CN1507943A - Method for preparing photocatalytic material sensitive to visible light - Google Patents
Method for preparing photocatalytic material sensitive to visible light Download PDFInfo
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- CN1507943A CN1507943A CNA02155188XA CN02155188A CN1507943A CN 1507943 A CN1507943 A CN 1507943A CN A02155188X A CNA02155188X A CN A02155188XA CN 02155188 A CN02155188 A CN 02155188A CN 1507943 A CN1507943 A CN 1507943A
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- titanium dioxide
- visible light
- ammonia
- argon gas
- catalysis material
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Abstract
The present invention discloses a method for preparing photocatalytic material capable of sensing visible light, and is characterized by that it adopts hydrated titanium dioxide as raw material, it can be reacted with mixed gas of ammonia gas and argon gas in high-temp. reaction farnace so as to obtain a photocatalytic material capable of sensing visible light. The present invention also provides a method for preparing said hydrated titanium dioxide. Said hydrated titanium dioxide powder body is placed in high-temp, tube furnace, the mixed gas formed from ammonia gas and argon gas can be introduced according to 2:1, and heated to 400 deg.C and reacted for 0.5 hr at said temperature.
Description
Technical field
The present invention relates to a kind of preparation method who is used for that photocatalysis curbs environmental pollution to the catalysis material of visible light sensitivity.Specifically, be a kind of preparation method of the nitrating photocatalysis material of titanium dioxide to the visible light sensitivity, belong to chemical compound preparation field or photochemical catalyst preparation field.
Background technology
Along with the raising of industrial expansion and living standards of the people, problem of environmental pollution has been mentioned on the very important agenda, develops efficient, energy-conservation, the environmental improvement of non-secondary pollution, the environmental protection new technology especially is subjected to people's attention.In all kinds of new technologies, photocatalysis technology is 21 century one of the most promising environmental friendliness cleaning new technology, the core of this technology is that illumination makes N-type semiconductor (being photochemical catalyst) produce photic carrier (hole and electronics), can produce multiple strong oxide group behind the oxygen G﹠W in the photic carrier contact water and air, can make most organic matter microorganisms of contact with it reach permineralization.The characteristics of this technology are easy to operate, non-secondary pollutions.This technology is in environmental protection, and promptly field such as the environmental protection problem of wastewater and exhaust gas purification, air cleaning aspect, new energy development, organic synthesis, self-cleaning and anti-biotic material production has broad application prospects.
But, extensive use at present with TiO
2Semiconductor for the existing main problem of semi-conducting material on basis is: light absorption wavelength is narrow.Because TiO
2Forbidden band broad (Eg=3.2eV), the absorbing wavelength threshold values is in the ultra-violet (UV) band, accounting in the sunshine about 95% visible light can't be used, so solar energy utilization ratio is low.This problem if can solve, and photocatalysis technology can really be used widely in fields such as environmental improvement and new materials.
The main means that address the above problem at present have doped transition metal ions, precious metal surface deposition, surface light sensitization etc.But noble metal or the metal oxide containing precious metals metal or the oxide of doping ion or coating in the light-catalyzed reaction process is easy to stripping, influences photocatalysis life-span and activity, also easily environment caused secondary pollution.Noble metal such as platinum and rhodium and oxide price thereof are too high in addition.Organic dye sensitized TiO
2After, TiO
2Photoelectric activity greatly improve; But because nano-TiO
2Have strong oxidability, taking place the light-catalysed while, sensitising agent was lost efficacy easily with sensitising agent oxidation together.
European patent EP 1160202A1 discloses a kind of preparation method of the nitrogenous titanium dioxide optical catalyst to the visible light sensitivity, this method is to be raw material with inorganic titanium salts such as titanyl sulfate, titanium tetrachloride or titanium trichlorides, it is made into the finite concentration aqueous solution, slow dropping ammonia under ice bath then, with the washing of gained sediment, and behind the high-temperature heat treatment certain hour, obtain product.This method step is many, the time is long, energy consumption is big, and severe reaction conditions is difficult to control.
Scholars such as R.Asahi [SCIENCE, 2001,293 (5528): 269] are raw material with the anatase titanium dioxide, with ammonia gas react 3 hours, have prepared the photocatalysis material of titanium dioxide of optical absorption peak red shift under 600 ℃ of high temperature.But raw materials used in this method is the titanium dioxide raw material of the crystallization of process calcining, and then under 600 ℃ high temperature nitrating, it is through 2 heat treatment, particularly the 2nd secondary response temperature is very high, time is very long again, causes the optically catalytic TiO 2 activity to descend greatly.
Summary of the invention
The objective of the invention is to avoid above-mentioned the deficiencies in the prior art and provide that a kind of raw material sources are extensive, technology is simple, lower-cost new technology is produced the catalysis material to the visible light sensitivity.
Purpose of the present invention can reach by following measure: the preparation method of a kind of catalysis material to the visible light sensitivity of the present invention, it is characterized in that adopting hydrated titanium dioxide is raw material, mixed gas with ammonia and argon gas in high temperature reaction stove reacts, and can obtain a kind of catalysis material to the visible light sensitivity; Described hydrated titanium dioxide can be the hydrolysate that titanium sulfate, titanium tetrachloride, metatitanic acid or other titanium-containing compounds get through certain technology.The source of the hydrated titanium dioxide described in the present invention is that its preparation method is: the accessory substance metatitanic acid that produces during at normal temperatures with the Production By Sulfuric Acid Process titanium white is mixed with TiO
2Content is 26% suspension, and stirs, and adding concentration is 30% hydrochloric acid solution, be heated to and boil and stirred 1 hour, add 20% sodium hydroxide solution then, regulating the pH of suspension value is 7.0～8.0, suction filtration washs filter cake to the AgNO with 0.1mol/l while hot
3Solution detects no Cl
-Till, with filter cake 120 ℃ down the oven dry back pulverize get final product the hydrated titanium dioxide powder.Place high temperature process furnances to feed the mixed gas of ammonia and argon gas the hydrated titanium dioxide powder of gained, the ratio of ammonia and argon gas is 2: 1 or 3: 1, and its flow is 0.15m
3/ h, heating-up temperature is 400～600 ℃, reacts under this temperature 0.5～2.0 hour, the product that obtains at last is a kind of nitrating titanium dioxide TiO that contains
2-xN
xCatalysis material.Described hydrated titanium dioxide particle diameter is 1 ~ 200nm.
The photocatalysis new material to the visible light sensitivity of the present invention's preparation, wherein TiO
2Be anatase structures, particle diameter is distributed as 10～20nm (through the transmission electron microscope tem observation).
The catalysis material that the inventive method makes has very strong photocatalytic activity under radiation of visible light, can make full use of sunshine and indoor visible light sources such as incandescent lamp.Preparation method's of the present invention advantage is the material low cost of manufacture, and technology is simple.In addition, the catalysis material to the visible light sensitivity of the present invention is different with existing photochemical catalyst at aspects such as preparation method, catalyst composition, catalyst performance and action principles.Because the present invention makes it to form the width that the part titanium nitride reduces the forbidden band by mix nitrogen in titanium dioxide, absorption band is moved to the visible light direction, improve the purpose that its utilization rate to sunshine is implemented in performance photo-catalysis function in the visible-range thereby reach.Compare advantage such as the catalysis material to the visible light sensitivity of the present invention has the photocatalysis efficiency height, the deep oxidation ability is strong and reactivity is stable with the titanium deoxide catalyst of routine.
The specific embodiment
Now the embodiment with the inventive method is described in the back:
Embodiment one: prepare the raw material hydrated titanium dioxide at first earlier, its preparation method is: the accessory substance metatitanic acid that produces during at normal temperatures with the Production By Sulfuric Acid Process titanium white is mixed with TiO
2Content is 26% suspension, and stirs, and adding concentration is 30% hydrochloric acid solution, and being heated to boils stirred 1 hour, added 20% sodium hydroxide solution then, and regulating the pH of suspension value is 7.0～8.0, and suction filtration washs filter cake to the AgNO with 0.1mol/l while hot
3Solution detects no Cl
-Till.With filter cake at 120 ℃ down after the oven dry, pulverize get final product the hydrated titanium dioxide powder.
Hydrated titanium dioxide powder after the above-mentioned gained oven dry is placed high temperature process furnances, feed ammonia and argon gas mist, the ratio of ammonia and argon gas is 2: 1, and flow is 0.15m
3/ h is heated to 400 ℃ then, and reaction is 0.5 hour under this temperature, obtains a kind of nitrating titanium dioxide TiO that contains at last
2-xN
xCatalysis material.Embodiment two: prepare the raw material hydrated titanium dioxide at first earlier, its preparation method is fully identical with the foregoing description one.
Hydrated titanium dioxide powder after the above-mentioned gained oven dry is placed high temperature process furnances, feed ammonia and argon gas mist, the ratio of ammonia and argon gas is 2: 1, and flow is 0.15m
3/ h is heated to 600 ℃ then, and reacts 2.0 hours under this temperature, obtains a kind of nitrating titanium dioxide TiO that contains at last
2-xN
xCatalysis material.Embodiment three: prepare the raw material hydrated titanium dioxide at first earlier, its preparation method is fully identical with the foregoing description one.
Hydrated titanium dioxide powder after the above-mentioned gained oven dry is placed high temperature process furnances, feed the mixed gas of ammonia and argon gas, the ratio of ammonia and argon gas is 3: 1, is heated to 400 ℃ then, reaction is 0.5 hour under this temperature, obtains a kind of nitrating titanium dioxide TiO that contains at last
2-xN
xCatalysis material.
Powder sample and German Degussa P-25 titanium dioxide powder to the foregoing description one, two, three are made photocatalytic activity evaluation contrast test under the sunshine, test is carried out under identical conditions, time is 10:00 to 14:00 on July 11st, 2002, the average intensity of illumination of sunshine this moment is through ultraviolet light illumination instrumentation amount, and irradiation intensity is 18.27W/M
2
The evaluation method of photocatalytic activity is: the reactive brilliant red dyestuff is made into the solution that concentration is 10mg/l, HCl with 1.0mol/ regulates pH=2.5, in the above-mentioned solution of 500ml, add 0.01g photochemical catalyst sample, disperseed 10 minutes with ultrasonic wave, catalyst is uniformly dispersed, and place on the magnetic stirring apparatus and stir, its rotating speed is 200rpm, surveys the initial absorbance of solution; React with solar light irradiation then, from the bottom bubbling air of reactor, air mass flow is 0.08m in the course of reaction
3/ h extracts the reactant liquor about 30ml at regular intervals, and uses micro-pore-film filtration, adopts the spectrophotometric determination solution absorbency then, weighs activity of such catalysts according to dye decolored rate.
Each catalyst samples evaluation correction data of photocatalytic activity under sunshine is as shown in the table:
Photocatalytic activity evaluation under the sunshine
As seen from the above table, under solar light irradiation, the photocatalytic activity of each sample all is higher than German Degussa P-25, and wherein the photocatalytic activity of embodiment one sample is the highest, than P-25 high approximately 20%.
From researching and analysing of ultraviolet-visible light spectrogram, the absworption peak of P-25 is within 400nm as can be known, and the obvious red shift of the absworption peak of embodiment sample promptly has certain visible light-sensitive perception.
From x-ray photoelectron spectroscopy XPS technical Analysis, there is no simple TiN as can be known in the nitrating titanium dioxide and exist, add bright at nitrating titanium dioxide TiO
2-xN
xMiddle O-Ti-O bond is closed tightr, also illustrates that N has replaced former some O and formed N-Ti-O key simultaneously.
Claims (3)
1. preparation method to the catalysis material of visible light sensitivity, it is characterized in that adopting hydrated titanium dioxide is raw material, mixed gas with ammonia and argon gas in high temperature reaction stove reacts, can obtain a kind of catalysis material to the visible light sensitivity, described hydrated titanium dioxide can be the hydrolysate that titanium sulfate, titanium tetrachloride, metatitanic acid or other titanium-containing compounds get through certain technology.
2. the preparation method of a kind of catalysis material to the visible light sensitivity as claimed in claim 1, it is characterized in that described hydrated titanium dioxide source is that its preparation method is: the accessory substance metatitanic acid that produces during at normal temperatures with the Production By Sulfuric Acid Process titanium white is mixed with TiO
2Content is 26% suspension, and stirs, and adding concentration is 30% hydrochloric acid solution, be heated to and boil and stirred 1 hour, add the solution of 20% NaOH then, regulating the pH of suspension value is 7.0～8.0, suction filtration washs filter cake to the AgNO with 0.1mol/l while hot
3Solution detects no Cl
-Till, with filter cake 120 ℃ down the oven dry back pulverize, get final product the hydrated titanium dioxide powder; The hydrated titanium dioxide powder of gained is placed high temperature process furnances, feed the mixed gas of ammonia and argon gas, the ratio of ammonia and argon gas is 2: 1 or 3: 1, and flow is 0.15m
3/ h, heating-up temperature is 400～600 ℃, reacts under this temperature 0.5～2.0 hour, the product that obtains at last is a kind of nitrating titanium dioxide TiO that contains
2-xN
xCatalysis material.
3. the preparation method of a kind of catalysis material to the visible light sensitivity as claimed in claim 2, it is characterized in that described hydrated titanium dioxide particle diameter is 1 ~ 200nm, place high temperature process furnances to feed the mist of ammonia and argon gas this hydrated titanium dioxide, the optimal proportion of ammonia and argon gas is 2: 1, and flow is 0.15m
3/ h, the optimum temperature of heating-up temperature is 400 ℃, and the optimum reaction time is 0.5 hour under this temperature, and the product that obtains at last is a kind of nitrating titanium dioxide TiO that contains
2-xN
xCatalysis material.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA02155188XA CN1507943A (en) | 2002-12-17 | 2002-12-17 | Method for preparing photocatalytic material sensitive to visible light |
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|---|---|---|---|
| CNA02155188XA CN1507943A (en) | 2002-12-17 | 2002-12-17 | Method for preparing photocatalytic material sensitive to visible light |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1321738C (en) * | 2005-04-29 | 2007-06-20 | 北京科技大学 | Production of nitrogen-doped anatase-type nanometer titanium dioxide |
| CN101235478B (en) * | 2008-02-26 | 2010-04-14 | 上海大学 | Steel plate surface nano induction nitrogen alloying method |
| CN101533720B (en) * | 2009-04-10 | 2011-05-25 | 南开大学 | Metal nitride electrode material for dye-sensitized solar cell |
| CN113499762A (en) * | 2021-05-18 | 2021-10-15 | 浙江大学 | Simple preparation method of blue/black titanium dioxide photocatalytic material |
-
2002
- 2002-12-17 CN CNA02155188XA patent/CN1507943A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1321738C (en) * | 2005-04-29 | 2007-06-20 | 北京科技大学 | Production of nitrogen-doped anatase-type nanometer titanium dioxide |
| CN101235478B (en) * | 2008-02-26 | 2010-04-14 | 上海大学 | Steel plate surface nano induction nitrogen alloying method |
| CN101533720B (en) * | 2009-04-10 | 2011-05-25 | 南开大学 | Metal nitride electrode material for dye-sensitized solar cell |
| CN113499762A (en) * | 2021-05-18 | 2021-10-15 | 浙江大学 | Simple preparation method of blue/black titanium dioxide photocatalytic material |
| CN113499762B (en) * | 2021-05-18 | 2022-05-10 | 浙江大学 | Simple preparation method of blue/black titanium dioxide photocatalytic material |
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