CN105618152B - 一种通过一步反应稳定及增强TiO2活性的方法 - Google Patents
一种通过一步反应稳定及增强TiO2活性的方法 Download PDFInfo
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- 238000006243 chemical reaction Methods 0.000 title claims abstract description 15
- 238000000034 method Methods 0.000 title claims abstract description 15
- 230000000694 effects Effects 0.000 title claims abstract description 13
- 230000006641 stabilisation Effects 0.000 title claims abstract description 8
- 238000011105 stabilization Methods 0.000 title claims abstract description 8
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 19
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 9
- DGEZNRSVGBDHLK-UHFFFAOYSA-N [1,10]phenanthroline Chemical compound C1=CN=C2C3=NC=CC=C3C=CC2=C1 DGEZNRSVGBDHLK-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000000463 material Substances 0.000 claims abstract description 6
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 4
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 7
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 6
- 238000012986 modification Methods 0.000 claims description 5
- 230000004048 modification Effects 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 3
- STZCRXQWRGQSJD-GEEYTBSJSA-M methyl orange Chemical compound [Na+].C1=CC(N(C)C)=CC=C1\N=N\C1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-GEEYTBSJSA-M 0.000 claims description 3
- 229940012189 methyl orange Drugs 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 4
- 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 abstract 1
- 238000010438 heat treatment Methods 0.000 abstract 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 abstract 1
- 239000002957 persistent organic pollutant Substances 0.000 abstract 1
- 230000001699 photocatalysis Effects 0.000 description 6
- 235000019441 ethanol Nutrition 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 206010013786 Dry skin Diseases 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 125000005909 ethyl alcohol group Chemical group 0.000 description 2
- 231100000252 nontoxic Toxicity 0.000 description 2
- 230000003000 nontoxic effect Effects 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 150000005041 phenanthrolines Chemical class 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 206010070834 Sensitisation Diseases 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000006399 behavior Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 230000002079 cooperative effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 230000008313 sensitization Effects 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/38—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of titanium, zirconium or hafnium
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J35/39—Photocatalytic properties
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Abstract
本发明涉及一种通过一步反应稳定及增强TiO2活性的方法,所得材料能在可见光下高效率地降解有机污染物甲基橙。所述方法包括:将邻菲啰啉与钛酸正丁酯溶解在乙醇中混合均匀后,转至水热釜反应。反应结束后将样品分离,清洗,即得产品。其特征是所得产品比TiO2具有更高的稳定性及更高效的可见光催化活性。
Description
技术领域
本发明涉及纳米半导体氧化物材料技术领域,尤其涉及一种通过一步反应稳定及增强TiO2活性的方法。
背景技术
二氧化钛(TiO2)是一种理化性质稳定、安全无毒、成本低廉的半导体氧化物,在光照射下形成强氧化氛围,几乎能将所有的有机毒物质彻底氧化分解成二氧化碳,水等无毒的小分子物质。太阳能是清洁而经济的能源,TiO2能利用太阳能进行催化的性能使其在降解环境污染领域的应用受到极大的关注。但TiO2的能带间隙较宽,为3.2 eV,这使得它只能吸收利用占到达地面太阳光能5%以下的紫外光(λ< 387nm),不能有效利用太阳光中占绝大数的可见光的能量,能太阳光能量的利用率极低。因此,探讨对TiO2的改性,拓宽其吸附光谱向可见光移动,从而提高对太阳光能量的利用率,是目前TiO2光催化剂研究的焦点。
大量研究实验表明,通过掺杂[J. Phys. Chem. C, 2007, 129, 4538]、贵金属沉积[J. Phys. Chem. C, 2010, 114, 16475]、染料敏化[J. Photochem. Photobiol., A,2009, 204, 168]等方法可有效拓宽TiO2的光响应范围,提高其光催化活性。最近的研究显示,以含有大π共轭键的聚合物与TiO2形成复合物,有可能可以增强其光催化活性。其原理可能是大π键的共轭体系有利于电子的传导,从而利于光生电子的产生及与光生空穴的分离。但目前这方面的研究还很有限。
在本发明方法中,提供了一种新颖的利用大π键单体化合物修饰TiO2,增强其光活性的方法。利用含有三个芳香环大π共轭键的邻菲啰啉,通过简单的一步水热合成法,修饰TiO2,得到TiO2-邻菲啰啉复合物。通过邻菲啰啉的协同作用,使得所得产品具有更好的热稳定性和更强的可见光催化活性。
本发明涉及一种通过一步反应稳定及增强TiO2活性的方法,原料易得,成本低,操作简单,所述方法未见报道。
发明内容
本发明的目的在于提供一种通过一步反应稳定及增强TiO2活性的方法,本发明采取如下手段:
(1)将邻菲啰啉与3 mL钛酸正丁酯溶解于20 mL的乙醇中,邻菲啰啉量的范围为:0.3-1.5 mmol;
(2)将(1)所得溶液加入至水热反应釜,180℃反应24 h后将所得固体离心分离、清洗、烘干后即得产品。
所得的材料为利用邻菲啰啉修饰TiO2,并且是通过一步水热反应完成修饰过程。
所得的材料具有比TiO2更好的热稳定性及可见光催化活性,可在可见光下降解甲基橙。
本发明的优点是:利用含有大π共轭键的单体有机化合物邻菲啰啉修饰TiO2,通过协同效应,增强TiO2的稳定性及光催化活性;原料易得,成本低,操作简单;所得产品具有优良的光催化性能,可利用可见光降解有机污染物甲基橙。
附图说明
图1为本发明之实施例1产品的热失重图;
图2为本发明之实施例1所得产品可见光降解甲基橙。
具体实施方式
实施例1
将0.3 mmol邻菲啰啉与3 mL钛酸正丁酯加入到20 mL无水乙醇中,剧烈搅拌1 h后,装入100 mL水热反应釜,180℃反应24 h。温度降至室温后,拿出反应釜,将所得产品用去离子水和无水乙醇交替洗涤多次。80℃干燥4小时,碾碎成粉。
实施例2
将1.5 mmol邻菲啰啉与3 mL钛酸正丁酯加入到20 mL无水乙醇中,剧烈搅拌1 h后,装入100 mL水热反应釜,180℃反应24 h。温度降至室温后,拿出反应釜,将所得产品用去离子水和无水乙醇交替洗涤多次。80℃干燥4小时,碾碎成粉。
Claims (3)
1.一种通过一步反应稳定及增强TiO2活性的方法,其特征在于:
(1)将邻菲啰啉与3 mL钛酸正丁酯溶解于20 mL的乙醇中,邻菲啰啉量的范围为:0.3-1.5 mmol;
(2)将(1)所得溶液加入至水热反应釜,180℃反应24 h后将所得固体离心分离、清洗、烘干后即得产品。
2.根据权利要求1所述的一种通过一步反应稳定及增强TiO2活性的方法,其特征在于:所得的材料为利用邻菲啰啉修饰TiO2,并且是通过一步水热反应完成修饰过程。
3.根据权利要求1所述的一种通过一步反应稳定及增强TiO2活性的方法,其特征在于:所得的材料具有比TiO2更好的热稳定性及可见光催化活性,可在可见光下降解甲基橙。
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CN104785304A (zh) * | 2015-05-07 | 2015-07-22 | 梅立维 | 一种新型纳米异质结太阳能光催化剂的制备及应用 |
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CN104785304A (zh) * | 2015-05-07 | 2015-07-22 | 梅立维 | 一种新型纳米异质结太阳能光催化剂的制备及应用 |
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