CN101428853A - Method for producing pyromelane type nano-TiO2 powder with Ti(SO4)2 hydrothemal method - Google Patents
Method for producing pyromelane type nano-TiO2 powder with Ti(SO4)2 hydrothemal method Download PDFInfo
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- CN101428853A CN101428853A CNA2008102436486A CN200810243648A CN101428853A CN 101428853 A CN101428853 A CN 101428853A CN A2008102436486 A CNA2008102436486 A CN A2008102436486A CN 200810243648 A CN200810243648 A CN 200810243648A CN 101428853 A CN101428853 A CN 101428853A
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Abstract
The invention relates to the technical field of photo-catalysis and material chemistry, in particular to the preparation of Brookite-type nanoscale TiO2 photocatalyst. The preparation comprises the following steps: adding NaOH solution in Ti(SO4)2 solution dropwise to generate white sediment; stirring; standing; centrifuging multiple times until no SO4<2->; subjecting the precursor obtained by the above reaction to hydrothermal reaction in a high-pressure hydrothermal reaction kettle at 150 to 180 DEG C for 2 to 60 h; washing; and drying to obtain the product. The pure-phase Brookite-type TiO2 photocatalyst has good photocatalytic activity in visual light.
Description
Technical field
The present invention relates to photochemical catalysis and material chemistry technical field, refer in particular to brookite type TiO
2The preparation of nano powder photocatalyst.
Background technology
The develop rapidly of human industrial technology has also brought the serious environmental pollution problem to people, is just threatening human existence and health.The method of traditional absorption, flocculation and bio-oxidation is not reaching satisfied effect aspect the trade effluent handling, and the big cost height of energy consumption, takies that resource is more to be applied it to be very restricted.People are badly in need of finding a kind of desirable high-efficiency method to handle industrial production waste water, and therefore, photocatalysis technology becomes one of focus of research in the great attention that causes people aspect environment protection and the sewage disposal.
Photocatalysis technology is a novel environmental improvement technology and a novel energy technology with broad prospect of application, and the advantage low with its cost, that efficient is high, secondary pollution is little is considered to solve the effective ways of present environmental pollution, has good application prospects.TiO
2Be the photocatalyst that generally uses at present, have powerful redox ability, high chemical stability and nontoxic characteristic, become the focus of research, however TiO
2Be that energy gap is big, the sun power utilising efficiency is low, has limited the application of its reality.In order to improve TiO
2Utilization ratio to sunlight, its photoresponse scope is extended in the visible-range, the researchist has carried out many trials, as adopt methods such as dye photoactivation, noble metal loading, metal and nonmetallic ion-doped, semi-conductor coupling, but, there is complex process again in these methods, unstable properties, the high deficiency of cost.Highly active TiO under the preparation visible light
2Be to use TiO
2One of key subject of photocatalysis technology.
TiO
2There are Detitanium-ore-type (Anatase), rutile-type (Rutile) and brookite type multiple crystal formations such as (Brookite).The nano-TiO of Detitanium-ore-type and rutile-type
2The preparation of material and rerum natura research work have obtained carrying out widely, for the nanometer brookite type TiO of metastable phase
2The research of material does not then almost appear in the newspapers because of synthetic difficulty.For a long time, owing to be difficult for the brookite type TiO of the single phase of preparation with manual method
2, about the research of its structure and aspect of performance also once was left in the basket.With anatase octahedrite and rutile TiO
2Compare brookite type TiO
2The character that many uniquenesses are arranged: TiO in the brookite structure
6Octahedral arrangement mode makes brookite type TiO
2Crystal in form along the axial passage of c, the positively charged ion that some are less can be incorporated into wherein as hydrogen ion or lithium ion, making it has the potential application prospect in fields such as catalysis and drying battery; In addition, the special mode of connection of octahedra chain in the brookite structure also causes having exposed O atom on its (100) crystal face, thereby makes it become the active atomic of catalyzed reaction etc.Other there are some researches show, brookite type TiO
2Photoelectric property and Detitanium-ore-type TiO
2Close, also can be used for fields such as photochemical catalysis and photocell.People such as R.Zallen have at room temperature measured the spectral absorption limit of mineral crystal brookite type titanium dioxide, and the result shows: measured spectral absorption band is a broad band, and its energy of absorption edge can be extended to visible region; Adsorbing spectral dependency shows that brookite type titanium dioxide is the semi-conductor of indirect transition, and band gap is 1.9eV.
Summary of the invention
The purpose of this invention is to provide a kind of brookite type TiO
2The preparation method of nano powder photocatalyst.
The preparation method of said brookite type TiO2 nano powder photocatalyst is: to Ti (SO
4)
2Drip NaOH solution in the solution, the adularescent precipitation generates in the titration process, stirs, leaves standstill, and centrifuge washing is repeatedly to there not being SO
4 2-Exist; Presoma with above-mentioned reaction gained takes out behind 150 ℃～200 ℃ hydro-thermal reaction 2-60h in high-pressure hydrothermal reaction kettle then, washing, and oven dry obtains product.
Among the above-mentioned preparation method, Ti (SO
4)
2The concentration of solution is 1mol/L, the 2mol/L of NaOH solution;
Among the above-mentioned preparation method, NaOH and Ti (SO in the system
4)
2Mol ratio 3: 1～5: 1;
Among the above-mentioned preparation method, centrifuge washing repeatedly after, filtrate BaCl
2Whether the adularescent precipitation generates in the solution titration, can check to have or not SO
4 2-Exist, centrifuge washing does not really have SO
4 2-PH value of solution when existing=10.61;
Among the above-mentioned preparation method, reactor takes out after 150 ℃～180 ℃ hydro-thermal reaction times are respectively 2h～60h, naturally cools to room temperature, records liquid pH=12.35 in back 6 reactors of reaction.Washing is put into 80 ℃ of oven dry in the electric heating constant temperature air dry oven with product, grinds, and obtains product.
The present invention has obtained pure phase brookite type titanium dioxide photocatalyst with Hydrothermal Preparation, and it has photocatalytic activity preferably under visible light.
Description of drawings
Fig. 1 is 60h for carrying out the hydro-thermal reaction time according to example 1,48h, 36h, 24h, 12h, the XRD spectra of the prepared sample of 2h.A, b, c, d, e, f represent 60h respectively, 48h, 36h, 24h, 12h, the sample of 2h
Fig. 2 is the brookite phase TiO according to example 1 hydro-thermal reaction 24h preparation
2Raman spectrum.
Fig. 3 is 24h (a) and 60h (b) sample for carry out the hydro-thermal reaction time respectively according to example 1.
Fig. 4 is 60h for carrying out the hydro-thermal reaction time according to example 1,48h, 36h, 24h, the fluorescence spectrum figure of the prepared sample of 12h.
Fig. 5 is for carrying out the degrade design sketch of rhodamine B of the obtained sample of hydro-thermal reaction 36h under visible light according to example 1
Embodiment
The present invention will be further described below in conjunction with concrete embodiment.
Embodiment 1:
Get the Ti (SO of 1mol/L
4)
2Solution 120mL transfers in 500 milliliters the beaker.At room temperature in the magnetic stirrer process, the new NaOH solution 250mL of the 2mol/L of preparation is added drop-wise to fills Ti (SO
4)
2In the beaker of solution.NaOH and Ti (SO in the system
4)
2Mol ratio 5: 1.The adularescent precipitation generates in the titration process, continues to stir 5 hours, leaves standstill a night.Centrifuge washing is repeatedly used BaCl
2The no SO of solution check
4 2-Exist, at this moment pH value of solution=10.61.The presoma of above-mentioned reaction gained divided equally transfer in 6 100mL high-pressure hydrothermal reaction kettles that indicate different sequence numbers, be placed in the electric heating constant temperature air dry oven.Reactor takes out behind 180 ℃ of hydro-thermal reaction different times, naturally cools to room temperature after reactor is taken out, and records liquid pH=12.35 in the reaction afterreaction still, and washing is put into 80 ℃ of oven dry in the electric heating constant temperature air dry oven with product, grinds.Obtain product.The hydro-thermal reaction time of investigating in this experiment is respectively 2h, 12h, 24h, 36,48,60.
Product adopts XRD, Raman spectrum, and transmission electron microscope, fluorescence spectrum characterizes sample, and photocatalytic activity is estimated.The evaluation method of photocatalytic activity provided by the invention: get 0.10g TiO of the present invention
2Place the rose-red aqueous solution of 100mL10mg/L to carry out light-catalyzed reaction at the cylindrical pyrex glass light of homemade 250mL reactor, sampling and carry out quantitative analysis from reactor regularly, test light with the UV-2450 spectrophotometer according to time sample to rosy photocatalytic degradation situation.
XRD spectra such as Fig. 1,2 hours sample of hydro-thermal reaction (shown in Fig. 1 f) crystallization is incomplete; 12 hours sample crystallization is better, has located a little assorted peak (among Fig. 1 e shown in the square) but be 27.8 ° at 2 θ; Along with the increase of hydro-thermal reaction time, the sample crystallization is tending towards perfect.24 hours sample is the single brookite type TiO of structure
2, diffraction angle 2 θ are 25.3 °, 30.7 °, 40.1 °, 48.0 °, 55.2 °, 64.5 °, 70.5 ° correspond respectively to crystal face (120), (121), (022), (231), (241), (251), (332).
Raman spectrum as shown in Figure 2, synthetic brookite sample has 14 the Raman diaphragms that can differentiate, belongs to A respectively
1g(155,195,247,414,636cm
-1); B
1g(215,323,414,503cm
-1); B2g (366,394,462,585cm
-1) and B
3g(287cm
-1) vibration modes.
The transmission electron microscope picture of sample as shown in Figure 3, the 24h sample is irregular bar-shaped (a), slightly agglomeration.Shown in, the 60h sample is a bunch shape rod (b), agglomeration is serious.
Fluorescence spectrum figure as shown in Figure 4, sample is fluorescence spectrum figure under the 380nm condition in excitation wavelength, 36h sample emitting fluorescence signal is the most weak, light induced electron and hole-recombination rate are low in this sample of surface, photocatalytic activity is better.
Fig. 5 carries out the degrade design sketch of rhodamine B of the obtained sample of hydro-thermal reaction 36h under visible light, increase along with hydro-thermal time of sample, rosy degradation rate is also in rising trend, the photodegradation activity of the sample that obtained under the synthesis condition in 36 hours the highest (left figure).Along with light application time prolongs, the obvious blue shift of main absorption peak of rhodamine B shows that catalyzer takes place simultaneously to the degraded of the rosy aromatic nucleus that adds lustre in the solution and the ethyl that dissociates.
Embodiment 2:
Get the Ti (SO of 1mol/L
4)
2Solution 120mL transfers in 500 milliliters the beaker.At room temperature in the magnetic stirrer process, the new NaOH solution 200mL of the 2mol/L of preparation is added drop-wise to fills Ti (SO
4)
2In the beaker of solution.NaOH and Ti (SO in the system
4)
2Mol ratio 3: 1.The adularescent precipitation generates in the titration process, continues to stir 5 hours, leaves standstill a night.Centrifuge washing is repeatedly used BaCl
2The no SO of solution check
4 2-Exist.The presoma of above-mentioned reaction gained divided equally transfer in 6 100mL high-pressure hydrothermal reaction kettles that indicate different sequence numbers, be placed in the electric heating constant temperature air dry oven.Reactor takes out behind 150 ℃ of hydro-thermal reaction different times, naturally cools to room temperature after reactor is taken out, and washing is put into 80 ℃ of oven dry in the electric heating constant temperature air dry oven with product, grinds.Obtain product.The hydro-thermal reaction time of investigating in this experiment is 36h.The analytical results of product is substantially the same manner as Example 1.
Embodiment 3:
Get the Ti (SO of 1mol/L
4)
2Solution 120mL transfers in 500 milliliters the beaker.At room temperature in the magnetic stirrer process, the new NaOH solution 250mL of the 2mol/L of preparation is added drop-wise to fills Ti (SO
4)
2In the beaker of solution.NaOH and Ti (SO in the system
4)
2Mol ratio 4: 1.The adularescent precipitation generates in the titration process, continues to stir 5 hours, leaves standstill a night.Centrifuge washing is repeatedly used BaCl
2The no SO of solution check
4 2-Exist.The presoma of above-mentioned reaction gained divided equally transfer in 6 100mL high-pressure hydrothermal reaction kettles that indicate different sequence numbers, be placed in the electric heating constant temperature air dry oven.Reactor takes out behind 180 ℃ of hydro-thermal reaction different times, naturally cools to room temperature after reactor is taken out, and washing is put into 80 ℃ of oven dry in the electric heating constant temperature air dry oven with product, grinds, and obtains product.The hydro-thermal reaction time of investigating in this experiment is respectively 48h.60h.
The analytical results of product is substantially the same manner as Example 1.
Claims (5)
1, a kind of brookite type TiO
2The preparation method of nano powder photocatalyst is characterized in that, step is: to Ti (SO
4)
2Drip NaOH solution in the solution, the adularescent precipitation generates in the titration process, stirs, leaves standstill, and centrifuge washing is repeatedly to there not being SO
4 2-Exist; Presoma with above-mentioned reaction gained takes out behind 150 ℃～180 ℃ hydro-thermal reaction 2-60h in high-pressure hydrothermal reaction kettle then, washing, and oven dry obtains product.
2, brookite type TiO according to claim 1
2The preparation method of nano powder photocatalyst is characterized in that: Ti (SO
4)
2The concentration of solution is 1mol/L, the 2mol/L of NaOH solution.
3, brookite type TiO according to claim 1
2The preparation method of nano powder photocatalyst is characterized in that: NaOH and Ti (SO in the system
4)
2Mol ratio 3:1～5:1.
4, brookite type TiO according to claim 1
2The preparation method of nano powder photocatalyst is characterized in that: centrifuge washing repeatedly after, filtrate BaCl
2Whether the adularescent precipitation generates in the solution titration, can check to have or not SO
4 2-Exist, centrifuge washing does not really have SO
4 2-PH value of solution when existing=10.61.
5, brookite type TiO according to claim 1
2The preparation method of nano powder photocatalyst is characterized in that: reactor is respectively 2h through 180 ℃ of hydro-thermal reaction times, 12h, and 24h, 36h, 48h takes out behind the 60h, naturally cools to room temperature, washing, oven dry is ground; Obtain product.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101880057A (en) * | 2010-06-04 | 2010-11-10 | 山东轻工业学院 | Method for preparing high-purity brookite titanium dioxide with controlled appearance |
| CN102303905A (en) * | 2011-08-18 | 2012-01-04 | 刘奕 | Method for producing brookite TiO2 in large scale at low cost |
| CN103058273A (en) * | 2011-10-20 | 2013-04-24 | 中国科学院福建物质结构研究所 | Monodispersed brookite phase titanium dioxide nanometer spindle body powder and preparation method thereof |
| CN106187051A (en) * | 2016-07-12 | 2016-12-07 | 中山市华山高新陶瓷材料有限公司 | Nano titanium dioxide inorganic coating and preparation method thereof |
| CN107244894A (en) * | 2017-06-08 | 2017-10-13 | 钦州学院 | The connection method of Nixing pottery base substrate |
| CN108686263A (en) * | 2018-06-11 | 2018-10-23 | 新乡学院 | A method of preparing HA biodegradable coatings in Mg alloy surface |
| CN111807712A (en) * | 2020-07-23 | 2020-10-23 | 长虹美菱股份有限公司 | Self-cleaning glass panel of refrigerator and preparation process thereof |
-
2008
- 2008-12-05 CN CNA2008102436486A patent/CN101428853A/en active Pending
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101880057A (en) * | 2010-06-04 | 2010-11-10 | 山东轻工业学院 | Method for preparing high-purity brookite titanium dioxide with controlled appearance |
| CN102303905A (en) * | 2011-08-18 | 2012-01-04 | 刘奕 | Method for producing brookite TiO2 in large scale at low cost |
| CN103058273A (en) * | 2011-10-20 | 2013-04-24 | 中国科学院福建物质结构研究所 | Monodispersed brookite phase titanium dioxide nanometer spindle body powder and preparation method thereof |
| CN106187051A (en) * | 2016-07-12 | 2016-12-07 | 中山市华山高新陶瓷材料有限公司 | Nano titanium dioxide inorganic coating and preparation method thereof |
| CN107244894A (en) * | 2017-06-08 | 2017-10-13 | 钦州学院 | The connection method of Nixing pottery base substrate |
| CN108686263A (en) * | 2018-06-11 | 2018-10-23 | 新乡学院 | A method of preparing HA biodegradable coatings in Mg alloy surface |
| CN111807712A (en) * | 2020-07-23 | 2020-10-23 | 长虹美菱股份有限公司 | Self-cleaning glass panel of refrigerator and preparation process thereof |
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Open date: 20090513 |