CN106423119A - 一种二氧化钛光催化剂的制备方法 - Google Patents
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 56
- 239000004408 titanium dioxide Substances 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 239000011941 photocatalyst Substances 0.000 title abstract description 4
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims abstract description 24
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910017604 nitric acid Inorganic materials 0.000 claims abstract description 10
- 238000005245 sintering Methods 0.000 claims abstract description 7
- 229910004353 Ti-Cu Inorganic materials 0.000 claims abstract description 6
- 239000003054 catalyst Substances 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 15
- 239000010936 titanium Substances 0.000 claims description 13
- 230000003287 optical effect Effects 0.000 claims description 9
- 229910000881 Cu alloy Inorganic materials 0.000 claims 2
- 239000006227 byproduct Substances 0.000 claims 1
- 230000001699 photocatalysis Effects 0.000 abstract description 6
- 238000006243 chemical reaction Methods 0.000 abstract description 3
- 229910000808 amorphous metal alloy Inorganic materials 0.000 abstract 1
- 239000000126 substance Substances 0.000 abstract 1
- 239000007788 liquid Substances 0.000 description 16
- 229910045601 alloy Inorganic materials 0.000 description 14
- 239000000956 alloy Substances 0.000 description 14
- 239000010949 copper Substances 0.000 description 10
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 description 8
- 229940043267 rhodamine b Drugs 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 239000000843 powder Substances 0.000 description 7
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 6
- 230000015556 catabolic process Effects 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 238000006731 degradation reaction Methods 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- 229910052719 titanium Inorganic materials 0.000 description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 5
- 229910052802 copper Inorganic materials 0.000 description 5
- 238000007146 photocatalysis Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 238000001027 hydrothermal synthesis Methods 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 238000007743 anodising Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 239000007857 degradation product Substances 0.000 description 1
- 238000005137 deposition process Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/063—Titanium; Oxides or hydroxides thereof
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
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Abstract
本发明公开了一种二氧化钛光催化剂的制备方法，该制备方法首先将Ti‑Cu非晶合金条带置于一含有质量分数为65％的硝酸溶液的密闭容器中，加入NaF以及柠檬酸；然后将此密闭容器在60～80℃下保温36～72小时后取出，最后将所得到的物质在450～550℃下烧结1～2小时即可。本发明所制二氧化钛为具有多孔六棱柱形貌的锐钛矿型二氧化钛，是一种具有良好光催化性能的二氧化钛。本发明制备方法操作简单，反应过程容易控制，所得到的二氧化钛性能优异，是一种高效经济的制备方法。
Description
技术领域：
本发明涉及一种TiO2光催化材料的制备方法，尤其涉及一种具有特殊微观形貌的二氧化钛光催化材料的制备方法。
背景技术：
自1972年日本科学家本多(Honda)和藤岛(Fujishima)在n型半导体二氧化钛电极上发现了水的光催化分解作用以来，二氧化钛作为光催化材料引起了越来越多的关注。其物理和化学性能不及取决于它本身的电子结构，而且和它的晶相，晶粒度和微观形貌有关，尤其是其微观形貌对光催化性能的影响是十分显著的。正是由于这些原因，各种各样具有不同微观形貌的二氧化钛被制备出来，利用纳米管状、纳米线状、纳米花状，杆状，六边形状等等。通过过程和反应条件控制调控二氧化钛粒子的形貌已成为重要研究方向。文献报道，F-可降低二氧化钛[001]面生长所需的能量，使其形成具有大量[001]暴露面的锐钛矿型二氧化钛，且具有优异的光催化剂性能。二氧化钛的制备方法主要包括溶胶凝胶法、水热法、气相沉积法、阳极氧化法等。目前被最为采用的方法是水热法。通过控制水热体系的反应物种类与浓度、反应液pH值、水热温度和时间等来控制水热产物的形貌结构与相组成。水热反应一般包括二氧化钛纳米颗粒的形核与长大，生长过程通过水热反应参数控制。但通常水热法所制二氧化钛结构均匀性较差，且容易产生杂晶。柠檬酸作为燃烧剂在150～200℃即可分解，在溶液中能与金属离子形成络合物，促进溶解，使反应体系升温，粉末颗粒原位长大。
发明内容：
本发明的目的是提供一种具有多孔六棱柱形貌的锐钛矿型二氧化钛的制备方法，所制二氧化钛具有大量[001]暴露面及较大的比表面积，晶型结构均匀，有利于吸附光电子及促进光生电子跃迁，光催化剂性能优异。本发明的技术解决方案是一种制备具有多孔六棱柱形貌的锐钛矿型二氧化钛的方法，具体技术方案如下：
本发明一种二氧化钛光催化剂的制备方法，该方法以非晶态Ti-Cu合金为钛源，具体步骤如下：首先将非晶态Ti-Cu合金条带置于含有浓硝酸溶液的密闭容器中，并加入浓度为0.025mol/L～0.1mol/L的NaF及浓度为0.01～0.1mol/L的柠檬酸；
然后，将该密闭容器在60～80℃下保温36～72小时；
最后，将密闭容器中反应所得的白色粉末用去离子水洗净，在450～550℃下烧结1～2小时即可。
在上述技术方案中所述非晶态Ti-Cu合金条带的总面积与浓硝酸溶液的体积比例为200～300cm2/L。
所述非晶态Ti-Cu合金条带中Ti的含量为40-45wt％。
本发明实施费用低，过程易控，操作简单，所值得的二氧化钛材料不仅具有独特的微观形貌，而且展现出优异的光催化性能。
附图说明
图1为本发明制备方法制得的二氧化钛光催化剂的SEM图。
图2为本发明制备方法制得的二氧化钛光催化剂的XRD图。
具体实施方法
对比例1
步骤一、将非晶钛铜合金Ti40Cu60(钛和铜的原子摩尔比为4:6)置于含有腐蚀液的密闭容器中，所述腐蚀液为质量分数为65％的硝酸水溶液，所述非晶钛铜合金的总面积与腐蚀液的体积比为300cm2/L。
步骤二、将该密闭容器在70℃下保温72小时。
步骤三、将密闭容器中反应所得的白色粉末用去离子水洗净，在550℃下烧结1小时。
以罗丹明B为降解物测试其光催化性能，实验操作如下：将1g/L的罗丹明B水溶液50ml倒入烧杯中。将10mg所制光催化剂放入烧杯中。浸泡0.5小时待其达到吸附饱和后，放置于40W紫外灯下(10cm)照射，80min后测其对罗丹明B的降解率。
实施例1：
步骤一、将非晶钛铜合金Ti40Cu60(钛和铜的原子摩尔比为4:6)置于含有腐蚀液的密闭容器中，所述腐蚀液为质量分数为65％的硝酸水溶液，其中加入浓度为0.025mol/L的NaF和0.01mol/L的柠檬酸，所述非晶钛铜合金的总面积与腐蚀液的体积比为300cm2/L。
步骤二、将该密闭容器在70℃下保温72小时。
步骤三、将密闭容器中反应所得的白色粉末用去离子水洗净，在550℃下烧结1小时。
按对比例1中所述方法测试催化剂对罗丹明B的降解率，结果如表1所示。
实施例2：
步骤一、将非晶钛铜合金Ti40Cu60(钛和铜的原子摩尔比为4:6)置于含有腐蚀液的密闭容器中，所述腐蚀液为质量分数为65％的硝酸水溶液，其中加入浓度为0.05mol/L的NaF及0.05mol/L的柠檬酸，所述非晶钛铜合金的总面积与腐蚀液的体积比为300cm2/L。
步骤二、将该密闭容器在70℃下保温72小时。
步骤三、将密闭容器中反应所得的白色粉末用去离子水洗净，在550℃下烧结1小时。
按对比例1中所述方法测试催化剂对罗丹明B的降解率，结果如表1所示。
实施例3：
步骤一、将非晶钛铜合金Ti40Cu60(钛和铜的原子摩尔比为4:6)置于含有腐蚀液的密闭容器中，所述腐蚀液为质量分数为65％的硝酸水溶液，其中加入浓度为0.75mol/L的NaF及0.1mol/L的柠檬酸，所述非晶钛铜合金的总面积与腐蚀液的体积比为300cm2/L。
步骤二、将该密闭容器在70℃下保温72小时。
步骤三、将密闭容器中反应所得的白色粉末用去离子水洗净，在550℃下烧结1小时。
按对比例1中所述方法测试催化剂对罗丹明B的降解率，结果如表1所示。
实施例4：
步骤一、将非晶钛铜合金Ti40Cu60(钛和铜的原子摩尔比为4:6)置于含有腐蚀液的密闭容器中，所述腐蚀液为质量分数为65％的硝酸水溶液，其中加入浓度为0.1mol/L的NaF及0.1mol/L的柠檬酸，所述非晶钛铜合金的总面积与腐蚀液的体积比为300cm2/L。
步骤二、将该密闭容器在70℃下保温72小时。
步骤三、将密闭容器中反应所得的白色粉末用去离子水洗净，在550℃下烧结1小时后制得，图1为制得的二氧化钛光催化剂的SEM图；图2为制得的二氧化钛光催化剂的XRD图。
按对比例1中所述方法测试催化剂对罗丹明B的降解率，结果如表1所示。
表1
| 催化剂 | 80min后罗丹明B降解率 |
| 对比例1 | 84.6％ |
| 实施例1 | 95.6％ |
| 实施例2 | 97.5％ |
| 实施例3 | 98.6％ |
| 实施例4 | 99.1％ |
Claims (3)
1.一种二氧化钛光催化剂的制备方法，其特征在于按照下列工序制备：将非晶态Ti-Cu合金条带置于含有浓硝酸溶液的密闭容器中，加入浓度为0.025～0.1mol/L的NaF及浓度为0.01～0.1mol/L的柠檬酸，在60-80℃下保温36～72h后取出；然后将所得产物在450～550℃下烧结1～2h后制得。
2.根据权利要求1所述的二氧化钛光催化剂的制备方法，其特征在于，所述非晶态Ti-Cu合金条带的总面积与浓硝酸的体积比例为200～300cm2/L。
3.根据权利要求1所述的二氧化钛光催化剂的制备方法，其特征在于，所述非晶态Ti-Cu合金条带中Ti的含量为40wt％-45wt％。
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20040120884A1 (en) * | 1999-12-13 | 2004-06-24 | Jonathan Sherman | Nanoparticulate titanium dioxide coatings, and processes for the production and use thereof |
| CN102580709A (zh) * | 2012-01-14 | 2012-07-18 | 天津大学 | 一种非晶纳米脱钛型二氧化钛材料及其制备方法 |
| CN104609468A (zh) * | 2013-11-04 | 2015-05-13 | 天津大学 | 一种制备具有多孔六棱柱形貌的锐钛矿型二氧化钛的方法及其应用 |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20040120884A1 (en) * | 1999-12-13 | 2004-06-24 | Jonathan Sherman | Nanoparticulate titanium dioxide coatings, and processes for the production and use thereof |
| CN102580709A (zh) * | 2012-01-14 | 2012-07-18 | 天津大学 | 一种非晶纳米脱钛型二氧化钛材料及其制备方法 |
| CN104609468A (zh) * | 2013-11-04 | 2015-05-13 | 天津大学 | 一种制备具有多孔六棱柱形貌的锐钛矿型二氧化钛的方法及其应用 |
Non-Patent Citations (1)
| Title |
|---|
| 宋秀莲: "纳米TiO2的可控制备及对丙烯酸树脂抗紫外光性能改善的研究", 《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》 * |
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