CN101342498A - Titanium dioxide nano-tube support with macroscopical shape and preparation method thereof - Google Patents
Titanium dioxide nano-tube support with macroscopical shape and preparation method thereof Download PDFInfo
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- CN101342498A CN101342498A CNA200810054137XA CN200810054137A CN101342498A CN 101342498 A CN101342498 A CN 101342498A CN A200810054137X A CNA200810054137X A CN A200810054137XA CN 200810054137 A CN200810054137 A CN 200810054137A CN 101342498 A CN101342498 A CN 101342498A
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Abstract
The invention discloses a titanium-oxide nano-pipe carrier with a macro-shape and a preparation method thereof. The specific surface area of the carrier is 150-200m2.g-1, the porosity is 70-85 percent, and the aperture is 50-70nm. The preparation procedures include that (1) the solution is washed by alkaline and acid successively; (2) the solution is condensed, and then filled into a mould with a certain size for drying; (3) the product after being dried is calcined under high temperature and then moulded. The invention overcomes the problems of difficult separation and difficult regeneration during the photocatalysis of titanium-oxide nano-pipe, decrease of catalyst due to catalyst loss accompanying the water discharge and influence to the quality of discharged water; the invention provides a carrier with a macro-shape, and the carrier can be used as the load carrier of metal oxides.
Description
Technical field
The present invention relates to a kind of photocatalyst material and preparation method thereof, especially relate to a kind of photocatalyst material and preparation method thereof with macroshape.
Background technology
At present, because photocatalysis can produce the very strong hydroxyl radical free radical of oxidability, it can non-selectivity ground be degraded the polluter reaction, so the exploitation of new and effective photochemical catalyst becomes focus.As a kind of photochemical catalyst, titania nanotube becomes the research focus of photochemical catalyst and ozone catalytic agent as the product that specific area is bigger in the titanium dioxide series.
But the titania nanotube that is used to study photochemical catalyst at present is generally powder, in actual use, powder titanium dioxide exists and is difficult to separate, inconvenience regeneration, and catalyst can cause the minimizing of catalytic amount along with the water outlet loss in the course of reaction, influence effluent quality, practical value is restricted.
Summary of the invention
The objective of the invention is to overcome existing titania nanotube is difficult to separate in photocatalytic process, inconvenience regeneration, catalyst can cause the minimizing of catalytic amount along with the water outlet loss in the course of reaction, influence the deficiency of effluent quality, a kind of titanium dioxide nano-tube support and preparation method thereof with macroshape is provided.
Titanium dioxide nano-tube support with macroshape of the present invention, specific area are 150-200m
2G
-1, porosity is 70%-85%, and the aperture is 50-70nm, and it prepares according to following steps:
(1) add titanium dioxide powder in concentrated alkali solution, stir 0.5-1h, hydro-thermal reaction takes place in reactor then, reaction temperature is 100-120 ℃, and reaction 20-30h is washed to neutrality at last;
(2) use the pH value of the solution that acid solution regulating step (1) obtains, make it less than 3, and in less than 3 solution, soak 0.4-1h, be washed to neutrality once more;
(3) solution that step (2) is obtained concentrates, and making its moisture content is 45%-60%;
(4) concentrated solution with step (3) preparation changes in the mould, under 50-70 ℃, and dry 5-7h under the normal pressure;
(5) the solid titania support of step (4) preparation is calcined, calcining heat is 300-700 ℃, and calcination time is 5-7h, can obtain to have the titanium dioxide nano-tube support of macroshape.
The concentrated alkali solution of described step (1) is sodium hydrate aqueous solution or the potassium hydroxide aqueous solution of 10-20mol/L.
The inner liner of reaction kettle of described step (1) has polytetrafluoroethylene (PTFE).
The acid solution of described step (2) is hydrochloric acid, sulfuric acid, phosphoric acid or the nitric acid of 0.1-0.5mol/L.
A kind of preparation of the present invention has the method for the titanium dioxide nano-tube support of macroshape, prepares according to following steps:
(1) add titanium dioxide powder in concentrated alkali solution, stir 0.5-1h, hydro-thermal reaction takes place in reactor then, reaction temperature is 100-120 ℃, and reaction 20-30h is washed to neutrality at last;
(2) use the pH value of the solution that acid solution regulating step (1) obtains, make it less than 3, and in less than 3 solution, soak 0.4-1h, be washed to neutrality once more;
(3) solution that step (2) is obtained concentrates, and making its moisture content is 45%-60%;
(4) concentrated solution with step (3) preparation changes in the mould, under 50-70 ℃, and dry 5-7h under the normal pressure;
(5) the solid titania support of step (4) preparation is calcined, calcining heat is 300-700 ℃, and calcination time is 5-7h, can obtain to have the titanium dioxide nano-tube support of macroshape.
The concentrated alkali solution of described step (1) is sodium hydrate aqueous solution or the potassium hydroxide aqueous solution of 10-20mol/L.
The inner liner of reaction kettle of described step (1) has polytetrafluoroethylene (PTFE).
The acid solution of described step (2) is hydrochloric acid, sulfuric acid, phosphoric acid or the nitric acid of 0.1-0.5mol/L.
A kind of load of the present invention has the titanium dioxide nano-tube support with macroshape of metal oxide, prepares according to following steps:
(1) disposes Cu (NO respectively
3)
2, Fe (NO
3)
3, Mn (NO
3)
2The aqueous solution, making wherein, the mass fraction of copper, iron, manganese is 6%-8%;
The titanium dioxide nano-tube support with macroshape that (2) will prepare is immersed in respectively in three kinds of solution of step (1) preparation, and the time is 10-24h;
(3) titanium dioxide nano-tube support after will flooding is 40-60 ℃ of oven dry down, at 500-600 ℃ of calcining 4-7h down, gets final product to such an extent that load has CuO, Fe
2O
3, the titanium dioxide nano-tube support of MnO with macroshape.
The metal oxide-loaded method of titanium dioxide nano-tube support that a kind of utilization of the present invention has macroshape prepares according to following steps:
(1) disposes Cu (NO respectively
3)
2, Fe (NO
3)
3, Mn (NO
3)
2The aqueous solution, making wherein, the mass fraction of copper, iron, manganese is 6%-8%;
The titanium dioxide nano-tube support with macroshape that (2) will prepare is immersed in respectively in three kinds of solution of step (1) preparation, and the time is 10-24h;
(3) titanium dioxide nano-tube support after will flooding is 40-60 ℃ of oven dry down, at 500-600 ℃ of calcining 4-7h down, gets final product to such an extent that load has CuO, Fe
2O
3, the titanium dioxide nano-tube support of MnO with macroshape.
With the preparation of traditional titanium dioxide, technical scheme of the present invention is filtered washed solution and is obtained concentrate, changes die for molding then over to, calcines again.When changing mould over to, note the gas of mould the inside is discharged, in case the column that generates is impaired, up progressively inject from the bottom of mould with syringe.Behind the drying and moulding, carry out high-temperature calcination again, can make carrier have good active, obtain different crystal formations by the control different temperatures, and then obtain different activity, for example during 300 ℃ of calcinings based on unformed and small amount of anatase, in the time of 400 ℃ based on Detitanium-ore-type, 500, Detitanium-ore-type changes to rutile 600 ℃ the time, in the time of 700 ℃ based on rutile.
By accompanying drawing 1-3, titania support of the present invention as can be seen has macroshape, shows as the about 2cm of diameter, the column of the about 3cm of length, and loose structure and titania nanotube structure (the about 5nm of internal diameter, the about 1nm of tube wall, the about 200nm of length) have been kept in microstructure.By accompanying drawing 4-6, the mould that uses among the present invention is cylindric as can be seen, and those skilled in the art can improve shape, size and the quantity of mould according to actual needs, for example spherical, cuboid or cube.
Preparation with traditional titanium dioxide, titanium dioxide nano-tube support of the present invention has macroshape, size according to the macroscopical titania support size for preparing, fluid bed or packed bed design are carried out in photocatalysis and catalysis ozone technology, solved the difficult shortcoming of separating of catalyst in traditional suspension processing procedure.In photo catalysis reactor, under the aeration of certain intensity, can make carbon dioxide nano-tube support reach fluidized state with macroshape, make it become the fluidized bed photo catalysis reactor, overcome the deficiency that powder morphology is difficult to separate and influence water quality.After reaction a period of time, the contaminated inactivation of carrier can conveniently be regenerated its taking-up, and the means of regeneration mainly contain high-temperature calcination, soda acid desorption etc. at present, and the carrier after the regeneration is promptly reusable.
Carrier of the present invention has not only solved difficult separation problem and reusable problem, comes other yuan of load usually to carry out catalyst modification or uses as adsorbent but also can be used as titania support.But Supported CuO for example, Fe
2O
3, metal oxides such as MnO, titanium dioxide nano-tube support flooded a period of time in the nitrate of this metalloid after, after the load, also need to calcine, purpose mainly is that the metal nitrate pyroreaction is generated metal oxide, finishes the load of carrier to metal oxide.
The beneficial effect of patent of the present invention is, can make catalyst be easy to separate in photocatalysis and catalysis ozone technology, and renewable repeated use reduces catalyst and adds cost.The titania support that this catalyst also can be used as bigger serface uses, and titania support is comparatively rare in the existing market, has certain market value.
Description of drawings
The microstructure of accompanying drawing 1 titania support
The vesicular texture of accompanying drawing 2 titania supports
The macroshape of accompanying drawing 3 titanium dioxide
The vertical view of accompanying drawing 4 preparation moulds
The cutaway view of accompanying drawing 5 preparation moulds
The stereogram of accompanying drawing 6 preparation moulds
The specific embodiment
Below in conjunction with the specific embodiment, further specify the technical scheme of preparation titania support of the present invention, it is that the titania powder (trade name is P25) of 25 nanometers is prepared that embodiments of the invention adopt business-like particle diameter.
(1) take by weighing 1gP25, adding 20mL concentration is the sodium hydrate aqueous solution of 10mol/L, stirs 0.5h, changes the reactor of inner liner polytetrafluoroethylene over to, and 100 ℃ are reacted 20h down, are washed to neutrality.
(2) the pH value that obtains solution with the hydrochloric acid regulating step (1) of 0.1mol/L is less than 3, and soaks 0.5h, is washed to neutrality.
(3) solution that step (2) is obtained concentrates, and making its moisture content is 50%.
(4) concentrated solution with step (3) preparation changes in the mould, under 60 ℃, and constant pressure and dry 7h.
(5) the solid titania support of step (4) preparation is calcined, calcining heat is 300 ℃, and calcination time is 7h, can obtain to have the titanium dioxide nano-tube support of macroshape.
Embodiment 2
(1) take by weighing 5gP25, adding 50mL concentration is the sodium hydrate aqueous solution of 15mol/L, stirs 0.8h, changes the reactor of inner liner polytetrafluoroethylene over to, and 100 ℃ are reacted 25h down, are washed to neutrality.
(2) the pH value that obtains solution with the hydrochloric acid regulating step (1) of 0.5mol/L is less than 3, and soaks 0.8h, is washed to neutrality.
(3) solution that step (2) is obtained concentrates, and making its moisture content is 45%.
(4) concentrated solution with step (3) preparation changes in the mould, under 70 ℃, and constant pressure and dry 5h.
(5) the solid titania support of step (4) preparation is calcined, calcining heat is 700 ℃, and calcination time is 5h, can obtain to have the titanium dioxide nano-tube support of macroshape.
Embodiment 3
(1) take by weighing 7gP25, adding 60mL concentration is the sodium hydrate aqueous solution of 20mol/L, stirs 1h, changes the reactor of inner liner polytetrafluoroethylene over to, and 120 ℃ are reacted 25h down, are washed to neutrality.
(2) the pH value that obtains solution with the sulfuric acid regulating step (1) of 0.5mol/L is less than 3, and soaks 1h, is washed to neutrality.
(3) solution that step (2) is obtained concentrates, and making its moisture content is 60%.
(4) concentrated solution with step (3) preparation changes in the mould, under 60 ℃, and constant pressure and dry 6h.
(5) the solid titania support of step (4) preparation is calcined, calcining heat is 400 ℃, and calcination time is 6h, can obtain to have the titanium dioxide nano-tube support of macroshape.
Embodiment 4
(1) take by weighing 4gP25, adding 60mL concentration is the potassium hydroxide aqueous solution of 16mol/L, stirs 0.8h, changes the reactor of inner liner polytetrafluoroethylene over to, and 120 ℃ are reacted 30h down, are washed to neutrality.
(2) the pH value that obtains solution with the phosphoric acid regulating step (1) of 0.3mol/L is less than 3, and soaks 0.8h, is washed to neutrality.
(3) solution that step (2) is obtained concentrates, and making its moisture content is 55%.
(4) concentrated solution with step (3) preparation changes in the mould, under 65 ℃, and constant pressure and dry 5h.
(5) the solid titania support of step (4) preparation is calcined, calcining heat is 500 ℃, and calcination time is 7h, can obtain to have the titanium dioxide nano-tube support of macroshape.
Embodiment 5
(1) take by weighing 4gP25, adding 70mL concentration is the potassium hydroxide aqueous solution of 10mol/L, stirs 0.5h, changes the reactor of inner liner polytetrafluoroethylene over to, and 110 ℃ are reacted 25h down, are washed to neutrality.
(2) the pH value that obtains solution with the nitric acid regulating step (1) of 0.2mol/L is less than 3, and soaks 0.4h, is washed to neutrality.
(3) solution that step (2) is obtained concentrates, and making its moisture content is 45%.
(4) concentrated solution with step (3) preparation changes in the mould, under 50 ℃, and constant pressure and dry 7h.
(5) the solid titania support of step (4) preparation is calcined, calcining heat is 600 ℃, and calcination time is 7h, can obtain to have the titanium dioxide nano-tube support of macroshape.
Embodiment 6
(1) take by weighing 7gP25, adding 50mL concentration is the potassium hydroxide aqueous solution of 20mol/L, stirs 0.7h, changes the reactor of inner liner polytetrafluoroethylene over to, and 120 ℃ are reacted 30h down, are washed to neutrality.
(2) the pH value that obtains solution with the hydrochloric acid regulating step (1) of 0.5mol/L is less than 3, and soaks 0.5h, is washed to neutrality.
(3) solution that step (2) is obtained concentrates, and making its moisture content is 50%.
(4) concentrated solution with step (3) preparation changes in the mould, under 55 ℃, and constant pressure and dry 6.5h.
(5) the solid titania support of step (4) preparation is calcined, calcining heat is 650 ℃, and calcination time is 6.5h, can obtain to have the titanium dioxide nano-tube support of macroshape.
Embodiment 7
(1) take by weighing 7gP25, adding 50mL concentration is the sodium hydrate aqueous solution of 15mol/L, stirs 1h, changes the reactor of inner liner polytetrafluoroethylene over to, and 100 ℃ are reacted 20h down, are washed to neutrality.
(2) the pH value that obtains solution with the hydrochloric acid regulating step (1) of 0.3mol/L is less than 3, and soaks 0.5h, is washed to neutrality.
(3) solution that step (2) is obtained concentrates, and making its moisture content is 60%.
(4) concentrated solution with step (3) preparation changes in the mould, under 70 ℃, and constant pressure and dry 5h.
(5) the solid titania support of step (4) preparation is calcined, calcining heat is 550 ℃, and calcination time is 5h, can obtain to have the titanium dioxide nano-tube support of macroshape.
Embodiment 8
(1) take by weighing 7gP25, adding 60mL concentration is the sodium hydrate aqueous solution of 10mol/L, stirs 0.6h, changes the reactor of inner liner polytetrafluoroethylene over to, and 110 ℃ are reacted 30h down, are washed to neutrality.
(2) the pH value that obtains solution with the hydrochloric acid regulating step (1) of 0.4mol/L is less than 3, and soaks 0.6h, is washed to neutrality.
(3) solution that step (2) is obtained concentrates, and making its moisture content is 55%.
(4) concentrated solution with step (3) preparation changes in the mould, under 55 ℃, and constant pressure and dry 5.5h.
(5) the solid titania support of step (4) preparation is calcined, calcining heat is 450 ℃, and calcination time is 5h, can obtain to have the titanium dioxide nano-tube support of macroshape.
Embodiment 9
(1) take by weighing 8gP25, adding 70mL concentration is the sodium hydrate aqueous solution of 18mol/L, stirs 0.8h, changes the reactor of inner liner polytetrafluoroethylene over to, and 120 ℃ are reacted 30h down, are washed to neutrality.
(2) the pH value that obtains solution with the sulfuric acid regulating step (1) of 0.4mol/L is less than 3, and soaks 0.8h, is washed to neutrality.
(3) solution that step (2) is obtained concentrates, and making its moisture content is 58%.
(4) concentrated solution with step (3) preparation changes in the mould, under 70 ℃, and constant pressure and dry 7h.
(5) the solid titania support of step (4) preparation is calcined, calcining heat is 350 ℃, and calcination time is 5.5h, can obtain to have the titanium dioxide nano-tube support of macroshape.
Embodiment 10
(1) take by weighing 7gP25, adding 40mL concentration is the potassium hydroxide aqueous solution of 12mol/L, stirs 1h, changes the reactor of inner liner polytetrafluoroethylene over to, and 100 ℃ are reacted 25h down, are washed to neutrality.
(2) the pH value that obtains solution with the phosphoric acid regulating step (1) of 0.3mol/L is less than 3, and soaks 1h, is washed to neutrality.
(3) solution that step (2) is obtained concentrates, and making its moisture content is 50%.
(4) concentrated solution with step (3) preparation changes in the mould, under 50 ℃, and constant pressure and dry 5h.
(5) the solid titania support of step (4) preparation is calcined, calcining heat is 650 ℃, and calcination time is 7h, can obtain to have the titanium dioxide nano-tube support of macroshape.
Below in conjunction with specific embodiment, further specify and utilize titania support of the present invention to come metal oxide-loaded technical scheme.
(1) configuration Cu (NO
3)
2The aqueous solution, wherein the mass fraction of copper is 6%;
(2) titanium dioxide nano-tube support with above-mentioned preparation is immersed in Cu (NO
3)
2The aqueous solution in, the time is 24h;
(3) titanium dioxide nano-tube support after will flooding is 60 ℃ of oven dry down, at 600 ℃ of calcining 7h down, gets final product to such an extent that load has the titanium dioxide nano-tube support with macroshape of CuO.
Embodiment 2
(1) configuration Cu (NO
3)
2The aqueous solution, wherein the mass fraction of copper is 8%;
(2) titanium dioxide nano-tube support with above-mentioned preparation is immersed in Cu (NO
3)
2The aqueous solution in, the time is 10h;
(3) titanium dioxide nano-tube support after will flooding is 40 ℃ of oven dry down, at 500 ℃ of calcining 4h down, gets final product to such an extent that load has the titanium dioxide nano-tube support with macroshape of CuO.
Embodiment 3
(1) configuration Fe (NO
3)
3The aqueous solution, wherein the mass fraction of iron is 6%;
(2) titanium dioxide nano-tube support with above-mentioned preparation is immersed in Fe (NO
3)
3The aqueous solution in, the time is 24h;
(3) titanium dioxide nano-tube support after will flooding is 50 ℃ of oven dry down, at 600 ℃ of calcining 6h down, gets final product to such an extent that load has Fe
2O
3The titanium dioxide nano-tube support with macroshape.
Embodiment 4
(1) configuration Fe (NO
3)
3The aqueous solution, wherein the mass fraction of iron is 8%;
(2) titanium dioxide nano-tube support with above-mentioned preparation is immersed in Fe (NO
3)
3The aqueous solution in, the time is 15h;
(3) titanium dioxide nano-tube support after will flooding is 60 ℃ of oven dry down, at 500 ℃ of calcining 7h down, gets final product to such an extent that load has Fe
2O
3The titanium dioxide nano-tube support with macroshape.
Embodiment 5
(1) configuration Mn (NO
3)
2The aqueous solution, wherein the mass fraction of iron is 8%;
(2) titanium dioxide nano-tube support with above-mentioned preparation is immersed in Mn (NO
3)
2The aqueous solution in, the time is 20h;
(3) titanium dioxide nano-tube support after will flooding is 60 ℃ of oven dry down, at 600 ℃ of calcining 4h down, gets final product to such an extent that load has the titanium dioxide nano-tube support with macroshape of MnO.
Embodiment 6
(1) configuration Mn (NO
3)
2The aqueous solution, wherein the mass fraction of iron is 6%;
(2) titanium dioxide nano-tube support with above-mentioned preparation is immersed in Mn (NO
3)
2The aqueous solution in, the time is 15h;
(3) titanium dioxide nano-tube support after will flooding is 50 ℃ of oven dry down, at 500 ℃ of calcining 6h down, gets final product to such an extent that load has the titanium dioxide nano-tube support with macroshape of MnO.
Preparation with traditional titanium dioxide, titanium dioxide nano-tube support of the present invention has macroshape, size according to the macroscopical titania support size for preparing, fluid bed or packed bed design are carried out in photocatalysis and catalysis ozone technology, solved the difficult shortcoming of separating of catalyst in traditional suspension processing procedure.In photo catalysis reactor, under the aeration of certain intensity, can make carbon dioxide nano-tube support reach fluidized state with macroshape, make it become the fluidized bed photo catalysis reactor, overcome the deficiency that powder morphology is difficult to separate and influence water quality.After reaction a period of time, the contaminated inactivation of carrier can conveniently be regenerated its taking-up, and the means of regeneration mainly contain high-temperature calcination, soda acid desorption etc. at present, and the carrier after the regeneration is promptly reusable.
Carrier of the present invention has not only solved difficult separation problem and reusable problem, comes other yuan of load usually to carry out catalyst modification or uses as adsorbent but also can be used as titania support.
The beneficial effect of patent of the present invention is, can make catalyst be easy to separate in photocatalysis and catalysis ozone technology, can repeat Regeneration is used, and reduces catalyst and adds cost. The titania support that this catalyst also can be used as bigger serface uses, order Titania support is comparatively rare in the front market, has certain market value.
Claims (10)
1. the titanium dioxide nano-tube support with macroshape is characterized in that, the specific area of carrier is 150-200m
2G
-1, porosity is 70%-85%, and the aperture is 50-70nm, and it prepares according to following steps:
(1) add titanium dioxide powder in concentrated alkali solution, stir 0.5-1h, hydro-thermal reaction takes place in reactor then, reaction temperature is 100-120 ℃, and reaction 20-30h is washed to neutrality at last;
(2) use the pH value of the solution that acid solution regulating step (1) obtains, make it less than 3, and in less than 3 solution, soak 0.4-1h, be washed to neutrality once more;
(3) solution that step (2) is obtained concentrates, and making its moisture content is 45%-60%;
(4) concentrated solution with step (3) preparation changes in the mould, under 50-70 ℃, and dry 5-7h under the normal pressure;
(5) the solid titania support of step (4) preparation is calcined, calcining heat is 300-700 ℃, and calcination time is 5-7h, can obtain to have the titanium dioxide nano-tube support of macroshape.
2. the titanium dioxide nano-tube support with macroshape according to claim 1 is characterized in that, the concentrated alkali solution of described step (1) is sodium hydrate aqueous solution or the potassium hydroxide aqueous solution of 10-20mol/L
3. the titanium dioxide nano-tube support with macroshape according to claim 1 is characterized in that, the inner liner of reaction kettle of described step (1) has polytetrafluoroethylene (PTFE).
4. the titanium dioxide nano-tube support with macroshape according to claim 1 is characterized in that, the acid solution of described step (2) is hydrochloric acid, sulfuric acid, phosphoric acid or the nitric acid of 0.1-0.5mol/L.
5. one kind prepares the method with titanium dioxide nano-tube support of macroshape as claimed in claim 1, it is characterized in that, prepares according to following steps:
(1) add titanium dioxide powder in concentrated alkali solution, stir 0.5-1h, hydro-thermal reaction takes place in reactor then, reaction temperature is 100-120 ℃, and reaction 20-30h is washed to neutrality at last;
(2) use the pH value of the solution that acid solution regulating step (1) obtains, make it less than 3, and in less than 3 solution, soak 0.4-1h, be washed to neutrality once more;
(3) solution that step (2) is obtained concentrates, and making its moisture content is 45%-60%;
(4) concentrated solution with step (3) preparation changes in the mould, under 50-70 ℃, and dry 5-7h under the normal pressure;
(5) the solid titania support of step (4) preparation is calcined, calcining heat is 300-700 ℃, and calcination time is 5-7h, can obtain to have the titanium dioxide nano-tube support of macroshape.
6. a kind of method with titanium dioxide nano-tube support of macroshape as claimed in claim 1 for preparing according to claim 5, it is characterized in that the concentrated alkali solution of described step (1) is sodium hydrate aqueous solution or the potassium hydroxide aqueous solution of 10-20mol/L.
7. a kind of method with titanium dioxide nano-tube support of macroshape as claimed in claim 1 for preparing according to claim 5 is characterized in that the inner liner of reaction kettle of described step (1) has polytetrafluoroethylene (PTFE).
8. a kind of method with titanium dioxide nano-tube support of macroshape as claimed in claim 1 for preparing according to claim 5 is characterized in that the acid solution of described step (2) is hydrochloric acid, sulfuric acid, phosphoric acid or the nitric acid of 0.1-0.5mol/L.
9. one kind is utilized the metal oxide-loaded method of titanium dioxide nano-tube support with macroshape as claimed in claim 1, it is characterized in that, prepares according to following steps:
(1) disposes Cu (NO respectively
3)
2, Fe (NO
3)
3, Mn (NO
3)
2The aqueous solution, making wherein, the mass fraction of copper, iron, manganese is 6%-8%;
(2) titanium dioxide nano-tube support with macroshape as claimed in claim 1 is immersed in respectively in three kinds of solution of step (1) preparation, the time is 10-24h;
(3) titanium dioxide nano-tube support after will flooding is 40-60 ℃ of oven dry down, and at 500-600 ℃ of calcining 4-7h down, can make load respectively has CuO, Fe
2O
3, the titanium dioxide nano-tube support of MnO with macroshape.
10. a load has the titanium dioxide nano-tube support with macroshape of metal oxide, it is characterized in that, prepares according to following steps:
(1) disposes Cu (NO respectively
3)
2, Fe (NO
3)
3, Mn (NO
3)
2The aqueous solution, making wherein, the mass fraction of copper, iron, manganese is 6%-8%;
(2) will be immersed in respectively in three kinds of solution of step (1) preparation as the described titanium dioxide nano-tube support with macroshape of claim I, the time is 10-24h;
(3) titanium dioxide nano-tube support after will flooding is 40-60 ℃ of oven dry down, at 500-600 ℃ of calcining 4-7h down, gets final product to such an extent that load has CuO, Fe
2O
3, the titanium dioxide nano-tube support of MnO with macroshape.
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| CN104525167A (en) * | 2014-12-16 | 2015-04-22 | 浙江理工大学 | Titanium dioxide nano tube and preparation method thereof |
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| CN109926037A (en) * | 2017-12-15 | 2019-06-25 | 中国科学院大连化学物理研究所 | One kind preparing TiO by titanium-based binder2The method of preformed catalyst carrier |
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| CN109926037A (en) * | 2017-12-15 | 2019-06-25 | 中国科学院大连化学物理研究所 | One kind preparing TiO by titanium-based binder2The method of preformed catalyst carrier |
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| CN112499673A (en) * | 2020-12-04 | 2021-03-16 | 中国地质大学（武汉） | Co-modified TiO with phosphorus-containing silicon self-assembled layer and metal oxide2Method for preparing nanotubes |
| CN114772684A (en) * | 2022-04-26 | 2022-07-22 | 南京理工大学 | Microporous titanium-based iridium tantalum whole body electrode applied to deep treatment of chemical tail water and preparation method and application thereof |
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