CN1261204C - Preparation of air purifier for visible light responded titanium dioxide photocatalytic chamber - Google Patents
Preparation of air purifier for visible light responded titanium dioxide photocatalytic chamber Download PDFInfo
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- CN1261204C CN1261204C CN 200410059680 CN200410059680A CN1261204C CN 1261204 C CN1261204 C CN 1261204C CN 200410059680 CN200410059680 CN 200410059680 CN 200410059680 A CN200410059680 A CN 200410059680A CN 1261204 C CN1261204 C CN 1261204C
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Abstract
The present invention relates to a preparation method of an air purifier for visible light responded titanium dioxide photocatalyst chambers. Titanium dioxides coated on the outer wall, which are high efficiency self-cleaning coating materials, are compounded with an oxide system containing rare metal and transition metal so that metal oxides/ titanium dioxide hetero junctions are formed, so the titanium dioxides are modified and easily activated by visible light to make the titanium dioxides be suitable for indoor air purification. The titanium dioxides are modified under the condition that the photocatalytic activity of the titanium dioxides is fully ensured; titanium dioxide photocatalysts are activated in a frequency spectrum area of the visible light after the titanium dioxide photocatalysts are modified. Thereby, the responded range of the titanium dioxide photocatalysts is widened. The titanium dioxide photocatalysts after being modified have the advantages shown by experiments of fast indoor air purification, high purification quality, and obvious effects on new decorated indoor air purification; the titanium dioxide photocatalysts have optical activity in the indoor light and do not need exciting by short wave light or irradiating by strong light, and the purification effects are free from the influence of the initial concentration of the pollutants in the air.
Description
Technical field
The present invention relates to a kind of preparation method of indoor air purification agent visible-light response type photocatalyst of titanium dioxide.
Background technology
Photocatalyst of titanium dioxide is as indoor air purification agent, and its convenience, security highlight just gradually.Usually used air freshener is just covered airborne penetrating odor, rather than the harmful substance of the penetrating odor that sends is thoroughly removed, and does not play the effect that purifies air in fact.Photocatalyst of titanium dioxide has deep oxidation efficiently, contained organic gaseous contamination thing and bacterium exhaustive oxidation in the room air can be become carbon dioxide and water, and self is nontoxic, and these two is the photocatalyst of titanium dioxide reason that agent more and more is much accounted of as indoor purifying just.
The main component of the photocatalyst of titanium dioxide that uses as the indoor purifying agent is a titanium dioxide.In countries such as Japan, Korea S, extensive studies has been carried out in the photocatalysis of titanium dioxide, but the research of domestic this respect is less, and rests on the preparation of titanium dioxide ultramicron and the titanium dioxide aspect such as compound in some simple oxidation things mostly.
Material with photocatalytic activity is a lot, but the non-toxic nature of titanium dioxide is the at first reason of titanium dioxide as indoor air purification agent.The semiconductor energy gap of titanium dioxide is 3.2 electron volts, and it just produces effective absorption at ultraviolet region, and producing has the positive electricity hole of strengthening oxidation to the air organic pollution, and produces light induced electron simultaneously.Since general indoor ultraviolet light very a little less than, outdoor sunshine medium ultraviolet light is stronger, the energy gap of titanium dioxide is 3.2 electron volts, this has just determined that titanium dioxide absorbs light can only be at ultraviolet region, so titanium dioxide is widely used in the self-cleaning coating of exterior wall.Indoor illumination medium ultraviolet light component is very faint, unmodified titanium dioxide is applied to indoor air purification has little effect.
Indoor for photocatalyst of titanium dioxide is used for, the present invention makes it produce effectively at visible region and absorbs by with titania modified, overcomes the more weak problem of using and bringing for unmodified photocatalyst of titanium dioxide of indoor ultraviolet light with this.
Summary of the invention
The object of the invention is, the preparation method of the visible-light response type photocatalyst of titanium dioxide indoor air purification agent that provides, this method is the efficient self-cleaning coating titanium dioxide that will be used for exterior wall by being that wherein any one is compound for rare metal lanthanum, cerium and transition metal oxide manganese, iron, cobalt, nickel, copper with titanium dioxide ultramicron and modified metal, form metal oxide/titanium dioxide heterogeneous knot, what make is titania modified, to be applicable to indoor air purification.The present invention makes improvements under the condition that fully guarantees the optically catalytic TiO 2 activity, is that the photocatalyst of titanium dioxide after the modification absorbs at visible region, has widened the photoresponse scope of photocatalyst of titanium dioxide.Show by test, photocatalyst of titanium dioxide after the modification has photolytic activity under indoor light, do not need it to be excited or uses strong illumination with short wavelength light, fast to indoor air purification, the depuration quality height, clean-up effect is not subjected to the influence of pollutant initial concentration in the air, and is particularly remarkable to newly-decorated indoor air purification effect.Simultaneously, metal oxide that modification of the present invention is used and titanium dioxide are all nontoxic, but and the photocatalyst of titanium dioxide after the modification with organic gas air pollutants exhaustive oxidation after automatic regeneration, thereby guaranteed air purifying preparation security and the effect permanence.
The preparation method of visible-light response type photocatalyst of titanium dioxide indoor air purification agent of the present invention, this method is passed through titanium dioxide ultramicron and rare metal lanthanum and cerium oxide, and be selected from manganese, iron, cobalt, nickel, the oxide of any one transition metal is compound in the copper, form metal oxide/titanium dioxide heterogeneous knot, make titania modified, wherein the modified metal gross mass accounts for the 2%-10% of titanium dioxide quality, rare metal lanthanum and cerium and be selected from manganese in the modified metal, iron, cobalt, nickel, the ratio of the atomicity in the copper between any one transition metal three is 0.7-1.2: 0.7-1.2: 0.7-1.2.
The preparation method of visible-light response type photocatalyst of titanium dioxide indoor air purification agent follows these steps to carry out:
A, at first prepare the titanium dioxide ultramicron aqueous solution of dynamic stabilization:
Hydrolyzable titanium-containing compound titanium tetrachloride or four alkoxytitaniums are slowly added in 0 ℃-20 ℃ the deionized water, wherein the quality of deionized water be hydrolyzable titanium-containing compound quality 55-60 doubly, hydrolyzable titanium-containing compound hydrolysis and to be dispersed into granularity be nanometer 10 under action of ultrasonic waves
-9The ultramicron of meter level, with this ultramicron aqueous solution clear under visible light, stand-by again;
B, the solution of lanthanum and cerium rare metal joined in the transparent ultramicron solution evenly dissolve each other, stirred 1-2 hour, stand-by;
C, the solution of any one transition metal in manganese, iron, cobalt, nickel, the copper is joined step b gained solution evenly dissolve each other, stirred 1-2 hour, stand-by;
D, with step c gained solution in 30 ℃ of-50 ℃ of following evaporated under reduced pressure of temperature and grind, in 700 ℃-900 ℃ air calcination 2-3 hour, grind again after the cooling, promptly get the visible-light response type photocatalyst of titanium dioxide.
The specific embodiment
Embodiment 1
A, at first prepare the titanium dioxide ultramicron aqueous solution of dynamic stabilization:
The hydrolyzable titanium-containing compound titanium tetrachloride of 3.5 grams slowly added in 1 ℃ the 200ml deionized water hydrolyzable titanium-containing compound hydrolysis and to be dispersed into granularity be nanometer 10 under action of ultrasonic waves
-9The ultramicron of meter level, with clear under this ultramicron aqueous solution and the visible light, stand-by again;
B, the solution atomicity that rare metal is contained lanthanum, cerium joined than 0.7: 0.7 in the transparent ultramicron solution and evenly dissolve each other, and stirred 1 hour, and be stand-by;
C, the solution atomicity that the oxide of transition metal is contained manganese join step b gained solution than 1.0 and evenly dissolve each other, and stir 1 hour, and be stand-by;
D, with step c gained solution in 30 ℃ of following evaporated under reduced pressure of temperature, grinding, calcination is 2 hours in 700 ℃ air, grinds after the cooling again, promptly gets the visible-light response type photocatalyst of titanium dioxide, wherein the modified metal gross mass accounts for 9% of titanium dioxide quality.
Embodiment 2
A, at first prepare the titanium dioxide ultramicron aqueous solution of dynamic stabilization:
Hydrolyzable titanium-containing compound four alkoxytitaniums of 4 grams are slowly added in 15 ℃ the 285ml deionized water hydrolyzable titanium-containing compound hydrolysis and to be dispersed into granularity be nanometer 10 under action of ultrasonic waves
-9The ultramicron of meter level, with clear under this ultramicron aqueous solution and the visible light, stand-by again;
B, the solution atomicity that rare metal is contained lanthanum, cerium joined than 1.0: 1.0 in the transparent ultramicron solution and evenly dissolve each other, and stirred 1.5 hours, and be stand-by;
C, the solution atomicity of the oxide iron content of transition metal is joined step b gained solution than 0.9 evenly dissolve each other, stirred 1.5 hours, stand-by;
D, with step c gained solution in 40 ℃ of following evaporated under reduced pressure of temperature and grind, calcination is 2.5 hours in 800 ℃ air, grinds after the cooling again, promptly gets the visible-light response type photocatalyst of titanium dioxide, wherein the modified metal gross mass accounts for 7% of titanium dioxide quality.
Embodiment 3
A, at first prepare the titanium dioxide ultramicron aqueous solution of dynamic stabilization:
The hydrolyzable titanium-containing compound titanium tetrachloride of 4.3 grams slowly added in 10 ℃ the 220ml deionized water hydrolyzable titanium-containing compound hydrolysis and to be dispersed into granularity be nanometer 10 under action of ultrasonic waves
-9The ultramicron of meter level, with clear under this ultramicron aqueous solution and the visible light, stand-by again;
B, with rare metal contain lanthanum, the solution of cerium atom number than 1.2: 1.2 joins in the transparent ultramicron solution and evenly dissolves each other, and stirs 2 hours, and is stand-by;
C, the solution atomicity that the oxide of transition metal is contained cobalt join step b gained solution than 0.7 and evenly dissolve each other, and stir 2 hours, and be stand-by;
D, with step c gained solution in 50 ℃ of following evaporated under reduced pressure of temperature and grind, calcination is 3 hours in 900 ℃ air, grinds after the cooling again, promptly gets the visible-light response type photocatalyst of titanium dioxide, wherein the modified metal gross mass accounts for 5% of titanium dioxide quality.
Embodiment 4
A, at first prepare the titanium dioxide ultramicron aqueous solution of dynamic stabilization:
Hydrolyzable titanium-containing compound four alkoxytitaniums of 3.2 grams are slowly added in 20 ℃ the 210ml deionized water hydrolyzable titanium-containing compound hydrolysis and to be dispersed into granularity be nanometer 10 under action of ultrasonic waves
-9The ultramicron of meter level, with clear under this ultramicron aqueous solution and the visible light, stand-by again;
B, the solution atomicity that rare metal is contained lanthanum, cerium joined than 0.9: 0.9 in the transparent ultramicron solution and evenly dissolve each other, and stirred 2 hours, and be stand-by;
C, the solution atomicity that the oxide of transition metal is nickeliferous join step b gained solution than 1.0 and evenly dissolve each other, and stir 2 hours, and be stand-by;
D, with step c gained solution in 35 ℃ of following evaporated under reduced pressure of temperature and grind, calcination is 2 hours in 750 ℃ air, grinds after the cooling again, promptly gets the visible-light response type photocatalyst of titanium dioxide, wherein the modified metal gross mass accounts for 8% of titanium dioxide quality.
Embodiment 5
A, at first prepare the titanium dioxide ultramicron aqueous solution of dynamic stabilization:
The hydrolyzable titanium-containing compound titanium tetrachloride of 4.5 grams slowly added in 20 ℃ the 440ml deionized water hydrolyzable titanium-containing compound hydrolysis and to be dispersed into granularity be nanometer 10 under action of ultrasonic waves
-9The ultramicron of meter level, with clear under this ultramicron aqueous solution and the visible light, stand-by again;
B, the solution atomicity that rare metal is contained lanthanum, cerium joined than 1.0: 1.0 in the transparent ultramicron solution and evenly dissolve each other, and stirred 1.5 hours, and be stand-by;
C, the solution atomicity of the oxide cupric of transition metal is joined step b gained solution than 1.2 evenly dissolve each other, stirred 1.5 hours, stand-by;
D, with step c gained solution in 45 ℃ of following evaporated under reduced pressure of temperature and grind, calcination is 2.5 hours in 850 ℃ air, grinds after the cooling again, promptly gets the visible-light response type photocatalyst of titanium dioxide, wherein the modified metal gross mass accounts for 10% of titanium dioxide quality.
Claims (1)
1, a kind of preparation method of visible-light response type photocatalyst of titanium dioxide indoor air purification agent, it is characterized in that by oxide titanium dioxide ultramicron and rare metal lanthanum and cerium, and be selected from manganese, iron, cobalt, nickel, the oxide of any one transition metal is compound in the copper, make titania modified, wherein the modified metal gross mass accounts for the 2%-10% of titanium dioxide quality, rare metal lanthanum and cerium and be selected from manganese in the modified metal, iron, cobalt, nickel, the ratio of the atomicity in the copper between any one the transition metal three is 0.7-1.2: 0.7-1.2: 0.7-1.2; Specifically follow these steps to carry out:
A, at first prepare the titanium dioxide ultramicron aqueous solution of dynamic stabilization:
Hydrolyzable titanium-containing compound titanium tetrachloride or four alkoxytitaniums are slowly added in 0 ℃-20 ℃ the deionized water, wherein the quality of deionized water be hydrolyzable titanium-containing compound quality 55-60 doubly, hydrolyzable titanium-containing compound hydrolysis and be dispersed into the ultramicron that granularity is a nanometer 10-9 meter level under action of ultrasonic waves, with this ultramicron aqueous solution clear under visible light, stand-by again;
B, the solution of lanthanum and cerium rare metal joined in the transparent ultramicron solution evenly dissolve each other, stirred 1-2 hour, stand-by;
C, the solution of any one transition metal in manganese, iron, cobalt, nickel, the copper is joined step b gained solution evenly dissolve each other, stirred 1-2 hour, stand-by;
D, with step c gained solution in 30 ℃ of-50 ℃ of following evaporated under reduced pressure of temperature and grind, in 700 ℃-900 ℃ air calcination 2-3 hour, grind again after the cooling, promptly get the visible-light response type photocatalyst of titanium dioxide.
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| CN 200410059680 CN1261204C (en) | 2004-06-15 | 2004-06-15 | Preparation of air purifier for visible light responded titanium dioxide photocatalytic chamber |
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Cited By (1)
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| CN101637695B (en) * | 2008-07-30 | 2011-08-10 | 北新集团建材股份有限公司 | Mineral wool decorative acoustic board with function of eliminating formaldehyde |
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| CN102580717B (en) * | 2011-12-30 | 2014-02-05 | 济南大学 | Gradient-structured metal oxide and preparation method thereof |
| CN105413629B (en) * | 2015-12-31 | 2018-03-16 | 湖北格林森绿色环保材料股份有限公司 | Algae calcium mineral air purifying medium and preparation method and application |
| CN105925021B (en) * | 2016-06-03 | 2018-06-22 | 浙江和谐光催化科技有限公司 | TiO2/Ga2O3The preparation method of composite photocatalyst colloid |
| CN106215940B (en) * | 2016-07-08 | 2018-10-02 | 湖南永清环保研究院有限责任公司 | A kind of preparation method and applications of the cerium modified titanium deoxide catalyst of iron copper |
| CN106179367B (en) * | 2016-07-08 | 2018-11-06 | 湖南永清环保研究院有限责任公司 | A kind of cerium modified titanium deoxide catalyst of copper and its preparation method and application |
| CN106345214A (en) * | 2016-08-26 | 2017-01-25 | 湖南集能新材料科技有限公司 | Water-base emergent rapid purifying agent for haze (fine particulate matters) |
| CN108786821A (en) * | 2017-04-28 | 2018-11-13 | 大族激光科技产业集团股份有限公司 | A kind of preparation method of photocatalyst |
| CN108404924A (en) * | 2018-04-11 | 2018-08-17 | 王彩兰 | It is a kind of that there is visible light-responded composite photo-catalyst preparation method |
| CN111116147A (en) * | 2020-01-20 | 2020-05-08 | 成都新柯力化工科技有限公司 | Diatom ooze for efficient air purification and preparation method thereof |
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| CN101637695B (en) * | 2008-07-30 | 2011-08-10 | 北新集团建材股份有限公司 | Mineral wool decorative acoustic board with function of eliminating formaldehyde |
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