CN104261466B - A kind of method utilizing hydrothermal synthesis method to prepare black titanium dioxide - Google Patents
A kind of method utilizing hydrothermal synthesis method to prepare black titanium dioxide Download PDFInfo
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- CN104261466B CN104261466B CN201410371619.3A CN201410371619A CN104261466B CN 104261466 B CN104261466 B CN 104261466B CN 201410371619 A CN201410371619 A CN 201410371619A CN 104261466 B CN104261466 B CN 104261466B
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Abstract
The invention discloses a kind of method utilizing hydrothermal synthesis method to prepare black titanium dioxide, the concrete steps of described method are as follows: (1) first adds sodium peroxide or Potassium peroxide in titanium hydride or titanium nitride powder, then mix, then add water, stir; (2) polytetrafluoroethyllining lining of reactor is at room temperature soaked 1h in chloroazotic acid, then three times are boiled with distilled water, then powder mixed solution prepared by step (1) is put into polytetrafluoroethyllining lining, polytetrafluoroethyllining lining is placed in supporting steel bushing, tightens; (3) reactor is placed in isothermal reactor, at 150-250 DEG C, reaction 3-7h; (4), after reaction terminates, the product that step (3) obtains is carried out centrifugal, abandoning supernatant, taking precipitate, with deionized water wash; (5) throw out step (4) obtained is dried, and obtains the titanium dioxide powder of black.
Description
Technical field
The present invention relates to titanium dioxide preparing technical field, particularly relate to a kind of method utilizing hydrothermal synthesis method to prepare black titanium dioxide.
Background technology
Along with economic growth, the raising of people's environmental consciousness, environmental problem is also day by day more and more paid close attention to.And the toxic and harmful contained in the middle of air also endangers the healthy of people, how safety, the content reducing toxic and harmful in air efficiently also becomes an important problem.Photocatalyst is nontoxic and efficient nano-photocatalyst as one, progresses in the middle of market, and has attracted increasing attention.Photochemical catalysis, as the term suggests the katalysis caused by light exactly, under the bringing out of light, this catalyzer can decomposing formaldehyde safely and efficiently, and toluene, the toxic and harmfuls such as TVOC, in addition also have the effect of disinfection.At present, because titanium dioxide is with low cost, functional, so domestic photocatalyst all selects titanium dioxide to be core material.Titanium dioxide without any doping treatment is white, is proper semiconductor, and its energy gap is 3.2eV.According to the principle of conductor photocatalysis, if white titania is wanted to play its photocatalysis characteristic, only have the ultraviolet portion absorbed in solar spectrum just can be activated.But in sunlight ultraviolet portion be only 5% less than, therefore the quantum yield of white titania is lower.
In order to solve the low problem of white titania quantum yield, people start titanium dioxide and other ions to adulterate, and reduce its energy gap.And the auto-doping of titanium dioxide (3 valency titaniums replace 4 valency titaniums) is because its wider spectral response had, higher catalytic effect, and the focus becoming research gradually.And therefore titanium dioxide be also provided with distinct colors.The TiO of black
2found in 2011 by X.Chen at first, its preparation process is by general T iO
2calcine in the atmosphere of hydrogen, after for some time, its color directly becomes black by white transition, and Absorption edge is also corresponding moves to far infrared region, in the experiment of photochemical catalyzing afterwards, and the TiO of black
2show splendid performance.The method for making of black titanium dioxide is substantially also similar afterwards, is all the titaniums by chemical reduction, the titanium of 4 valencys being reduced to 3 valencys, thus reaches the object of auto-doping.But the method power consumption is large, and working condition is harsh, and productive rate is also lower, and quality product also cannot ensure, thus cost is caused to remain high.
In sum, the black titanium dioxide prepared by auto-doping method, it serves vital effect to raising photocatalyst quantum yield.And how to find out the black titanium dioxide that a kind of easy method of cheapness prepares low cost, then become the major subjects of current research.
Summary of the invention
For the problems referred to above, the present invention proposes a kind of technique preparing black titanium dioxide completely newly, by adopting the method for Hydrothermal Synthesis, self-doping type black titanium dioxide can be obtained.
The present invention adopts following technical scheme:
The concrete steps utilizing hydrothermal synthesis method to prepare the method for black titanium dioxide of the present invention are as follows:
(1) in the titanium hydride or titanium nitride powder of 80-100 weight part, first add sodium peroxide or the Potassium peroxide of 80-100 weight part, then mix, then add the water of 90-100 weight part, stir;
(2) polytetrafluoroethyllining lining of reactor is at room temperature soaked 1h in chloroazotic acid, then three times are boiled with distilled water, then powder mixed solution prepared by step (1) is put into polytetrafluoroethyllining lining, polytetrafluoroethyllining lining is placed in supporting steel bushing, tightens;
(3) reactor is placed in isothermal reactor, at 150-250 DEG C, reaction 3-7h;
(4), after reaction terminates, undertaken centrifugal by the product that step (3) obtains, rotating speed is 3000-5000r/min, and the time is 10-15min, abandoning supernatant, taking precipitate, with deionized water wash;
(5) throw out step (4) obtained is dried, and obtains the titanium dioxide powder of black.
In step (2), the compactedness of powder mixed solution in polytetrafluoroethyllining lining prepared by step (1) is 80%.
In step (3), preferably at 200 DEG C, reaction 5h.
In step (4), preferred rotating speed is 4000r/min, and the time is 15min.
Hydrothermal method refers in special autoclave, adopts the aqueous solution as reaction medium, by reaction vessel heating, creates high temperature, a reaction under high pressure environment, makes usual indissoluble or insoluble substance dissolves and recrystallization.Because hydro-thermal reaction is carried out under the condition of untethered, therefore have many advantages compared with other wet chemical method preparing on nano-powder, once complete at high temperature under high pressure as having, without the need to later stage Crystallizing treatment, obtained powder granularity narrowly distributing, reunion degree is low, and composition is pure, preparation process is polluted little, easily realizes the advantages such as suitability for industrialized production and is regulated by controlling reaction conditions by the product cut size that the method is obtained.The method preparation technology is simple, and equipment is cheap, is extremely suitable for the scale operation of enterprise.Employing hydrothermal method prepares black titanium dioxide can obtain different performance black titanium dioxide product by control reaction conditions control product cut size and doping content in addition.
Positively effect of the present invention is as follows:
1. the present invention utilizes the hydride of titanium or nitride as starting material, and abundance is with low cost;
2. step of the present invention is simple, and the reaction times is short, can greatly enhance productivity, and reduces production cost;
3. the hydrothermal synthesis method in the present invention can regulate and control the particle diameter of product more accurately, and doping level, can meet different environments for use.
Accompanying drawing explanation
Fig. 1 is the XRD figure spectrum of black titanium dioxide powder prepared by embodiment 1.
Fig. 2 is the scanning electron microscope collection of illustrative plates of black titanium dioxide powder prepared by embodiment 1.
Fig. 3 be embodiment 1 prepare black titanium dioxide and P25 type ordinary white titanium dioxide degradable methylene blue efficiency comparative scheme.
Embodiment
The following examples describe in further detail of the present invention.
Embodiment 1
Get Beijing sold on the market great fortune FTiH2 type titanium hydride powders 100g, the sodium peroxide 100g of Tianjin great Mao chemical reagent work, water 100g, is placed in beaker, after mixing, adds in reactor polytetrafluoroethyllining lining.Compactedness is 80%.Inner bag is inserted in reactor, tightens steel lid.By reactor as in isothermal reactor, temperature of reaction is 200 DEG C, and the reaction times is 5h.Reaction terminate after, by centrifugal for the product obtained, rotating speed is 4000r/min, and centrifugation time is 15min, abandoning supernatant, taking precipitate, with deionized water wash repeatedly, in an oven by throw out dry, obtain black titanium dioxide powder.
Embodiment 2
Get sold on the market Jinzhou sky sky FTiH2 type titanium hydride powders 90g, the sodium peroxide 100g of Dagu, Tianjin chemical industry, water 100g, is placed in beaker, after mixing, adds in reactor polytetrafluoroethyllining lining.Compactedness is 80%.Inner bag is inserted in reactor, tightens steel lid.By reactor as in isothermal reactor, temperature of reaction is 200 DEG C, and the reaction times is 5h.Reaction terminate after, by centrifugal for the product obtained, rotating speed is 4000r/min, and centrifugation time is 15min, abandoning supernatant, taking precipitate, with deionized water wash repeatedly, in an oven by throw out dry, obtain black titanium dioxide powder.
Embodiment 3
Get the prosperous FTiH in sea, Jinzhou sold on the market
2-2 type titanium hydride powders 80g, the sodium peroxide 80g of Tianjin good fortune chemical reagent factory in morning, water 90g, is placed in beaker, after mixing, adds in reactor polytetrafluoroethyllining lining.Compactedness is 80%.Inner bag is inserted in reactor, tightens steel lid.By reactor as in isothermal reactor, temperature of reaction is 200 DEG C, and the reaction times is 5h.Reaction terminate after, by centrifugal for the product obtained, rotating speed is 4000r/min, and centrifugation time is 15min, abandoning supernatant, taking precipitate, with deionized water wash repeatedly, in an oven by throw out dry, obtain black titanium dioxide powder.
Embodiment 4
Get Beijing Xing Rongyuan TIMP1 type titanium nitride powder 80g sold on the market, the sodium peroxide 80g of Tianjin good fortune chemical reagent factory in morning, water 100g, is placed in beaker, after mixing, adds in reactor polytetrafluoroethyllining lining.Compactedness is 80%.Inner bag is inserted in reactor, tightens steel lid.By reactor as in isothermal reactor, temperature of reaction is 200 DEG C, and the reaction times is 5h.Reaction terminate after, by centrifugal for the product obtained, rotating speed is 4000r/min, and centrifugation time is 15min, abandoning supernatant, taking precipitate, with deionized water wash repeatedly, in an oven by throw out dry, obtain black titanium dioxide powder.
Embodiment 5
Get the prosperous TiN type titanium nitride powder 100g in sea, Jinzhou sold on the market, the Potassium peroxide 100g of Beijing China industry whole world chemical industry, water 100g, is placed in beaker, after mixing, adds in reactor polytetrafluoroethyllining lining.Compactedness is 80%.Inner bag is inserted in reactor, tightens steel lid.By reactor as in isothermal reactor, temperature of reaction is 200 DEG C, and the reaction times is 5h.Reaction terminate after, by centrifugal for the product obtained, rotating speed is 4000r/min, and centrifugation time is 15min, abandoning supernatant, taking precipitate, with deionized water wash repeatedly, in an oven by throw out dry, obtain black titanium dioxide powder.
The catalytic performance of black titanium dioxide powder prepared by embodiment 6 the present invention
Experimental technique:
1. get two cuvettes, clean and dry, load a certain amount of methylene blue solution, measure the absorbancy C of now methylene blue solution with spectrophotometric
0;
2. take commercially available PM25 type TiO
2powder 2g, with black TiO obtained in present method
2powder 2g, joins respectively in two test tubes, and test tube is labeled as A, B;
3. by two test tubes as in fluorescent lamp, start timing, and get isopyknic methylene blue solution every 5min, by its absorbancy of Spectrophotometric Determination, and with the methylene blue dulling luminosity ratio recorded at first comparatively, obtain C/C
0value;
4. according to C/C
0value and timing relationship, can obtain Fig. 3.
As shown in Figure 3, with P25 type TiO
2compare, black TiO prepared by present method
2under ordinary lamps rayed, there is more excellent photocatalysis characteristic.
Although illustrate and describe embodiments of the invention, for the ordinary skill in the art, be appreciated that and can carry out multiple change, amendment, replacement and modification to these embodiments without departing from the principles and spirit of the present invention, scope of the present invention is by claims and equivalents thereof.
Claims (3)
1. utilize hydrothermal synthesis method to prepare a method for black titanium dioxide, it is characterized in that: the concrete steps of described method are as follows:
(1) in the titanium nitride powder of 80-100 weight part, first add sodium peroxide or the Potassium peroxide of 80-100 weight part, then mix, then add the water of 90-100 weight part, stir;
(2) polytetrafluoroethyllining lining of reactor is at room temperature soaked 1h in chloroazotic acid, then three times are boiled with distilled water, then powder mixed solution prepared by step (1) is put into polytetrafluoroethyllining lining, polytetrafluoroethyllining lining is placed in supporting steel bushing, tightens;
(3) reactor is placed in isothermal reactor, at 200 DEG C, reaction 5h;
(4), after reaction terminates, undertaken centrifugal by the product that step (3) obtains, rotating speed is 3000-5000r/min, and the time is 10-15min, abandoning supernatant, taking precipitate, with deionized water wash;
(5) throw out step (4) obtained is dried, and obtains the titanium dioxide powder of black.
2. the method for claim 1, is characterized in that: in step (2), and the compactedness of powder mixed solution in polytetrafluoroethyllining lining prepared by step (1) is 80%.
3. the method for claim 1, is characterized in that: in step (4), and rotating speed is 4000r/min, and the time is 15min.
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Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104828865B (en) * | 2015-03-26 | 2016-06-29 | 中国科学院新疆理化技术研究所 | A kind of preparation method of the single brookite titanium dioxide of black |
| CN106698367B (en) * | 2015-11-13 | 2019-04-30 | 中国科学院金属研究所 | A method of preparing nitridation titanium composite material |
| CN105600820B (en) * | 2015-12-30 | 2017-06-06 | 中国科学院上海硅酸盐研究所 | A kind of green titanium dioxide and preparation method thereof, method of modifying and application |
| CN106076307B (en) * | 2016-06-06 | 2018-11-20 | 吕浩然 | A kind of preparation method of rare earth element coblended nano TiO 2 photocatalyst |
| CN107128969A (en) * | 2017-05-15 | 2017-09-05 | 重庆森盟新能源开发有限公司 | A kind of methods for making and using same for the coating material for making glass that there is automatically cleaning effect |
| CN108940245B (en) * | 2018-08-10 | 2020-10-23 | 大连工业大学 | Black TiO2White TiO2Composite material and preparation method thereof |
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| CN103191707A (en) * | 2013-04-28 | 2013-07-10 | 中国科学院上海硅酸盐研究所 | Method for preparing black titanium dioxide by using dual-temperature area reducing method |
| CN103726092A (en) * | 2013-12-31 | 2014-04-16 | 天津新实能源科技有限公司 | Method for preparing auto-doping black titanium dioxide |
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| CN103191707A (en) * | 2013-04-28 | 2013-07-10 | 中国科学院上海硅酸盐研究所 | Method for preparing black titanium dioxide by using dual-temperature area reducing method |
| CN103726092A (en) * | 2013-12-31 | 2014-04-16 | 天津新实能源科技有限公司 | Method for preparing auto-doping black titanium dioxide |
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