CN104941629A - Nano photocatalytic hydrosol and preparation method thereof - Google Patents
Nano photocatalytic hydrosol and preparation method thereof Download PDFInfo
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- CN104941629A CN104941629A CN201510229095.9A CN201510229095A CN104941629A CN 104941629 A CN104941629 A CN 104941629A CN 201510229095 A CN201510229095 A CN 201510229095A CN 104941629 A CN104941629 A CN 104941629A
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Abstract
The invention provides photocatalytic hydrosol with a wide light absorption and responding range and a preparation method thereof. The photocatalytic hydrosol is characterized by consisting of spherical nano WO3/TiO2 with a core-shell structure and water, wherein the pH value of the hydrosol is ranged from 3 to 6, and nano WO3 is a core of which the average particle diameter is 5-80nm; nano TiO2 is a shell which is 5-50nm in thickness; the total particle average diameter is 10-100nm. The hydrosol is prepared by two steps of preparing nano WO3 hydrosol by a hydrothermal reaction method and then preparing hydrosol wrapped by nano TiO2 to form the nano WO3/TiO2 hydrosol with the core-shell structure. The hydrosol with the core-shell structure, which is prepared by the preparation method, has a wide light absorption range and is high in photocatalysis capacity; as the hydrosol is an aqueous preparation, the problem of environmental pollution is solved; the preparation method has the advantages of simplicity, low cost, wide use range and the like.
Description
Technical field
The invention belongs to field of nanometer material technology, particularly relate to a kind of nano-photo catalytic hydrosol with wide absorption region and preparation method thereof.
Technical background
Development along with global industry process and the pay attention to day by day to home air quality; the problems such as environmental pollution and interior decoration air pollution are day by day serious; environmental protection, healthy and sustainable development become the matter of utmost importance that the mankind must consider; photocatalysis technology is as a representative of Green Chemistry; it can convert solar energy into chemical energy, electric energy under light illumination; various organic pollutions in degradable water and air, have that oxidability is strong, organic pollutant degradation completely, can reuse, the advantage such as efficient energy-saving.
Owing to having good photocatalysis performance and the advantage such as stability is strong, nontoxic, the nano titanium oxide as N-type semiconductor metal oxide has broad application prospects in purification of air, sewage disposal, antibacterial and deodouring etc.Prepare forward position and focus direction that the nano titanium dioxide photocatalyst with higher catalytic activity is photocatalysis research always.The energy gap with the anatase-type nanometer titanium dioxide of photocatalytic activity is 3.2eV, only can absorb the ultraviolet light of below 387nm, this part ultraviolet (300-400nm) only accounts for the 4-6% reaching solar energy on ground, and it is very weak to the absorbability occupying the most visible ray of sunshine, cause solar energy utilization ratio low, therefore, research and development can be that research is crucial by the nano titanium dioxide photocatalyst of excited by visible light.
At present, developer mainly adopts the method for the various ion that adulterates to expand light abstraction width, as elements such as doped F, B, N, Cl, C, Fe, Mo, Si, Ag, Pt, Cu and rare earth elements.Chinese invention patent application 201410148268.x discloses the nano titanium oxide of the fluorine boron codope adopting precious metals ag, Pr to modify, and adopts expensive Platinous Potassium Chloride, silver nitrate, HBF
4for raw material synthesizes.The nano-TiO that a kind of Ag, N mix altogether is disclosed in Chinese invention patent application numbers 201410217409.9
2and the preparation method of photocatalyst glazing emulsion, adopt silver nitrate to be that raw material synthesizes.Disclose a kind of nano titanium oxide utilizing W, La to adulterate and preparation method thereof in Chinese invention patent application numbers 201410139406.8, use ammonium tungstate and lanthanum nitrate to be raw material.Chinese invention patent application numbers 201410291066.0 discloses the nano-TiO of La, In codope
2, employing indium nitrate, lanthanum chloride are raw material.Doping Nd is proposed in document (Appl ied Surface Science, 2014,307:333-345)
3+/ Er
3+, Nd
3+/ Eu
3+, Eu
3+/ Ho
3+etc. the response improving visible region.The raw material of these methods or employing is as very expensive in Ag, Pt, rare earth etc., or process is more complicated, all need the process adopting high temperature to burn till to obtain the anatase-phase nano titanium dioxide powder adulterated, during as the needs use hydrosol, need to add additive dispersion treatment.
In addition, developer adopts the method forming nucleocapsid structure to improve photoresponse, and the core of employing is mainly oxide, comprises ZnO, MoO
3, V
2o
5, Al
2o
3, SiO
2with WO3 etc., wherein, WO
3be gap semiconductor, its energy gap is adjustable at 2.5-3.5eV, effectively can absorb the sunshine of below 496nm, compare TiO when energy gap is 2.5eV
2absorption region is wider, is also a kind of excellent catalysis material.Due to WO
3oxidation and reduction potential compare TiO
2height therefore, WO
3oxidability be better than TiO
2and reducing power is weaker than TiO
2.Work as TiO
2for shell WO
3during for core, due to TiO
2energy gap is large, and it absorbs ultraviolet portion and through visible ray, through visible ray again can by WO
3absorption excites formation electron hole pair, due to WO
3higher energy level, can be transferred to the TiO with more low-lying level
2on shell, thus make the nanometer WO of nucleocapsid structure
3/ TiO
2in wide absorption region, there is strong oxidation and reducing power.As document (Journal of Materials Chemistry, 2011,21:10792) adopts the synthesis of the method for electro-deposition to know clearly, there is nucleocapsid structure TiO
2/ WO
3nanometer rods, WO
3for core.Owing to which employs the method for electro-deposition, need to carry out at the smooth surface of good process, the hydrosol with superior dispersibility can not be obtained, therefore can not be applicable to need to carry out the occasion such as roller coat, spraying.
Summary of the invention
In order to solve the problem, the present invention proposes a kind of photocatalysis hydrosol with wide light absorption and response range and preparation method thereof, it is characterized in that this photocatalysis hydrosol is by the ball shaped nano WO with nucleocapsid structure
3/ TiO
2form with water, the pH value range of this hydrosol is 3-6, nanometer WO
3for core, its average particulate diameter is 5-80nm, nano-TiO
2for shell, thickness is 5-50nm, and total particle average diameter is 10-100nm; The quality solid content of the hydrosol is 0.05-20%.
Work as TiO
2for shell, WO
3for the nano-TiO of the nucleocapsid structure of core
2/ WO
3when particle is subject to illumination, due to TiO
2energy gap is large, and it absorbs ultraviolet portion and through visible ray, through visible ray again can by WO
3absorption excites formation electron hole pair, due to WO
3higher energy level, can be transferred to the TiO with more low-lying level
2on shell, thus make the nanometer WO of nucleocapsid structure
3/ TiO
2in wide absorption region, there is strong oxidation and reducing power.From WO
3electron hole pair transfer to TiO
2absorption loss water may be caused, thus nano-TiO because defect exists in shell surface process
2the thickness of shell needs within the scope of 5-50nm.Due to WO
3energy gap is variable, and the too little then energy gap of particle is too large, and the nano particle overall size that particle is then formed too greatly cannot form the stable hydrosol too greatly, and suitable particle size range is 5-80nm.
The quality solid content of the hydrosol is 0.05-20%, the solid content of 0.05-5% scope can be used for spraying, roll coating process carries out air pollution treatment, prepares self-cleaning glass, pottery etc., the solid content of 5-20% scope can be used for dip-coating, spraying process prepares air purifier photocatalyst filtering net, the stable hydrosol can not be formed, lower than 0.05% active ingredient very little higher than 20%.
The preparation method of the described photocatalysis hydrosol, is characterized in that comprising the following steps:
(1) nanometer WO is prepared
3the hydrosol: by water-soluble for the 0.001-0.04mol/L ammonium metatungstate formation aqueous solution, adding the inorganic acids such as hydrochloric acid, nitric acid, acetic acid makes pH value of water solution be 1-4, be placed on after being incubated 3-18 hour in hydrothermal reaction kettle at 160-280 DEG C and be cooled to room temperature, obtain the nanometer WO of average diameter of particles 5-50nm
3the hydrosol, the pH value of the hydrosol is 3-6;
(2) the nanometer WO that pH value is 3-6 is prepared
3/ TiO
2the hydrosol: nanometer WO prepared by heating steps one
3the hydrosol to 80-100 DEG C, then adds the organic matter of titaniferous, and wherein the mol ratio of Ti:W is 3:1-30:1, constant temperature 0.5-5h, and cold cut, to room temperature, can obtain the hydrosol that solid content is 0.5-20%, then be diluted with water into the hydrosol of 0.05-20%.
Described preparation nanometer WO
3in hydrosol method, hydro-thermal reaction is be incubated 3-18 hour at 160-280 DEG C, lower than 160 DEG C, can not obtain WO
3, higher than 280 DEG C, then energy consumption is harsh to reaction vessel requirement greatly; Temperature retention time was lower than 3 hours, and particle is too little, and higher than 18 hours, then particle was too large.
Described preparation nanometer WO
3/ TiO
2in hydrosol method, first by nanometer WO
3the hydrosol is heated to 80-100 DEG C of constant temperature 0.5-5 hour, and temperature, lower than 80 DEG C, can not get nano-TiO
2, heating-up temperature can not more than 100 DEG C; Constant temperature time lower than 0.5 hour, then TiO
2shell is too thin, and higher than 5 hours, then shell was too thick;
The organic matter of described titaniferous be one in metatitanic acid methyl esters, tetraethyl titanate, titanium propanolate and butyl titanate and more than.
The nanometer WO of nucleocapsid structure prepared by the present invention
3/ TiO
2it is wide that the hydrosol has light abstraction width, and photo-catalysis capability is strong, aqueous formulation non-environmental-pollution problem, the advantages such as the simple cost of preparation method is low, and the scope of application is wide.
Accompanying drawing explanation
Fig. 1: the transmission electron microscope photo of embodiment one;
Fig. 2: the transmission electron microscope photo of embodiment two;
Fig. 3: the transmission electron microscope photo of embodiment three;
Fig. 4: the photoresponse curve of embodiment one;
Fig. 5: the photoresponse curve of embodiment two;
Fig. 6: the photoresponse curve of embodiment three;
Detailed description of the invention
Embodiment one
In the ammonium metatungstate aqueous solution of 100ml 0.04mol/L, add hydrochloric acid makes solution ph be 1, is placed on after being incubated 15 hours in hydrothermal reaction kettle at 280 DEG C and is cooled to room temperature, and acquisition average diameter of particles 30nm, pH value are the nanometer WO of 3
3the hydrosol, heating water colloidal sol to 80 DEG C, add 20g metatitanic acid methyl esters, the mol ratio of Ti:W is made to be 3:1, constant temperature 2h, cold cut, to room temperature, can obtain the hydrosol that solid content is 20% average grain diameter 50nm, and the transmission electron microscope photo of its nano particle and photoresponse curve are respectively as shown in figs. 1 and 4.
Embodiment two
In the ammonium metatungstate aqueous solution of 100ml 0.001mol/L, add acetic acid makes solution ph be 4, is placed on after being incubated 3 hours in hydrothermal reaction kettle at 160 DEG C and is cooled to room temperature, and acquisition average diameter of particles 10nm, pH value are the nanometer WO of 6
3the hydrosol, heating water colloidal sol to 100 DEG C, add 8.2g tetraethyl titanate, the mol ratio of Ti:W is made to be 30:1, constant temperature 5h, cold cut, to room temperature, can obtain the hydrosol that solid content is 5.6% average grain diameter 80nm, and the transmission electron microscope photo of its nano particle and photoresponse curve are respectively as shown in figures 2 and 5.
Embodiment three
In the ammonium metatungstate aqueous solution of 100ml 0.005mol/L, add nitric acid makes solution ph be 2, is placed on after being incubated 18 hours in hydrothermal reaction kettle at 260 DEG C and is cooled to room temperature, and acquisition average diameter of particles 60nm, pH value are the nanometer WO of 4
3the hydrosol, heating water colloidal sol to 80 DEG C, add 10.2g butyl titanate, the mol ratio of Ti:W is made to be 5:1, constant temperature 3h, cold cut, to room temperature, can obtain the hydrosol that solid content is 3.8% average grain diameter 90nm, and the transmission electron microscope photo of its nano particle and photoresponse curve are respectively as shown in figs. 3 and 6.
Claims (6)
1. a nano-photo catalytic hydrosol, is characterized in that this hydrosol is the ball shaped nano WO with nucleocapsid structure of 10-100nm by average diameter of particles
3/ TiO
2form with water, wherein, nano-TiO
2for shell, thickness is 5-50nm, nanometer WO
3for stratum nucleare, its average particulate diameter is 5-80nm, and the quality solid content of the hydrosol is 0.05-20%.
2. the photocatalysis hydrosol according to claim 1, is characterized in that the pH value of the described hydrosol is 3-6.
3. a preparation method for the nano-photo catalytic hydrosol, is characterized in that the preparation method of this hydrosol comprises the following steps: (1) prepares nanometer WO
3the hydrosol: by water-soluble for the ammonium metatungstate formation aqueous solution, adds inorganic acids and makes pH value of water solution be 1-4, be cooled to room temperature after being incubated 3-18 hour in hydrothermal reaction kettle at 160-280 DEG C; (2) the nanometer WO that pH value is 3-6 is prepared
3/ TiO
2the hydrosol: heating nanometer WO
3the hydrosol to 80-100 DEG C, then adds the organic matter of titaniferous, and wherein the mol ratio of Ti:W is 3:1-30:1, and constant temperature 0.5-5h, is cooled to room temperature, obtains the hydrosol that solid content is 0.5-20%, then is diluted to the hydrosol that solid content is 0.05-20%.
4. the preparation method of the photocatalysis hydrosol according to claim 3, is characterized in that the concentration of described ammonium metatungstate aqueous solution is 0.001-0.04mol/L.
5. the preparation method of the photocatalysis hydrosol according to claim 3, it is characterized in that described described inorganic acids be in hydrochloric acid, nitric acid, acetic acid a kind of and more than.
6. the preparation method of the photocatalysis hydrosol according to claim 3, it is characterized in that the organic matter of described titaniferous be one in metatitanic acid methyl esters, tetraethyl titanate, titanium propanolate and butyl titanate and more than.
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| CN104941629B CN104941629B (en) | 2018-03-30 |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105540671A (en) * | 2015-12-30 | 2016-05-04 | 河南科技大学 | Stepwise hydrothermal method for preparing hydrated alumina coated tungsten oxide powder |
| CN106111126A (en) * | 2016-06-23 | 2016-11-16 | 上海交通大学 | The metal-modified titania hydrosol of high visible-light activity and synthesis and application |
| CN108587370A (en) * | 2018-04-24 | 2018-09-28 | 赵阳 | A kind of emulsion paint for modifying nano-negative ion colloidal sol based on CdTe quantum |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101618351A (en) * | 2009-08-06 | 2010-01-06 | 上海理工大学 | Nanometer or micrometer structure composite material and preparation method thereof |
| WO2012112120A1 (en) * | 2011-02-17 | 2012-08-23 | Nanyang Technological University | Inorganic nanorods and a method of forming the same, and a photoelectrode and a photovoltaic device comprising the inorganic nanorods |
-
2015
- 2015-05-07 CN CN201510229095.9A patent/CN104941629B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101618351A (en) * | 2009-08-06 | 2010-01-06 | 上海理工大学 | Nanometer or micrometer structure composite material and preparation method thereof |
| WO2012112120A1 (en) * | 2011-02-17 | 2012-08-23 | Nanyang Technological University | Inorganic nanorods and a method of forming the same, and a photoelectrode and a photovoltaic device comprising the inorganic nanorods |
Non-Patent Citations (1)
| Title |
|---|
| 董幼青: "钨的氧化物及复合氧化物纳米材料的合成表征与性能研究", 《中国优秀硕士学位论文全文数据库 工程科技I辑》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105540671A (en) * | 2015-12-30 | 2016-05-04 | 河南科技大学 | Stepwise hydrothermal method for preparing hydrated alumina coated tungsten oxide powder |
| CN106111126A (en) * | 2016-06-23 | 2016-11-16 | 上海交通大学 | The metal-modified titania hydrosol of high visible-light activity and synthesis and application |
| CN106111126B (en) * | 2016-06-23 | 2019-01-18 | 上海交通大学 | The metal-modified titania hydrosol of high visible-light activity and synthesis and application |
| CN108587370A (en) * | 2018-04-24 | 2018-09-28 | 赵阳 | A kind of emulsion paint for modifying nano-negative ion colloidal sol based on CdTe quantum |
| CN108587370B (en) * | 2018-04-24 | 2021-11-05 | 广东好仕迪新材料科技有限公司 | Emulsion paint based on CdTe quantum dot modified nano anion sol |
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| CN104941629B (en) | 2018-03-30 |
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