CN106179442A - 一种铈与氮共掺杂的二氧化钛光催化剂及其制备方法和应用 - Google Patents
一种铈与氮共掺杂的二氧化钛光催化剂及其制备方法和应用 Download PDFInfo
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 73
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 title claims abstract description 69
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 title claims abstract description 35
- 229910052684 Cerium Inorganic materials 0.000 title claims abstract description 33
- 229910052757 nitrogen Inorganic materials 0.000 title claims abstract description 33
- 239000004408 titanium dioxide Substances 0.000 title claims abstract description 33
- 239000003054 catalyst Substances 0.000 title claims abstract description 22
- 230000003287 optical effect Effects 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 239000011941 photocatalyst Substances 0.000 claims abstract description 16
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 6
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims abstract description 6
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 claims abstract description 6
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000000376 reactant Substances 0.000 claims abstract description 5
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 4
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims abstract description 3
- JCXJVPUVTGWSNB-UHFFFAOYSA-N nitrogen dioxide Inorganic materials O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 claims abstract description 3
- 239000002244 precipitate Substances 0.000 claims abstract description 3
- 238000003756 stirring Methods 0.000 claims abstract description 3
- 230000001699 photocatalysis Effects 0.000 claims description 7
- 238000007146 photocatalysis Methods 0.000 claims description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 3
- HGWOWDFNMKCVLG-UHFFFAOYSA-N [O--].[O--].[Ti+4].[Ti+4] Chemical group [O--].[O--].[Ti+4].[Ti+4] HGWOWDFNMKCVLG-UHFFFAOYSA-N 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 7
- 238000010521 absorption reaction Methods 0.000 abstract description 6
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical class [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 abstract description 2
- 238000000926 separation method Methods 0.000 abstract description 2
- 239000012467 final product Substances 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 239000002994 raw material Substances 0.000 description 3
- 230000015556 catabolic process Effects 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- STZCRXQWRGQSJD-UHFFFAOYSA-M sodium;4-[[4-(dimethylamino)phenyl]diazenyl]benzenesulfonate Chemical compound [Na+].C1=CC(N(C)C)=CC=C1N=NC1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-UHFFFAOYSA-M 0.000 description 2
- 238000002336 sorption--desorption measurement Methods 0.000 description 2
- 229910021642 ultra pure water Inorganic materials 0.000 description 2
- 239000012498 ultrapure water Substances 0.000 description 2
- 150000000703 Cerium Chemical class 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
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- 238000004146 energy storage Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- -1 hydroxyl radical free radical Chemical class 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- MCPLVIGCWWTHFH-UHFFFAOYSA-L methyl blue Chemical compound [Na+].[Na+].C1=CC(S(=O)(=O)[O-])=CC=C1NC1=CC=C(C(=C2C=CC(C=C2)=[NH+]C=2C=CC(=CC=2)S([O-])(=O)=O)C=2C=CC(NC=3C=CC(=CC=3)S([O-])(=O)=O)=CC=2)C=C1 MCPLVIGCWWTHFH-UHFFFAOYSA-L 0.000 description 1
- 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 description 1
- 229940012189 methyl orange Drugs 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
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- 238000013033 photocatalytic degradation reaction Methods 0.000 description 1
- 208000017983 photosensitivity disease Diseases 0.000 description 1
- 231100000434 photosensitization Toxicity 0.000 description 1
- 229950000845 politef Drugs 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
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- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
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Abstract
本发明提供了一种铈与氮共掺杂的二氧化钛光催化剂及其制备方法和应用,该光催化剂由铈、氮和二氧化钛组成,其中铈和氮以颗粒状沉着在二氧化钛表面。其制备方法是将硝酸铈、氨水和钛酸丁酯混合,滴加乙醇水溶液,搅拌,超声,然后将所得反应液在150~180℃水热反应12~24h,离心,沉淀经清洗、干燥,即得。本发明采用铈与氮共掺杂对二氧化钛进行改性,可提高二氧化钛光催化剂的可见光吸收范围及电荷分离效率,增加其可见光吸收,从而显著提高二氧化钛的可见光活性。
Description
技术领域
本发明属于光催化剂技术领域,具体涉及一种铈与氮共掺杂的二氧化钛光催化剂及其制备方法和应用。
背景技术
TiO2具有良好的生物、化学、光化学稳定性,已被广泛应用于废水处理、有害气体净化、化妆品制造、建筑材料、纺织用品、涂料、太阳能存储与转换、激光化学转化等领域。但是TiO2是宽带导体,具有较宽的禁带宽度(3.0~3.2eV),只有在近紫外光区才有活性。纯TiO2对太阳光的利用率为4%,所以,近年来为了提高TiO2的光电子效应和对太阳光的利用率,采用金属掺杂、染料的光敏化、贵金属的沉积等方法对TiO2进行改性。
发明内容
解决的技术问题:本发明的目的是解决TiO2只有在近紫外光区才有活性、仅采用金属掺杂对TiO2进行改性的技术问题,提供一种铈与氮共掺杂的二氧化钛光催化剂及其制备方法和应用,该铈与氮共掺杂的二氧化钛光催化剂不仅具有可见光活性,而且光催化活性得到明显提升。
技术方案:一种铈与氮共掺杂的二氧化钛光催化剂,该光催化剂由铈、氮和二氧化钛组成,其中铈和氮以颗粒状沉着在二氧化钛表面。
所述铈与氮共掺杂的二氧化钛光催化剂的制备方法,包括以下步骤:
步骤1,将硝酸铈、氨水和钛酸丁酯混合,滴加乙醇水溶液,搅拌,超声,得到反应液;
步骤2,将步骤2所得反应液在150~180℃水热反应12~24h,离心,沉淀经清洗、干燥,即得。
进一步地,硝酸铈、氨水和钛酸丁酯的摩尔比为0.5~1: 0.5~1:10。
进一步地,乙醇水溶液中无水乙醇与水的体积比为1:0.8~1。
进一步地,步骤1中超声功率为70W。
所述铈与氮共掺杂的二氧化钛纳米光催化剂在光催化领域的应用。
有益效果:
1. 采用铈与氮共掺杂对二氧化钛进行改性,可提高二氧化钛光催化剂的可见光吸收范围及电荷分离效率,增加其可见光吸收,从而显著提高二氧化钛的可见光活性;
2.以廉价易得的原料,通过微波法迅速制备了铈与氮共掺杂改性的二氧化钛光催化剂,操作简单、合成方便,并且效果明显;
3. 本发明的铈与氮共掺杂二氧化钛光催化剂与纯二氧化钛光催化剂相比,铈与氮共掺杂改性二氧化钛光催化剂的光催化活性得到明显提升。
附图说明
图1为实施例1的铈与氮共掺杂的二氧化钛光催化剂的SEM照片,放大倍数为50nm;
图2为实施例1的铈与氮共掺杂的二氧化钛光催化剂紫外可见漫反射谱图;
图3为实施例1的铈与氮共掺杂的二氧化钛光催化剂吸附脱附曲线图;
图4为实施例2的铈与氮共掺杂的二氧化钛光催化剂光催化降解活性曲线图。
具体实施方式
实施例1
铈与氮共掺杂的二氧化钛光催化剂的制备方法,包括以下步骤:
步骤1,将硝酸铈、氨水和钛酸丁酯按摩尔比1:1:10混合,逐滴加入50v/v%乙醇水溶液,持续搅拌半小时,70W的功率下超声2小时;
步骤2,将步骤1的溶液装入聚四氟乙烯水热反应釜水热180℃反应24小时,将最终获得的产品离心分离,用超纯水与无水乙醇分别清洗三次,放在烘箱中60℃干燥12小时,研磨备用。
本实施方式中采用的原料为市售分析纯原料。
采用扫描电子显微镜对制得的Ce-N-MT光催化剂进行电镜扫描,如图1所示,所得Ce-N-MT光催化剂为纳米片,表面有少量铈与氮共掺杂覆盖。
采用紫外可见漫反射光谱仪对制得的Ce-N-MT光催化剂进行扫描,如图2所示,所得Ce-N-MT光催化剂相对于Ce-MT和N-MT在可见光区对光的吸收明显增强,因此可以产生更多光电子与空穴分离,有助于对于污染物的降解。掺杂铈与氮越多,光催化剂在全光谱对光的吸收能力得到明显增强,这说明掺杂铈与氮共掺杂的二氧化钛对光能利用明显得到增强,吸收得到的光能越多,光电子-空穴对产生得越多,能够利用的空穴与光电子越多,空穴与光电子进而产生羟基自由基,并且空穴自身也可以氧化有机污染物。
采用全自动比表面积仪对制得的Ce-N-MT光催化剂进行扫描,如图3所示,所得Ce-N-MT光催化剂的表面积较大。表面积较大可能是超声辅助中,产生的空化作用对Ce-N-MT的分散有较大作用,表面积较大,活性位点较多,有助于光催化反应的产生,降解污染物的作用增强。
实施例2
采用实施例1制备得到的光催化剂用于氧化处理甲基橙溶液。降解步骤为:
步骤1,准确称取20mg的甲基蓝,将其溶于超纯水中,并定容至1000mL,制得20mg/L的甲基橙溶液;
步骤2,用移液管准确移取50mL步骤1得到的甲基橙溶液至反应器中,并分别加入40mg掺杂质量分数为1% AC的TiO2光催化剂(Ce-N-MT),反应体系控制在25℃,分别调节催化剂浓度为,在暗光处先吸附平衡半小时,使其达到吸附脱附平衡;
步骤3:以300w氙灯作为可见光源,将步骤2所得溶液在光照下进行光催化降解反应,每间隔5~30min时间取样,并用紫外-可见分光光度法测量甲基橙吸光度,并计算其转化率。结果见图4。从图中可以看出当催化剂为Ce-N-MT时,催化效果最好,因为铈与氮共掺杂的引入对材料对可见光吸收加强,并且铈与氮共掺杂还可以传导二氧化钛导带的电子,二氧化钛的光生电子与空穴分离效果增强。
Claims (6)
1.一种铈与氮共掺杂的二氧化钛光催化剂,其特征在于:该光催化剂由铈、氮和二氧化钛组成,其中铈和氮以颗粒状沉着在二氧化钛表面。
2.权利要求1所述的铈与氮共掺杂的二氧化钛光催化剂的制备方法,其特征在于:包括以下步骤:
步骤1,将硝酸铈、氨水和钛酸丁酯混合,滴加乙醇水溶液,搅拌,超声,得到反应液;
步骤2,将步骤2所得反应液在150~180℃水热反应12~24h,离心,沉淀经清洗、干燥,即得。
3.根据权利要求2所述的铈与氮共掺杂的二氧化钛光催化剂的制备方法,其特征在于:硝酸铈、氨水和钛酸丁酯的摩尔比为0.5~1: 0.5~1:10。
4.根据权利要求2所述的铈与氮共掺杂的二氧化钛光催化剂的制备方法,其特征在于:乙醇水溶液中无水乙醇与水的体积比为1:0.8~1。
5.根据权利要求2所述的铈与氮共掺杂的二氧化钛光催化剂的制备方法,其特征在于:步骤1中超声功率为70W。
6.权利要求1所述铈与氮共掺杂的二氧化钛纳米光催化剂在光催化领域的应用。
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