN113856659B (zh) * | 2021-10-27 | 2024-04-05 | 合肥工业大学 | 一种BiOCl纳米片修饰N掺杂TiO2纳米管阵列的制备方法 |
CN116832837A (zh) * | 2023-03-21 | 2023-10-03 | 武汉理工大学 | 一种花球状TiO2/BiOBr核壳结构异质结材料及其制备方法、应用 |
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