CN102674451A - Preparation method of {001} face exposed titanium dioxide nanocrystals - Google Patents
Preparation method of {001} face exposed titanium dioxide nanocrystals Download PDFInfo
- Publication number
- CN102674451A CN102674451A CN201210159220XA CN201210159220A CN102674451A CN 102674451 A CN102674451 A CN 102674451A CN 201210159220X A CN201210159220X A CN 201210159220XA CN 201210159220 A CN201210159220 A CN 201210159220A CN 102674451 A CN102674451 A CN 102674451A
- Authority
- CN
- China
- Prior art keywords
- titanium dioxide
- alcohol
- exposed
- nanocrystals
- solution
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 144
- 239000004408 titanium dioxide Substances 0.000 title claims abstract description 58
- 239000002159 nanocrystal Substances 0.000 title claims abstract description 53
- 238000002360 preparation method Methods 0.000 title claims description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 64
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000000034 method Methods 0.000 claims abstract description 21
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000002244 precipitate Substances 0.000 claims abstract description 20
- LLZRNZOLAXHGLL-UHFFFAOYSA-J titanic acid Chemical compound O[Ti](O)(O)O LLZRNZOLAXHGLL-UHFFFAOYSA-J 0.000 claims abstract description 17
- 239000007864 aqueous solution Substances 0.000 claims abstract description 10
- -1 polytetrafluoroethylene Polymers 0.000 claims abstract description 10
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims abstract description 7
- 239000004810 polytetrafluoroethylene Substances 0.000 claims abstract description 7
- 238000012546 transfer Methods 0.000 claims abstract description 6
- 239000000243 solution Substances 0.000 claims description 39
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 25
- 238000003756 stirring Methods 0.000 claims description 20
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- 238000006243 chemical reaction Methods 0.000 claims description 12
- 239000003513 alkali Substances 0.000 claims description 10
- 239000008367 deionised water Substances 0.000 claims description 10
- 229910021641 deionized water Inorganic materials 0.000 claims description 10
- 150000003608 titanium Chemical class 0.000 claims description 9
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 6
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims description 6
- DCKVFVYPWDKYDN-UHFFFAOYSA-L oxygen(2-);titanium(4+);sulfate Chemical compound [O-2].[Ti+4].[O-]S([O-])(=O)=O DCKVFVYPWDKYDN-UHFFFAOYSA-L 0.000 claims description 6
- 230000007935 neutral effect Effects 0.000 claims description 5
- 239000006228 supernatant Substances 0.000 claims description 5
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 3
- 238000000227 grinding Methods 0.000 claims description 3
- 238000004321 preservation Methods 0.000 claims description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 3
- 229910000349 titanium oxysulfate Inorganic materials 0.000 claims description 3
- 229910000348 titanium sulfate Inorganic materials 0.000 claims description 3
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 3
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 239000013078 crystal Substances 0.000 abstract description 15
- 239000000047 product Substances 0.000 abstract description 10
- 239000002245 particle Substances 0.000 abstract description 7
- 238000002474 experimental method Methods 0.000 description 25
- 230000001699 photocatalysis Effects 0.000 description 9
- HFZWRUODUSTPEG-UHFFFAOYSA-N 2,4-dichlorophenol Chemical compound OC1=CC=C(Cl)C=C1Cl HFZWRUODUSTPEG-UHFFFAOYSA-N 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 239000002243 precursor Substances 0.000 description 5
- 239000010936 titanium Substances 0.000 description 5
- 229910052719 titanium Inorganic materials 0.000 description 4
- 238000002371 ultraviolet--visible spectrum Methods 0.000 description 4
- 229910010413 TiO 2 Inorganic materials 0.000 description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 238000003917 TEM image Methods 0.000 description 2
- 239000002800 charge carrier Substances 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 238000003795 desorption Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000002336 sorption--desorption measurement Methods 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- ISPYQTSUDJAMAB-UHFFFAOYSA-N 2-chlorophenol Chemical compound OC1=CC=CC=C1Cl ISPYQTSUDJAMAB-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 238000004887 air purification Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000011941 photocatalyst Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000004729 solvothermal method Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 239000011882 ultra-fine particle Substances 0.000 description 1
- 238000012795 verification Methods 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
Images
Landscapes
- Catalysts (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
一种{001}面暴露二氧化钛纳米晶的制备方法，它涉及一种纳米晶的制备方法。本发明解决了现有方法制备的{001}面暴露二氧化钛纳米晶颗粒尺寸大、比表面积小的技术问题。本方法如下：一、制备质子化水合钛酸；二、将质子化水合钛酸用醇洗涤，然后转移到聚四氟乙烯水热釜中，加入醇和氢氟酸水溶液，保温，离心分离出沉淀，水洗、醇洗、干燥、研磨，即得{001}面暴露二氧化钛纳米晶。采用本方法得到的二氧化钛产品为纯锐钛矿相，{001}面暴露率为26％～66％，比表面积最高为155m2g-1，晶体平均粒径最小为11nm。
The invention discloses a method for preparing titanium dioxide nanocrystals with {001} faces exposed, which relates to a method for preparing nanocrystals. The invention solves the technical problem that the {001} surface exposed titanium dioxide nanocrystal particle size is large and the specific surface area is small. The method is as follows: 1. Prepare protonated hydrated titanic acid; 2. Wash the protonated hydrated titanic acid with alcohol, then transfer it to a polytetrafluoroethylene hydrothermal kettle, add alcohol and hydrofluoric acid aqueous solution, keep warm, and centrifuge to separate out the precipitate , washed with water, washed with alcohol, dried, and ground to obtain titanium dioxide nanocrystals with exposed {001} surfaces. The titanium dioxide product obtained by the method is a pure anatase phase, the {001} plane exposure rate is 26%-66%, the specific surface area is the highest 155m 2 g -1 , and the average crystal particle size is the smallest 11nm.
Description
技术领域 technical field
本发明涉及一种纳米晶的制备方法。The invention relates to a preparation method of nano crystals.
背景技术 Background technique
近年来，光催化技术作为治理环境问题最有效的方法之一而引起世界各国的广泛关注。二氧化钛光催化剂因其具有价廉、无毒、催化活性高、氧化能力强、化学稳定性好、抗磨损性和可以循环利用等优点，而成为环境处理中最为理想的催化剂。TiO2的光催化性能主要取决于晶相、暴露晶面、晶粒尺寸和比表面积。常见的TiO2有三种晶型，分别是锐钛矿、金红石和板钛矿。其中锐钛矿由于光生载荷子的氧化还原能力较强，并且表面易于吸附氧而增强光生载荷子的寿命，所以具有更高的光催化活性。理论和实验都表明，锐钛矿{001}面是高能晶面，其活性优于热力学更稳定的{101}面(表面能：{001}面为0.90J m-2，而{101}面为0.44J m-2)。因此，制备高能{001}面就成为二氧化钛晶面工程中的研究热点。In recent years, photocatalytic technology, as one of the most effective methods to control environmental problems, has attracted widespread attention from all over the world. Titanium dioxide photocatalyst has become the most ideal catalyst in environmental treatment because of its advantages of low price, non-toxicity, high catalytic activity, strong oxidation ability, good chemical stability, wear resistance and recyclability. The photocatalytic performance of TiO2 mainly depends on the crystal phase, exposed crystal plane, grain size and specific surface area. Common TiO 2 has three crystal forms, namely anatase, rutile and brookite. Among them, anatase has a higher photocatalytic activity due to the strong redox ability of photogenerated charge carriers and the easy adsorption of oxygen on the surface to enhance the life of photogenerated charge carriers. Both theory and experiments show that the {001} plane of anatase is a high-energy crystal plane, and its activity is better than that of the more thermodynamically stable {101} plane (surface energy: {001} plane is 0.90J m -2 , while {101} plane is 0.44J m -2 ). Therefore, the preparation of high-energy {001} facets has become a research hotspot in the facet engineering of titania.
2008年，Yang Huagui课题组克服了相关的技术困难，通过水热法合成出了{001}面暴露率为47％的锐钛矿相二氧化钛单晶(H.G.Yang，C.H.Sun，S.Z.Qiao，J.Zou，G.Liu，S.C.Smith，H.M.Cheng and G.Q.Lu，Nature，2008，453，638.)，随后又将比例提高至64％，但是所得二氧化钛单晶的平均尺寸达1.09μm，比表面积仅有1.6m2g-1(H.G.Yang，G.Liu，S.Z.Qiao，C.H.Sun，Y.G.Jin，S.C.Smith，J.Zou，H.M.Cheng and G.Q.Lu，J.Am.Chem.Soc.，2009，131，4078)。对于异质反应，较小的晶粒尺寸意味着较大的比表面积和更多的活性位点，这有利于反应物跟二氧化钛纳米晶体的充分接触，并最终增强材料的光催化活性。而目前{001}面暴露锐钛矿相二氧化钛的制备方法中，大多直接以钛盐、钛醇盐或钛粉为前躯体，所得产物的晶粒尺寸普遍为数百纳米左右甚至微米级。原因在于，钛盐、钛醇盐和钛粉在含水的溶剂热体系反应活性较高(B.H.Wu，C.Y.Guo，N.F.Zheng，Z.X.Xieand G.D.Stucky，J.Am.Chem.Soc.，2008，130，17563.)，如果直接用于制备{001}面暴露锐钛矿相二氧化钛，则产物的晶体生长过程较难控制，所得二氧化钛颗粒尺寸往往比较大，比表面积也较小，不利于材料催化活性的提高(S.W.Liu，J.G.Yu and M.Jaroniec，J.Am.Chem.Soc.，2010，132，11914.)。因此，寻找新型前躯体来制备纳米级{001}面暴露锐钛矿相二氧化钛，已成为该领域研究的重要突破点。In 2008, Yang Huagui's research group overcame the relevant technical difficulties and synthesized an anatase titanium dioxide single crystal with {001} surface exposure rate of 47% by hydrothermal method (HGYang, CHSun, SZQiao, J.Zou, G .Liu, SCSmith, HMCheng and GQLu, Nature, 2008, 453, 638.), and then increased the proportion to 64%, but the average size of the obtained titanium dioxide single crystal reached 1.09 μm, and the specific surface area was only 1.6m 2 g -1 (HG Yang, G. Liu, SZ Qiao, CH Sun, YG Jin, SCSmith, J. Zou, HM Cheng and GQ Lu, J. Am. Chem. Soc., 2009, 131, 4078). For heterogeneous reactions, smaller grain size means larger specific surface area and more active sites, which is conducive to the full contact of reactants with titanium dioxide nanocrystals, and ultimately enhances the photocatalytic activity of the material. However, most of the current preparation methods of {001} surface-exposed anatase phase titanium dioxide directly use titanium salt, titanium alkoxide or titanium powder as the precursor, and the grain size of the obtained product is generally around hundreds of nanometers or even micrometers. The reason is that titanium salt, titanium alkoxide and titanium powder have higher reactivity in aqueous solvothermal systems (BHWu, CYGuo, NFZheng, ZXXieand GDStucky, J.Am.Chem.Soc., 2008, 130, 17563.), if If it is directly used to prepare {001} exposed anatase phase titanium dioxide, the crystal growth process of the product is difficult to control, and the obtained titanium dioxide particle size is often relatively large, and the specific surface area is also small, which is not conducive to the improvement of the catalytic activity of the material (SWLiu, JGYu and M. Jaroniec, J. Am. Chem. Soc., 2010, 132, 11914.). Therefore, finding new precursors to prepare nanoscale {001} facet-exposed anatase phase titanium dioxide has become an important breakthrough in research in this field.
发明内容Contents of the invention
本发明是为了解决现有方法制备的{001}面暴露二氧化钛纳米晶颗粒尺寸大、比表面积小的技术问题，提供了一种{001}面暴露二氧化钛纳米晶的制备方法。The present invention aims to solve the technical problem of large particle size and small specific surface area of {001} surface-exposed titanium dioxide nanocrystals prepared by the existing method, and provides a preparation method of {001} surface-exposed titanium dioxide nanocrystals.
一种{001}面暴露二氧化钛纳米晶的制备方法，具体步骤如下：A method for preparing titanium dioxide nanocrystals exposed on a {001} surface, the specific steps are as follows:
一、将钛盐加入到乙醇或异丙醇中，配制成50mL～100mL浓度为0.1mol/L～0.5mol/L的醇溶液；1. Add titanium salt to ethanol or isopropanol to prepare 50mL-100mL alcohol solution with a concentration of 0.1mol/L-0.5mol/L;
二、在搅拌条件下将步骤一制备的醇溶液滴入到60mL～120mL去离子水中，然后在水浴温度为60℃～90℃的条件下，以300～1000转/分钟的搅拌速度搅拌30分钟～100分钟，加入0.5mol/L～5.0mol/L的碱溶液50mL～300mL，密封，然后在60℃～90℃继续搅拌4小时～12小时，离心分离出白色沉淀，并用去离子水洗涤白色沉淀3～5次，至上清液pH值为中性，得到质子化水合钛酸；2. Drop the alcohol solution prepared in Step 1 into 60mL-120mL deionized water under stirring conditions, and then stir for 30 minutes at a stirring speed of 300-1000 rpm at a water bath temperature of 60°C-90°C ～100 minutes, add 50mL～300mL of 0.5mol/L～5.0mol/L alkali solution, seal it, then continue to stir at 60℃～90℃ for 4 hours～12 hours, centrifuge to separate the white precipitate, and wash the white precipitate with deionized water Precipitate for 3 to 5 times until the pH value of the supernatant is neutral to obtain protonated hydrated titanic acid;
三、将质子化水合钛酸用醇洗涤3～5次，然后转移到聚四氟乙烯水热釜中，加入2mL～6mL醇和0.5mL～5mL质量浓度为20％～40％的氢氟酸水溶液，在150℃～220℃保温12小时～48小时；3. Wash the protonated hydrated titanic acid with alcohol for 3 to 5 times, then transfer it to a polytetrafluoroethylene hydrothermal kettle, add 2mL to 6mL of alcohol and 0.5mL to 5mL of hydrofluoric acid aqueous solution with a mass concentration of 20% to 40%. , heat preservation at 150°C to 220°C for 12 hours to 48 hours;
四、将步骤三得到的反应液在转速为3000转/分钟～8000转/分钟的条件下离心分离出沉淀，然后在60℃～100℃下干燥24h～48h，经水洗、醇洗、干燥、研磨，即得{001}面暴露二氧化钛纳米晶。4. Centrifuge the reaction solution obtained in step 3 to separate the precipitate at a speed of 3000 rpm to 8000 rpm, then dry at 60°C to 100°C for 24h to 48h, wash with water, wash with alcohol, dry, Grinding to obtain titanium dioxide nanocrystals exposed on the {001} surface.
步骤一中所述的钛盐为四氯化钛、硫酸钛、硫酸氧钛、钛酸丁酯或钛酸异丙酯。The titanium salt described in step 1 is titanium tetrachloride, titanium sulfate, titanium oxysulfate, butyl titanate or isopropyl titanate.
步骤二中所述的碱溶液为氢氧化钠溶液、氢氧化钾溶液或碳酸钠溶液。The alkali solution described in step 2 is sodium hydroxide solution, potassium hydroxide solution or sodium carbonate solution.
步骤三中所述的醇为乙醇或异丙醇。The alcohol described in step 3 is ethanol or Virahol.
步骤四中醇洗所用的醇为乙醇或异丙醇。Alcohol used for alcohol washing in step 4 is ethanol or isopropanol.
本发明针对现有前躯体制得的{001}面暴露锐钛矿相二氧化钛粒径偏大，比表面积过低，光催化活性不高等严重缺陷，采用质子化水合钛酸为新颖的前驱体，在溶剂热体系制备{001}面暴露二氧化钛纳米晶。采用本方法得到的二氧化钛产品为纯锐钛矿相，{001}面暴露率为26％～66％，比表面积最高为155m2g-1，晶体平均粒径最小为11nm，其光催化效率显著优于传统方法制备的大尺寸{001}面暴露二氧化钛。且使用的原材料价廉易得，操作简便，设备与工艺简单，可以广泛用作光催化材料和光电材料，能够用于治理废水、净化空气、光电转换等方面。The present invention aims at serious defects such as large particle size, too low specific surface area and low photocatalytic activity of the {001} surface-exposed anatase phase titanium dioxide produced by the existing precursor, and adopts protonated hydrated titanic acid as a novel precursor, Preparation of {001} facet-exposed titania nanocrystals in a solvothermal system. The titanium dioxide product obtained by this method is a pure anatase phase, the {001} surface exposure rate is 26% to 66%, the specific surface area is the highest at 155m 2 g -1 , and the average crystal particle size is the smallest at 11nm, and its photocatalytic efficiency is remarkable It is superior to the large-size {001} surface exposed titanium dioxide prepared by traditional methods. Moreover, the raw materials used are cheap and easy to obtain, the operation is simple, the equipment and the process are simple, and can be widely used as photocatalytic materials and photoelectric materials, and can be used in wastewater treatment, air purification, photoelectric conversion and other aspects.
质子化水合钛酸(H2Ti5O11·3H2O)具有和锐钛矿似的晶格结构，例如边共享和锯齿形结构。溶剂热反应过程中，层状的质子化水合钛酸可以保持锯齿形晶格结构不变而直接裂解生成锐钛矿超细颗粒，随后通过晶体生长过程逐渐长大，故可以通过调控体系组成和反应条件实现产物形貌和尺寸的可控制备，更重要的是，与钛盐、钛醇盐和钛粉相比，这种层状的质子化钛酸在和氢氟酸反应的过程中表现更加温和，从而更有利于晶体的生长控制。因此，采用质子化水合钛酸为新颖的前驱体制备{001}面暴露二氧化钛纳米晶，反应过程温和，所得产物{001}面暴露率与晶粒尺寸可控，比表面积大，催化活性高，在环境治理和光电材料等方面具有潜在的应用价值和广阔的市场前景。Protonated hydrated titanic acid (H 2 Ti 5 O 11 ·3H 2 O) has a lattice structure similar to anatase, such as edge-sharing and zigzag structures. During the solvothermal reaction, the layered protonated hydrated titanic acid can keep the zigzag lattice structure unchanged and directly crack to generate anatase ultrafine particles, and then gradually grow up through the crystal growth process, so it can be controlled by adjusting the composition of the system and The reaction conditions achieve controllable preparation of product morphology and size. More importantly, compared with titanium salts, titanium alkoxides and titanium powders, this layered protonated titanic acid behaves better during the reaction with hydrofluoric acid. It is milder, which is more conducive to the growth control of crystals. Therefore, using protonated hydrated titanic acid as a novel precursor to prepare {001} surface-exposed titanium dioxide nanocrystals, the reaction process is mild, and the obtained product {001} surface exposure rate and grain size are controllable, with large specific surface area and high catalytic activity. It has potential application value and broad market prospects in environmental governance and photoelectric materials.
附图说明 Description of drawings
图1是实验一制备的{001}面暴露二氧化钛纳米晶的透射电镜照片；Figure 1 is a transmission electron microscope photo of the {001} surface exposed titanium dioxide nanocrystals prepared in Experiment 1;
图2是实验一制备的{001}面暴露二氧化钛纳米晶的高分辨透射电镜照片；Figure 2 is a high-resolution transmission electron microscope photo of the {001} surface exposed titanium dioxide nanocrystals prepared in Experiment 1;
图3是实验一制备的{001}面暴露二氧化钛纳米晶的XRD图谱；Fig. 3 is the XRD spectrum of the {001} surface exposed titanium dioxide nanocrystal prepared in Experiment 1;
图4是实验二制备的{001}面暴露二氧化钛纳米晶的透射电镜照片；Fig. 4 is the transmission electron micrograph of the {001} surface exposed titanium dioxide nanocrystal prepared in Experiment 2;
图5是实验三制备的{001}面暴露二氧化钛纳米晶的透射电镜照片；Figure 5 is a transmission electron micrograph of the {001} surface exposed titanium dioxide nanocrystals prepared in Experiment 3;
图6是实验三制备的{001}面暴露二氧化钛纳米晶的透射电镜照片；Fig. 6 is a transmission electron microscope photograph of {001} surface exposed titanium dioxide nanocrystals prepared in Experiment 3;
图7是实验三制备的{001}面暴露二氧化钛纳米晶的XRD图谱；Figure 7 is the XRD spectrum of the {001} surface exposed titanium dioxide nanocrystals prepared in Experiment 3;
图8是实验二制备的{001}面暴露二氧化钛纳米晶的N2气吸附/脱附等温线，图中-●-代表脱附等温线，-◆-代表吸附等温线；Fig. 8 is the N 2 gas adsorption/desorption isotherm of titanium dioxide nanocrystals exposed to the {001} surface prepared in Experiment 2, in which -●- represents the desorption isotherm, and -◆- represents the adsorption isotherm;
图9是实验三制备的{001}面暴露二氧化钛纳米晶的N2气吸附/脱附等温线，图中-●-代表脱附等温线，-■-代表吸附等温线；Fig. 9 is the N2 gas adsorption/desorption isotherm of titanium dioxide nanocrystals exposed to the {001} surface prepared in Experiment 3, in which -●- represents the desorption isotherm, and -■- represents the adsorption isotherm;
图10是实验二制备的{001}面暴露二氧化钛纳米晶与实验三制备的{001}面暴露二氧化钛纳米晶紫外光催化降解有机染料2，4-二氯苯酚，随时间变化的紫外-可见光谱图，图中a表示实验三制备的{001}面暴露二氧化钛纳米晶紫外光催化降解有机染料2，4-二氯苯酚，随时间变化的紫外-可见光谱图，b表示实验二制备的{001}面暴露二氧化钛纳米晶紫外光催化降解有机染料2，4-二氯苯酚，随时间变化的紫外-可见光谱图。Figure 10 is the ultraviolet-visible spectrum of the photocatalytic degradation of the organic dye 2,4-dichlorophenol for the {001} surface-exposed titanium dioxide nanocrystals prepared in Experiment 2 and the {001} surface-exposed titanium dioxide nanocrystals prepared in Experiment 3. In the figure, a represents the ultraviolet-visible spectrum of the {001} surface exposed titanium dioxide nanocrystals prepared in Experiment 3 for UV photocatalytic degradation of organic dye 2,4-dichlorophenol, and time-varying UV-Vis spectra, and b represents the {001} prepared in Experiment 2 UV photocatalytic degradation of organic dye 2,4-dichlorophenol by exposure of TiO nanocrystals on the surface of } surface, UV-visible spectrum changing with time.
具体实施方式 Detailed ways
本发明技术方案不局限于以下所列举具体实施方式，还包括各具体实施方式间的任意组合。The technical solution of the present invention is not limited to the specific embodiments listed below, but also includes any combination of the specific embodiments.
具体实施方式一：本实施方式一种{001}面暴露二氧化钛纳米晶的制备方法，具体步骤如下：Specific implementation mode 1: In this implementation mode, a method for preparing titanium dioxide nanocrystals exposed on the {001} surface, the specific steps are as follows:
一、将钛盐加入到乙醇或异丙醇中，配制成50mL～100mL浓度为0.1mol/L～0.5mol/L的醇溶液；1. Add titanium salt to ethanol or isopropanol to prepare 50mL-100mL alcohol solution with a concentration of 0.1mol/L-0.5mol/L;
二、在搅拌条件下将步骤一制备的醇溶液滴入到60mL～120mL去离子水中，然后在水浴温度为60℃～90℃的条件下，以300～1000转/分钟的搅拌速度搅拌30分钟～100分钟，加入0.5mol/L～5.0mol/L的碱溶液50mL～300mL，密封，然后在60℃～90℃继续搅拌4小时～12小时，离心分离出白色沉淀，并用去离子水洗涤白色沉淀3～5次，至上清液pH值为中性，得到质子化水合钛酸；2. Drop the alcohol solution prepared in Step 1 into 60mL-120mL deionized water under stirring conditions, and then stir for 30 minutes at a stirring speed of 300-1000 rpm at a water bath temperature of 60°C-90°C ～100 minutes, add 50mL～300mL of 0.5mol/L～5.0mol/L alkali solution, seal it, then continue to stir at 60℃～90℃ for 4 hours～12 hours, centrifuge to separate the white precipitate, and wash the white precipitate with deionized water Precipitate for 3 to 5 times until the pH value of the supernatant is neutral to obtain protonated hydrated titanic acid;
三、将质子化水合钛酸用醇洗涤3～5次，然后转移到聚四氟乙烯水热釜中，加入2mL～6mL醇和0.5mL～5mL质量浓度为20％～40％的氢氟酸水溶液，在150℃～220℃保温12小时～48小时；3. Wash the protonated hydrated titanic acid with alcohol for 3 to 5 times, then transfer it to a polytetrafluoroethylene hydrothermal kettle, add 2mL to 6mL of alcohol and 0.5mL to 5mL of hydrofluoric acid aqueous solution with a mass concentration of 20% to 40%. , heat preservation at 150°C to 220°C for 12 hours to 48 hours;
四、将步骤三得到的反应液在转速为3000转/分钟～8000转/分钟的条件下离心分离出沉淀，然后在60℃～100℃下干燥24h～48h，经水洗、醇洗、干燥、研磨，即得{001}面暴露二氧化钛纳米晶。4. Centrifuge the reaction solution obtained in step 3 to separate the precipitate at a speed of 3000 rpm to 8000 rpm, then dry at 60°C to 100°C for 24h to 48h, wash with water, wash with alcohol, dry, Grinding to obtain titanium dioxide nanocrystals exposed on the {001} surface.
采用本实施方式方法得到的二氧化钛产品为纯锐钛矿相，{001}面暴露率为26％～66％，比表面积最高为155m2g-1，晶体平均粒径最小为11nm，The titanium dioxide product obtained by the method of this embodiment is a pure anatase phase, the {001} surface exposure rate is 26% to 66%, the specific surface area is up to 155m 2 g -1 , and the average crystal particle size is the smallest 11nm.
具体实施方式二：本实施方式与具体实施方式一不同的是步骤一中所述的钛盐为四氯化钛、硫酸钛、硫酸氧钛、钛酸丁酯或钛酸异丙酯。其它与具体实施方式一相同。Embodiment 2: This embodiment differs from Embodiment 1 in that the titanium salt described in Step 1 is titanium tetrachloride, titanium sulfate, titanium oxysulfate, butyl titanate or isopropyl titanate. Others are the same as in the first embodiment.
具体实施方式三：本实施方式与具体实施方式一不同的是步骤二中所述的碱溶液为氢氧化钠溶液、氢氧化钾溶液或碳酸钠溶液。其它与具体实施方式一相同。Embodiment 3: The difference between this embodiment and Embodiment 1 is that the alkali solution described in step 2 is sodium hydroxide solution, potassium hydroxide solution or sodium carbonate solution. Others are the same as in the first embodiment.
具体实施方式四：本实施方式与具体实施方式一不同的是步骤三中所述的醇为乙醇或异丙醇。其它与具体实施方式一相同。Embodiment 4: This embodiment differs from Embodiment 1 in that the alcohol described in step 3 is ethanol or isopropanol. Others are the same as in the first embodiment.
具体实施方式五：本实施方式与具体实施方式一不同的是步骤四中醇洗所用的醇为乙醇或异丙醇。其它与具体实施方式一相同。Embodiment 5: This embodiment is different from Embodiment 1 in that the alcohol used for alcohol washing in step 4 is ethanol or isopropanol. Others are the same as in the first embodiment.
具体实施方式六：本实施方式与具体实施方式一至五之一不同的是步骤一中所述醇溶液的浓度为0.2mol/L～0.4mol/L。其它与具体实施方式一至五之一相同。Embodiment 6: This embodiment differs from Embodiments 1 to 5 in that the concentration of the alcohol solution in step 1 is 0.2 mol/L-0.4 mol/L. Others are the same as one of the specific embodiments 1 to 5.
具体实施方式七：本实施方式与具体实施方式一至五之一不同的是步骤一中所述醇溶液的浓度为0.3mol/L。其它与具体实施方式一至五之一相同。Embodiment 7: This embodiment is different from Embodiment 1 to
具体实施方式八：本实施方式与具体实施方式一至五之一不同的是步骤二中所述碱溶液的浓度为1mol/L～4mol/L。其它与具体实施方式一至五之一相同。Embodiment 8: This embodiment differs from Embodiments 1 to 5 in that the concentration of the alkali solution in step 2 is 1 mol/L-4 mol/L. Others are the same as one of the specific embodiments 1 to 5.
具体实施方式九：本实施方式与具体实施方式一至五之一不同的是步骤二中所述碱溶液的浓度为1mol/L。其它与具体实施方式一至五之一相同。Embodiment 9: This embodiment differs from Embodiment 1 to
具体实施方式十：本实施方式与具体实施方式一至五之一不同的是步骤三中所述氢氟酸水溶液的质量浓度为40％。其它与具体实施方式一至五之一相同。Embodiment 10: The difference between this embodiment and one of Embodiments 1 to 5 is that the mass concentration of the hydrofluoric acid aqueous solution in step 3 is 40%. Others are the same as one of the specific embodiments 1 to 5.
采用下述实验验证本发明效果：Adopt following experiment verification effect of the present invention:
实验一：experiment one:
一种{001}面暴露二氧化钛纳米晶的制备方法如下：A preparation method of {001} surface exposed titanium dioxide nanocrystals is as follows:
一、将钛酸丁酯加入到乙醇中，配制成75mL浓度为0.35mol/L的醇溶液；1. Add butyl titanate to ethanol to prepare 75 mL of alcohol solution with a concentration of 0.35 mol/L;
二、在搅拌条件下将步骤一制备的醇溶液滴入到90mL去离子水中，然后在水浴温度为70℃的条件下，以500转/分钟的搅拌速度继续搅拌50分钟，加入1mol/L的氢氧化钠溶液300mL，密封，然后在70℃继续搅拌12小时，离心分离出白色沉淀，并用去离子水洗涤白色沉淀4次，至上清液pH值为中性，得到质子化水合钛酸；2. Drop the alcohol solution prepared in Step 1 into 90 mL of deionized water under stirring conditions, then continue stirring at a stirring speed of 500 rpm for 50 minutes at a water bath temperature of 70 ° C, and add 1 mol/L of Sodium hydroxide solution 300mL, sealed, then continued to stir at 70°C for 12 hours, centrifuged to separate the white precipitate, and washed the white precipitate with deionized water 4 times until the pH value of the supernatant was neutral to obtain protonated hydrated titanic acid;
三、将质子化水合钛酸用异丙醇洗涤3次，然后转移到聚四氟乙烯水热釜(容积为40mL)中，加入6mL异丙醇和0.5mL质量浓度为40％的氢氟酸水溶液，在180℃保温12小时；3. Wash the protonated hydrated titanic acid 3 times with isopropanol, then transfer it to a polytetrafluoroethylene hydrothermal kettle (40 mL in volume), add 6 mL of isopropanol and 0.5 mL of 40% hydrofluoric acid aqueous solution , kept at 180°C for 12 hours;
四、将步骤三得到的反应液在转速为4000转/分钟的条件下离心分离出沉淀，然后在60℃下干燥24h，经水洗、乙醇洗涤、干燥、研磨，即得{001}面暴露二氧化钛纳米晶。4. Centrifuge the reaction solution obtained in step 3 at a speed of 4000 rpm to separate the precipitate, then dry it at 60°C for 24 hours, wash with water, wash with ethanol, dry, and grind to obtain {001} surface-exposed titanium dioxide Nanocrystalline.
由图1(图中标尺为100纳米)看出产物为均匀分散的纳米晶，尺寸分布均匀，大约为11nm，{001}面所占比例约为26％。It can be seen from Figure 1 (the scale in the figure is 100 nanometers) that the product is uniformly dispersed nanocrystals with a uniform size distribution of about 11 nm, and the proportion of {001} planes is about 26%.
由图2可知两组交叉晶面分别为锐钛矿的{101}面和{011}面。It can be seen from Figure 2 that the two sets of intersecting crystal planes are the {101} plane and {011} plane of anatase, respectively.
由图3可知TiO2为纯锐钛矿相，且结晶性能良好。It can be seen from Figure 3 that TiO 2 is a pure anatase phase with good crystallization properties.
由图8可知本实验制备的{001}面暴露二氧化钛纳米晶的比表面积为155m2g-1。It can be seen from Fig. 8 that the specific surface area of the {001} plane-exposed titanium dioxide nanocrystals prepared in this experiment is 155 m 2 g -1 .
实验二：Experiment 2:
一种{001}面暴露二氧化钛纳米晶的制备方法如下：A preparation method of {001} surface exposed titanium dioxide nanocrystals is as follows:
一、将钛酸丁酯加入到乙醇中，配制成75mL浓度为0.35mol/L的醇溶液；1. Add butyl titanate to ethanol to prepare 75 mL of alcohol solution with a concentration of 0.35 mol/L;
二、在搅拌条件下将步骤一制备的醇溶液滴入到90mL去离子水中，然后在水浴温度为70℃的条件下，以500转/分钟的搅拌速度搅拌50分钟，加入1.0mol/L的氢氧化钠溶液300mL，密封，然后在70℃继续搅拌12小时，离心分离出白色沉淀，并用去离子水洗涤白色沉淀4次，至上清液pH值为中性，得到质子化水合钛酸；2. Drop the alcohol solution prepared in Step 1 into 90 mL of deionized water under stirring conditions, then stir at a stirring speed of 500 rpm for 50 minutes at a water bath temperature of 70 ° C, and add 1.0 mol/L of Sodium hydroxide solution 300mL, sealed, then continued to stir at 70°C for 12 hours, centrifuged to separate the white precipitate, and washed the white precipitate with deionized water 4 times until the pH value of the supernatant was neutral to obtain protonated hydrated titanic acid;
三、将质子化水合钛酸用醇洗涤3次，然后转移到聚四氟乙烯水热釜中，加入6mL异丙醇和1mL质量浓度为40％的氢氟酸水溶液，在180℃保温12小时；3. Wash the protonated hydrated titanic acid 3 times with alcohol, then transfer it to a polytetrafluoroethylene hydrothermal kettle, add 6mL isopropanol and 1mL hydrofluoric acid aqueous solution with a mass concentration of 40%, and keep warm at 180°C for 12 hours;
四、将步骤三得到的反应液在转速为4000转/分钟的条件下离心分离出沉淀，然后在60℃下干燥24h，经水洗、乙醇洗涤、干燥、研磨，即得{001}面暴露二氧化钛纳米晶。4. Centrifuge the reaction solution obtained in step 3 at a speed of 4000 rpm to separate the precipitate, then dry it at 60°C for 24 hours, wash with water, wash with ethanol, dry, and grind to obtain {001} surface-exposed titanium dioxide Nanocrystalline.
由图4(图中标尺为100纳米)看出产物为均匀分散的纳米晶，尺寸分布均匀，大约为24nm，{001}面所占比例约为66％。。It can be seen from Figure 4 (the scale in the figure is 100 nanometers) that the product is uniformly dispersed nanocrystals with a uniform size distribution of about 24 nm, and the proportion of {001} planes is about 66%. .
实验三：Experiment three:
一种{001}面暴露二氧化钛纳米晶的制备方法如下：A preparation method of {001} surface exposed titanium dioxide nanocrystals is as follows:
一、将3.8mL钛酸丁酯加入到聚四氟乙烯水热釜中，加入6mL异丙醇和0.5mL质量浓度为40％的氢氟酸水溶液，在180℃保温12小时；1. Add 3.8mL butyl titanate to a polytetrafluoroethylene hydrothermal kettle, add 6mL isopropanol and 0.5mL hydrofluoric acid aqueous solution with a mass concentration of 40%, and keep warm at 180°C for 12 hours;
二、将步骤一得到的反应液在转速为4000转/分钟的条件下离心分离出沉淀，然后在60℃下干燥24h，经水洗、乙醇洗涤、干燥、研磨，即得{001}面暴露二氧化钛纳米晶2. Centrifuge the reaction solution obtained in step 1 to separate the precipitate at a speed of 4000 rpm, then dry it at 60°C for 24 hours, wash with water, wash with ethanol, dry and grind to obtain {001} surface exposed titanium dioxide Nanocrystalline
由图5(图中标尺为100纳米)看出产物为均匀分散的纳米晶，尺寸分布均匀，边长大约为76nm，{001}面所占比例约为88％。It can be seen from Figure 5 (the scale in the figure is 100 nanometers) that the product is uniformly dispersed nanocrystals with uniform size distribution, the side length is about 76nm, and the proportion of {001} plane is about 88%.
由图6可知间距为0.235nm的晶面为{001}晶面。It can be seen from Fig. 6 that the crystal plane with a pitch of 0.235 nm is the {001} crystal plane.
由图7可知TiO2为纯锐钛矿相，且结晶性能良好。It can be seen from Figure 7 that TiO 2 is a pure anatase phase with good crystallization properties.
由图9可知本实验制备的{001}面暴露二氧化钛纳米晶的比表面积为58m2g-1。It can be seen from Fig. 9 that the specific surface area of the {001} surface-exposed titanium dioxide nanocrystals prepared in this experiment is 58 m 2 g -1 .
验证实验一得到的{001}面暴露二氧化钛纳米晶与实验三得到的{001}面暴露二氧化钛纳米晶的光催化活性：Verify the photocatalytic activity of TiO2 nanocrystals with {001} surface exposed in Experiment 1 and TiO2 nanocrystals with {001} surface exposed in Experiment 3:
1.分别取实验一得到的{001}面暴露二氧化钛纳米晶与实验三得到的{001}面暴露二氧化钛纳米晶10mg放置于2个50mL烧杯中，然后再分别加入10mL 0.005mol/L的稀盐酸(pH约为2.3)；1. Take the {001} surface exposed titanium dioxide nanocrystals obtained in Experiment 1 and the {001} surface exposed titanium dioxide nanocrystals obtained in Experiment 3. Put 10 mg into two 50mL beakers, and then add 10mL of 0.005mol/L dilute hydrochloric acid (pH about 2.3);
2.分别加入40μL质量浓度为0.2％的2，4-二氯苯酚水溶液于上述两种反应体系，静置于100W的高压汞灯下照射，通过紫外-可见吸收光谱测试计算2，4-二氯苯酚浓度随时间的变化。2. Add 40 μL of 0.2% 2,4-dichlorophenol aqueous solution to the above two reaction systems, place it under a 100W high-pressure mercury lamp for irradiation, and calculate the 2,4-dichlorophenol by ultraviolet-visible absorption spectrum test. Chlorophenol concentration as a function of time.
由图10可以看出，实验一制备的{001}面暴露二氧化钛纳米晶具有更高的光催化活性。It can be seen from Fig. 10 that the {001} surface exposed titanium dioxide nanocrystals prepared in Experiment 1 have higher photocatalytic activity.
Claims (10)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210159220XA CN102674451A (en) | 2012-05-22 | 2012-05-22 | Preparation method of {001} face exposed titanium dioxide nanocrystals |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210159220XA CN102674451A (en) | 2012-05-22 | 2012-05-22 | Preparation method of {001} face exposed titanium dioxide nanocrystals |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN102674451A true CN102674451A (en) | 2012-09-19 |
Family
ID=46807096
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210159220XA Pending CN102674451A (en) | 2012-05-22 | 2012-05-22 | Preparation method of {001} face exposed titanium dioxide nanocrystals |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102674451A (en) |
Cited By (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102976403A (en) * | 2012-12-06 | 2013-03-20 | 南京大学 | A controllable preparation method of TiO2 nanocrystals with different exposed crystal planes |
| CN103232064A (en) * | 2013-04-28 | 2013-08-07 | 奇瑞汽车股份有限公司 | Nano titanium dioxide and preparation method thereof as well as dye-sensitized solar battery |
| CN103555048A (en) * | 2013-10-18 | 2014-02-05 | 上海交通大学 | Preparation method of monomolecular-layer titanium oxide quantum dot semiconductor ink |
| CN103626225A (en) * | 2013-10-25 | 2014-03-12 | 河南大学 | Anatase titanium dioxide nanocrystal containing single-electron-trapped oxygen vacancies and with exposed {001} face and preparation method thereof |
| CN103818954A (en) * | 2014-02-19 | 2014-05-28 | 东华大学 | A preparation method of anatase TiO2 hollow microspheres with (001) surface exposure |
| CN103861576A (en) * | 2014-03-06 | 2014-06-18 | 天津大学 | Heterojunction nano-tube array film photocatalysis material for exposing high-energy surface of anatase titanium dioxide, and preparation method and application of photocatalysis material |
| CN104078244A (en) * | 2013-03-26 | 2014-10-01 | 中国科学院大连化学物理研究所 | Metallic-niobium-doping titanium dioxide nanometer sheet, and preparing method and application of metallic-niobium-doping titanium dioxide nanometer sheet |
| CN104071833A (en) * | 2013-03-26 | 2014-10-01 | 中国科学院大连化学物理研究所 | A kind of preparation method and application of anatase type TiO2 nanosheet |
| CN104275170A (en) * | 2014-09-12 | 2015-01-14 | 西安科技大学 | A normal temperature preparation method of {001} plane anatase TiO2 single crystal |
| CN105063719A (en) * | 2015-08-18 | 2015-11-18 | 合肥工业大学 | A homogeneous nanocrystal modified TiO2 nanotube array and its preparation method |
| CN107500350A (en) * | 2017-09-25 | 2017-12-22 | 首都师范大学 | A kind of anatase TiO of the crystal face of exposure 0012And preparation method thereof |
| CN108404898A (en) * | 2018-01-22 | 2018-08-17 | 华中科技大学 | To protonate the method that titanate prepares the titanic oxide nano compound material of graphene/{ 001 } face exposure |
| CN109046305A (en) * | 2018-09-03 | 2018-12-21 | 哈尔滨工业大学 | A kind of in-situ synthetic method of titanium dioxide/titanium sesquioxide nanocomposite |
| CN109967062A (en) * | 2019-03-11 | 2019-07-05 | 浙江万里学院 | A kind of preparation method of high-energy crystal face exposed TiO2 photocatalyst |
| CN112028119A (en) * | 2020-09-09 | 2020-12-04 | 晋中学院 | Anatase TiO with co-exposed {101}, {100} and {111} -crystal faces2Nanocrystal |
| CN115806313A (en) * | 2022-12-26 | 2023-03-17 | 常州纳欧新材料科技有限公司 | Preparation method of micron-sized rutile type titanium dioxide nanocrystal aggregate |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003002791A (en) * | 2001-06-15 | 2003-01-08 | Zenji Hiroi | Member controlled in transition temperature |
| CN101660203A (en) * | 2009-09-09 | 2010-03-03 | 中国科学院电工研究所 | Preparation method of anatase single crystal TiO2 with large active surface |
| CN101880056A (en) * | 2010-07-14 | 2010-11-10 | 中国科学院电工研究所 | A flower-like TiO2 nanomaterial with (001) outer surface and its preparation method |
| CN101892512A (en) * | 2010-07-14 | 2010-11-24 | 中国科学院电工研究所 | A preparation method of anatase TiO2 single crystal with large (001) surface area |
-
2012
- 2012-05-22 CN CN201210159220XA patent/CN102674451A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003002791A (en) * | 2001-06-15 | 2003-01-08 | Zenji Hiroi | Member controlled in transition temperature |
| CN101660203A (en) * | 2009-09-09 | 2010-03-03 | 中国科学院电工研究所 | Preparation method of anatase single crystal TiO2 with large active surface |
| CN101880056A (en) * | 2010-07-14 | 2010-11-10 | 中国科学院电工研究所 | A flower-like TiO2 nanomaterial with (001) outer surface and its preparation method |
| CN101892512A (en) * | 2010-07-14 | 2010-11-24 | 中国科学院电工研究所 | A preparation method of anatase TiO2 single crystal with large (001) surface area |
Non-Patent Citations (2)
| Title |
|---|
| 《Chemical Communications》 20120516 Liuan Gu et al. "Synthesis of nano-sized anatase TiO2 with reactive {001} facets using lamellar protonated titanate as precursor" 6978-6980 1-10 , * |
| LIUAN GU ET AL.: ""Synthesis of nano-sized anatase TiO2 with reactive {001} facets using lamellar protonated titanate as precursor"", 《CHEMICAL COMMUNICATIONS》, 16 May 2012 (2012-05-16), pages 6978 - 6980 * |
Cited By (20)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102976403B (en) * | 2012-12-06 | 2015-08-26 | 南京大学 | A kind of controlled difference exposes the TiO of crystal face 2nanocrystalline preparation method |
| CN102976403A (en) * | 2012-12-06 | 2013-03-20 | 南京大学 | A controllable preparation method of TiO2 nanocrystals with different exposed crystal planes |
| CN104078244A (en) * | 2013-03-26 | 2014-10-01 | 中国科学院大连化学物理研究所 | Metallic-niobium-doping titanium dioxide nanometer sheet, and preparing method and application of metallic-niobium-doping titanium dioxide nanometer sheet |
| CN104071833A (en) * | 2013-03-26 | 2014-10-01 | 中国科学院大连化学物理研究所 | A kind of preparation method and application of anatase type TiO2 nanosheet |
| CN103232064A (en) * | 2013-04-28 | 2013-08-07 | 奇瑞汽车股份有限公司 | Nano titanium dioxide and preparation method thereof as well as dye-sensitized solar battery |
| CN103232064B (en) * | 2013-04-28 | 2016-01-27 | 奇瑞汽车股份有限公司 | Nano titanium oxide and preparation method thereof, dye sensitization solar battery |
| CN103555048A (en) * | 2013-10-18 | 2014-02-05 | 上海交通大学 | Preparation method of monomolecular-layer titanium oxide quantum dot semiconductor ink |
| CN103626225A (en) * | 2013-10-25 | 2014-03-12 | 河南大学 | Anatase titanium dioxide nanocrystal containing single-electron-trapped oxygen vacancies and with exposed {001} face and preparation method thereof |
| CN103626225B (en) * | 2013-10-25 | 2015-08-26 | 河南大学 | A kind of expose that { 001} face anatase titania is nanocrystalline and preparation method thereof containing constraint single electron Lacking oxygen |
| CN103818954A (en) * | 2014-02-19 | 2014-05-28 | 东华大学 | A preparation method of anatase TiO2 hollow microspheres with (001) surface exposure |
| CN103861576A (en) * | 2014-03-06 | 2014-06-18 | 天津大学 | Heterojunction nano-tube array film photocatalysis material for exposing high-energy surface of anatase titanium dioxide, and preparation method and application of photocatalysis material |
| CN104275170A (en) * | 2014-09-12 | 2015-01-14 | 西安科技大学 | A normal temperature preparation method of {001} plane anatase TiO2 single crystal |
| CN105063719A (en) * | 2015-08-18 | 2015-11-18 | 合肥工业大学 | A homogeneous nanocrystal modified TiO2 nanotube array and its preparation method |
| CN107500350A (en) * | 2017-09-25 | 2017-12-22 | 首都师范大学 | A kind of anatase TiO of the crystal face of exposure 0012And preparation method thereof |
| CN108404898A (en) * | 2018-01-22 | 2018-08-17 | 华中科技大学 | To protonate the method that titanate prepares the titanic oxide nano compound material of graphene/{ 001 } face exposure |
| CN109046305A (en) * | 2018-09-03 | 2018-12-21 | 哈尔滨工业大学 | A kind of in-situ synthetic method of titanium dioxide/titanium sesquioxide nanocomposite |
| CN109967062A (en) * | 2019-03-11 | 2019-07-05 | 浙江万里学院 | A kind of preparation method of high-energy crystal face exposed TiO2 photocatalyst |
| CN112028119A (en) * | 2020-09-09 | 2020-12-04 | 晋中学院 | Anatase TiO with co-exposed {101}, {100} and {111} -crystal faces2Nanocrystal |
| CN112028119B (en) * | 2020-09-09 | 2022-10-11 | 晋中学院 | Anatase TiO with co-exposed {101}, {100} and {111} -crystal faces 2 Nanocrystal |
| CN115806313A (en) * | 2022-12-26 | 2023-03-17 | 常州纳欧新材料科技有限公司 | Preparation method of micron-sized rutile type titanium dioxide nanocrystal aggregate |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102674451A (en) | Preparation method of {001} face exposed titanium dioxide nanocrystals | |
| CN104772158B (en) | A kind of preparation method of WO3/C3N4 mixed photocatalyst | |
| Wu et al. | Progress in the synthesis and applications of hierarchical flower-like TiO2 nanostructures | |
| CN107126944B (en) | A kind of more doping titanium dioxide nano particles of more defects with high visible light catalytic activity and preparation method | |
| CN103551136B (en) | Attapulgite loaded quasi-one-dimensional titanium dioxide composite photocatalyst and preparation method thereof | |
| CN102921443B (en) | Nickel titanium hydrotalcite and graphene composite photocatalyst responsive to visible lights and method for preparing same | |
| CN101302036A (en) | A kind of preparation method of doped titanium dioxide nanotube | |
| CN101116808A (en) | Photocatalysis powder having a negative ion releasing function and method for preparing the same | |
| CN103240073B (en) | A kind of Zn2+ doped BiVO4 visible light catalyst and preparation method thereof | |
| CN103626225B (en) | A kind of expose that { 001} face anatase titania is nanocrystalline and preparation method thereof containing constraint single electron Lacking oxygen | |
| CN101734615A (en) | Method for preparing metal/titanium dioxide composite nano material at low temperature by gamma-irradiation | |
| CN110586058B (en) | A kind of preparation method of nanometer titanium dioxide/zirconia composite photocatalyst | |
| CN107008246A (en) | Graphene quantum dot is sensitized the preparation method of sea urchin shape photocatalysis material of titanium dioxide | |
| CN110433830A (en) | Preparation method of modified flower-shaped bismuth oxyiodide photocatalyst | |
| CN110227515B (en) | Bi2MoO6/BiPO4p-n heterojunction photocatalyst, preparation method and application thereof | |
| CN106076312B (en) | A kind of Nb (OH)5Nano wire/redox graphene composite photo-catalyst and the preparation method and application thereof | |
| CN102491415A (en) | Preparation method of monodispersed anatase titanium dioxide nano porous microspheres | |
| CN102718255B (en) | Preparation method of titanium dioxide hollow nano structure | |
| CN105233821A (en) | Strontium-doped and silver-doped nanometer titanium dioxide visible light catalyst | |
| CN105399138A (en) | A kind of preparation method and product of perovskite SrTiO tetragonal nanoparticles | |
| CN111151233B (en) | A kind of preparation method of oxygen-deficient TiO2 normal temperature and normal pressure water phase | |
| CN103708544A (en) | One-step preparation method of mono-dispersed decahedral anatase titanium dioxide powder | |
| CN107188234A (en) | A kind of sheet Bi2WO6Preparation method | |
| CN103700503B (en) | Method for preparing shape-controllable dye-sensitized solar cell photo-anode | |
| CN1752016A (en) | A kind of novel nano-titanium dioxide powder preparation method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20120919 |