CN114700061B - Preparation method of surface nano titanium substrate photocatalyst - Google Patents

Preparation method of surface nano titanium substrate photocatalyst Download PDF

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Publication number
CN114700061B
CN114700061B CN202210172567.1A CN202210172567A CN114700061B CN 114700061 B CN114700061 B CN 114700061B CN 202210172567 A CN202210172567 A CN 202210172567A CN 114700061 B CN114700061 B CN 114700061B
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cooling
titanium
titanium sheet
furnace
water
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CN114700061A (en
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刘彤宙
李雨阳
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Shenzhen Graduate School Harbin Institute of Technology
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Shenzhen Graduate School Harbin Institute of Technology
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
    • B01J21/063—Titanium; Oxides or hydroxides thereof
    • B01J35/39—
    • B01J35/59—
    • B01J35/613—
    • B01J35/633—
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/06—Washing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/08—Heat treatment
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/12—Oxidising
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
    • B01J37/341—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation
    • B01J37/343—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of ultrasonic wave energy
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/30—Treatment of water, waste water, or sewage by irradiation
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D9/00—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor
    • C21D9/46—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor for sheet metals
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
    • C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
    • C22F1/16—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of other metals or alloys based thereon
    • C22F1/18—High-melting or refractory metals or alloys based thereon
    • C22F1/183—High-melting or refractory metals or alloys based thereon of titanium or alloys based thereon
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
    • C23C22/68—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous solutions with pH between 6 and 8
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
    • C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
    • C23G1/02—Cleaning or pickling metallic material with solutions or molten salts with acid solutions
    • C23G1/10—Other heavy metals
    • C23G1/106—Other heavy metals refractory metals
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/30—Organic compounds
    • C02F2101/308—Dyes; Colorants; Fluorescent agents
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/30—Organic compounds
    • C02F2101/34—Organic compounds containing oxygen
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/30—Organic compounds
    • C02F2101/36—Organic compounds containing halogen
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/30—Organic compounds
    • C02F2101/38—Organic compounds containing nitrogen
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2305/00—Use of specific compounds during water treatment
    • C02F2305/10—Photocatalysts

Abstract

The invention discloses a preparation method of a surface nano titanium substrate photocatalyst, which comprises the following steps: s1, ultrasonic cleaning; s2, acid washing; s3, deepening: immersing the pickled titanium sheet into 50-52 parts by weight of H with the mass concentration of 30% 2 O 2 Adding melamine 18-22 weight parts into the solution, continuously stirring for 30min, and dropwise adding nitric acid solution with mass concentration of 60-63% 1-2 weight partsAfter the addition is finished, the titanium sheet and the mixed solution are put into an oven together to react for 72 hours at 80 ℃; s4, cooling and cleaning; s5, annealing treatment. The nano-structure TiO prepared by the preparation method of the surface nano-titanium substrate photocatalyst 2 Directly grow on the titanium substrate, the adhesion strength is high, and the nano-structure TiO is 2 The photocatalyst has good mechanical stability, is not easy to fall off, has no change of microstructure after out-of-furnace quenching and ultrasonic cleaning, is easy to recycle, and has good cycle performance.

Description

Preparation method of surface nano titanium substrate photocatalyst
Technical Field
The invention relates to the technical field of water treatment photocatalysts, in particular to a preparation method of a surface nano titanium substrate photocatalyst.
Background
TiO 2 The history of use is long, since the beginning of commercial production in the 20 th century, tiO 2 Is widely used as pigment, sun protection product, ointment, etc. In 1972, foreign scholars found that water was exposed to TiO under ultraviolet light 2 Photocatalytic decomposition phenomena at the electrodes. From this point on, the scholars at home and abroad are about TiO 2 Materials have been studied in a large number and many important research results have been achieved in the fields of environment, energy and the like. Anatase TiO 2 As the photocatalyst which is most widely used at present, the photocatalyst is widely used due to the characteristics of good ultraviolet light catalytic activity, chemical stability, low price and the like. A number of studies have shown that TiO is utilized 2 The photocatalytic oxidation method can effectively remove refractory organic matters in the wastewater. Compared with nano TiO 2 The powder is easy to aggregate, easy to inactivate, difficult to recycle and the like, and the thin film catalyst has the advantages of good cycle performance, no secondary pollution and the like. Currently carrying nanostructured TiO 2 The substrate of (a) is mainly FTO, glass, ceramic and the like. The method is characterized in that metallic titanium (titanium plate or titanium net) is taken as a substrate, and surface nanocrystallization treatment is carried out on the metallic titanium, so that nano-structure TiO directly grows on the surface of the metallic titanium 2 Compared with the existing substrate additionally loaded with TiO 2 The prepared catalyst material, film TiO 2 The nano structure has higher strength, is not easy to fall off, is easy to recycle and is convenient for repeated use.
Titanium metal oxidation processes include anodic oxidation and oxidant system direct oxidation. Anodic oxidation is the preparation of TiO 2 Common methods for nanotubes. Anodic oxidation is typically carried out in an electrolyte comprising an aqueous solution based on hydrofluoric acid. Electrically connecting titanium foilThe electrode and the counter electrode are immersed in an electrolyte, both of which are connected to a power source to apply a constant voltage. After the anodic oxidation process, tiO with straight channels is formed on the foil surface 2 A nanotube array; the direct oxidation method of the oxidant system is to realize the oxidation of titanium metal based on a reaction system of a titanium substrate and an oxidant, and directly prepare the nano-structure TiO 2 Or first obtaining an intermediate product (typically amorphous TiO 2 Or hydrogen titanic acid) and then is converted into TiO by subsequent high-temperature heat treatment or low-temperature crystallization 2 . By controlling the types and the addition amount of the additives in the oxidation reaction system or the subsequent heat treatment process of the intermediate, tiO with different morphologies can be realized 2 Is prepared by the following steps.
Preparation of nanostructured TiO for direct oxidation of metallic titanium with hydrogen peroxide 2 Various preparation methods have been proposed by researchers, and the invention patent of a method for preparing a directional arrangement titanium dioxide nanorod array on the surface of metallic titanium (application number 200510060751.3, publication number CN 100352970C) is taken as an example. The invention relates to a method for preparing a directional arrangement titanium dioxide nano rod array on the surface of metallic titanium, which comprises the following steps: hydrofluoric acid with the mass percentage concentration of 50-60%, nitric acid with the mass percentage concentration of 60-68% and deionized water are mixed according to the volume ratio of 1:3:6, cleaning the metal titanium plate with the mixed acid at 50-70 ℃, then cleaning the metal titanium plate with deionized water in ultrasonic, immersing the clean titanium plate in 30% hydrogen peroxide solution by mass percent concentration, and reacting for 24-72 hours at 60-85 ℃. The method is simple and easy to implement, the prepared nano rod array grows in a regular orientation, has good crystallization, fine crystal grains and good combination between the film and the matrix, but has low photocatalytic activity and more strict requirements on reaction conditions, and the preparation method is more complex, so that the application difficulty of the catalyst is increased.
Disclosure of Invention
Aiming at the problems, the invention provides a preparation method of a surface nano titanium substrate photocatalyst.
The technical scheme of the invention is as follows:
the preparation method of the surface nano titanium substrate photocatalyst comprises the following steps:
s1, ultrasonic cleaning: taking titanium sheets with purity of more than 99.8%, placing the titanium sheets into an acetone solution for ultrasonic cleaning for 15-20min, placing the titanium sheets into an ethanol solution for ultrasonic cleaning for 10-15min, placing the titanium sheets into deionized water for ultrasonic cleaning for 10-15min, and removing greasy dirt on the surfaces of the titanium sheets;
s2, acid washing: immersing the titanium sheet after ultrasonic cleaning in a cleaning solution, wherein the cleaning solution comprises hydrofluoric acid solution, nitric acid solution and deionized water according to a proportion of 1:3:6, mixing the titanium sheets in a volume ratio, wherein the soaking time is 1-2min, and then taking out the titanium sheets and repeating the process of the step S1;
s3, deepening: immersing the pickled titanium sheet into 50-52 parts by weight of H with the mass concentration of 30% 2 O 2 Adding 18-22 parts by weight of melamine into the solution, continuously stirring for 30min, dropwise adding 1-2 parts by weight of nitric acid solution with the mass concentration of 60-63%, and putting the titanium sheet and the mixed solution into an oven together after the dropwise adding is finished to react for 72h at 80 ℃; the weight part ratio of the melamine and the nitric acid solution is selected to lead TiO to be 2 The needle-like nano structure stably develops on a specific crystal face, and TiO is caused by selecting other proportions 2 The needle-like nanostructures are not fully developed.
S4, cooling and cleaning: taking out the titanium sheet after the deepening treatment, performing deionized water flowing cooling, reducing the temperature of the surface of the titanium sheet to 12-16 ℃, and then placing the titanium sheet into deionized water for ultrasonic cleaning for 1-2min;
s5, annealing treatment: airing the titanium sheet at the dark room temperature, then placing the titanium sheet in a muffle furnace for heating treatment, heating to 440-460 ℃ at the heating rate of 10 ℃/min, then carrying out heat treatment for 1h, and cooling to obtain the titanium sheet with the surface coated with TiO 2 Titanium platelet-based photocatalyst of nanowire array film.
Further, the length, width and height of the titanium sheet in the step S1 are 40mm, 40mm and 0.1mm respectively. And the subsequent treatment is convenient.
Further, the mass concentration of the acetone solution in the step S1 is 11-13.5mol/L, the mass concentration of the ethanol solution is 40%, the volumes of the acetone solution, the ethanol solution and the deionized water are all 30-40 times that of the titanium sheet, and the ultrasonic frequency of ultrasonic cleaning in the step S1 and the step S4 is 40kHz. The ultrasonic treatment can better remove the greasy dirt on the surface of the titanium sheet, and simultaneously has little damage to the titanium sheet.
Further, in the step S2, the mass concentration of the hydrofluoric acid solution is 40%, and the mass concentration of the nitric acid solution is 70%. Is beneficial to improving the pickling effect.
Further, in the step S3, the stirring speed is 120-140r/min, and the dropping speed of the nitric acid solution is 1-2ml/S. The reasonable stirring speed and the dropping speed are controlled, so that the stable reaction is facilitated.
Further, the temperature of the deionized water for flow cooling in the step S4 is 8-10 ℃, and the flow speed of the deionized water on the surface of the titanium sheet is 5-6ml/cm 2 S. Avoiding the water from rushing out of already grown but still fragile nanostructures.
Still further, the mobile cooling heat sink that mobile cooling was used in step S4 includes the water tank, and is located cooling box of water tank one side, cooling box inside is equipped with a plurality of cooling plates, communicates each other between all cooling plates and constitutes baffling cooling circuit, cooling box top one side is equipped with the delivery port, and the baffling cooling circuit end of every group cooling plate all is equipped with the water hole, and cooling box bottom baffling cooling circuit end is equipped with the return water mouth, and the equidistant standing groove that is used for placing the titanium piece that is equipped with of cooling plate upper surface, standing groove is equipped with the drainage groove relative baffling cooling circuit one end, the coating of drainage groove surface has the cooling coating, and the standing groove bottom is equipped with a plurality of through-holes, and cooling box both sides inner wall is equipped with the spout, and cooling box openly bottom is equipped with the fixed plate, the fixed plate top is equipped with spacing seal groove, and the fixed plate top is equipped with movable seal plate with spout sliding connection, movable seal plate bottom with spacing seal groove joint, the water storage tank that the return water mouth is located the water tank, one side of water storage tank is equipped with the temperature controller, temperature controller one side is equipped with the water pump, the water pump with the delivery port is connected. The cooling by flowing is better matched.
Preferably, the cooling coating is formed by mixing the following components: the high-molecular acrylic resin comprises, by weight, 10-12 parts of high-molecular acrylic resin liquid, 3-4 parts of ceramic powder, 1-2 parts of vacuum glass beads, 0.5-0.8 part of bentonite and 0.2 part of dispersing agent. Can promote the cooling effect and can not cause the injury to the titanium piece.
Further, in the step S5, the room temperature is 25-27 ℃, and the cooling process of the annealing treatment is divided into slow cooling in the furnace and quenching outside the furnace, wherein the steps of slow cooling in the furnace and quenching outside the furnace are as follows:
s5-1, slow cooling in the furnace: after the heat treatment is finished, the temperature in the furnace is reduced to 33-35 ℃ at a cooling speed of 20-30 ℃/min, and then the titanium sheet is naturally cooled in the furnace for 30-45min;
s5-2, quenching outside the furnace: taking out the titanium sheet from the furnace, quenching and cooling the surface of the titanium sheet by using an atomized liquid nitrogen quenching and cooling mode, setting 6 or 8 cooling points on the surface of the titanium sheet, setting the cooling points in a ring shape, correspondingly setting 3 or 4 liquid nitrogen spraying points at the same time, separating one cooling point between every two adjacent liquid nitrogen spraying points, and sequentially and synchronously moving the liquid nitrogen spraying points after cooling of one cooling point is completed, wherein the residence time of the liquid nitrogen spraying points at the cooling points is 2-3s, the spraying amount is 0.035-0.06ml/s, and the surface temperature of the titanium sheet is reduced to 18-21 ℃. The nano structure on the surface of the titanium sheet is primarily shaped through slow cooling in the furnace, and then the shaping effect of the nano structure is improved through quenching outside the furnace, so that further development of surface oxide is effectively prevented, influence on surface morphology is avoided, and meanwhile, damage to the nano structure is avoided by strictly controlling quenching parameters.
The beneficial effects of the invention are as follows:
(1) The nano-structure TiO prepared by the preparation method of the surface nano-titanium substrate photocatalyst 2 Directly grows on the titanium substrate, has high adhesive strength, and utilizes the compounded hydrogen peroxide to oxidize, cool, clean and anneal to lead the nano-structure TiO directly grows on the titanium substrate 2 The mechanical stability is good, the falling is not easy, the microstructure is not changed after the quenching outside the furnace and ultrasonic cleaning, and the TiO can be realized by selecting the weight part ratio of the specific melamine and the nitric acid solution 2 Needle-like nanostructures in a specific mannerStable development on crystal face, while other proportions can lead to TiO 2 The needle-like nanostructures are not fully developed.
(2) The surface nano titanium substrate photocatalyst provided by the invention directly grows on a titanium substrate, and has good recoverability. And, the preparation process can be repeated for the spent catalyst growing on the titanium substrate, and has good regeneration and recycling performance, which is the traditional TiO 2 Not provided with the particulate catalyst. In the actual production process, the titanium sheet-based catalyst can still keep good and stable photocatalytic performance until the fifth cycle, and can degrade 64% of RhB after 2 hours of reaction.
(3) The preparation method of the surface nano titanium substrate photocatalyst further introduces a special flowing cooling device for flowing cooling, further improves the cooling effect during cooling treatment, and simultaneously avoids the phenomenon that water rushes out of the grown but fragile nano structure.
(4) According to the preparation method of the surface nano titanium substrate photocatalyst, the nano structure on the surface of the titanium sheet is primarily shaped through slow cooling in the furnace, and then the shaping effect of the nano structure is improved through quenching outside the furnace, so that further development of surface oxide is effectively prevented, influence on surface morphology is avoided, and meanwhile, damage to the nano structure is avoided by strictly controlling quenching parameters.
Drawings
FIG. 1 is a process flow diagram of a method for preparing a surface nano-titanium substrate photocatalyst of the present invention;
FIG. 2 is a schematic view of the overall structure of the flow cooler of the present invention;
FIG. 3 is a schematic view of the internal structure of the flow cooler of the present invention;
FIG. 4 is a front view of the flow cooler of the present invention;
FIG. 5 is a top view and an internal schematic of the flow cooler of the present invention;
FIG. 6 is a schematic illustration of liquid nitrogen spray point movement for off-road quenching in example 1 of the present invention;
FIG. 7 is a schematic illustration of liquid nitrogen spray point movement for off-road quenching in example 9 of the present invention;
FIG. 8 is a TiO film prepared in example 1 of the present invention 2 SEM image of the film;
FIG. 9 is a TiO film prepared in example 1 of the present invention 2 A cross-sectional view of the film;
FIG. 10 is a TiO prepared in example 1 of the present invention 2 XRD pattern of the film;
FIG. 11 is a TiO film prepared in example 1 of the present invention 2 Nitrogen isothermal desorption drawing of nanowire powder scraped by a film;
FIG. 12 is a graph showing the recycling experiment of the surface nano-titanium substrate photocatalyst prepared in example 1 of the present invention.
The device comprises a 1-water tank, a 11-water storage tank, a 12-temperature controller, a 13-water suction pump, a 2-cooling tank, a 21-water outlet, a 22-water return port, a 23-chute, a 3-cooling plate, a 31-water through hole, a 32-placing groove, a 33-drainage groove, a 4-fixing plate, a 41-limit sealing groove and a 5-movable sealing plate.
Detailed Description
Example 1
The preparation method of the surface nano titanium substrate photocatalyst is shown in figure 1, and comprises the following steps:
s1, ultrasonic cleaning: taking titanium sheets with purity of more than 99.8%, wherein the length, width and height of the titanium sheets are 40mm, 40mm and 0.1mm respectively, putting the titanium sheets into an acetone solution for ultrasonic cleaning for 18min, putting the titanium sheets into an ethanol solution for ultrasonic cleaning for 12min, putting the titanium sheets into deionized water for ultrasonic cleaning for 14min, wherein the mass concentration of substances in the acetone solution is 12mol/L, the mass concentration of the ethanol solution is 40%, the volumes of the acetone solution, the ethanol solution and the deionized water are 36 times that of the titanium sheets, and the ultrasonic frequency of ultrasonic cleaning is 40kHz to remove greasy dirt on the surfaces of the titanium sheets;
s2, acid washing: immersing the titanium sheet after ultrasonic cleaning in a cleaning solution, wherein the cleaning solution comprises hydrofluoric acid solution, nitric acid solution and deionized water according to a proportion of 1:3:6, mixing the titanium sheet with the solution of hydrofluoric acid with the mass concentration of 40%, the solution of nitric acid with the mass concentration of 70% and the soaking time of 1min, and then taking out the titanium sheet and repeating the process of the step S1;
s3, deepening: immersing the pickled titanium sheet in 51 parts by weight of H with the mass concentration of 30% 2 O 2 Adding 20 parts by weight of melamine into the solution, continuously stirring for 30min at the stirring speed of 130r/min, dropwise adding 1.5 parts by weight of a nitric acid solution with the mass concentration of 62%, wherein the dropwise adding speed of the nitric acid solution is 1.5ml/s, and putting the titanium sheet and the mixed solution into an oven together after the dropwise adding is finished, and reacting for 72h at the temperature of 80 ℃;
s4, cooling and cleaning: taking out the deepened titanium sheet, performing flow cooling and cooling of deionized water, reducing the temperature of the surface of the titanium sheet to 14 ℃, then placing the titanium sheet into deionized water for ultrasonic cleaning for 1.5min, wherein the ultrasonic frequency of ultrasonic cleaning is 40kHz, the temperature of the deionized water for flow cooling and cooling is 9 ℃, and the flow speed of the deionized water on the surface of the titanium sheet is 5.5ml/cm 2 ·s；
As shown in fig. 2-5, the flow cooling device for flow cooling comprises a water tank 1 and a cooling box 2 positioned at one side of the water tank 1, a plurality of cooling plates 3 are arranged in the cooling box 2, all the cooling plates 3 are mutually communicated to form a baffling cooling circuit, a water outlet 21 is arranged at one side of the top of the cooling box 2, water passing holes 31 are arranged at the tail end of the baffling cooling circuit of each group of cooling plates 3, a water return port 22 is arranged at the tail end of the baffling cooling circuit at the bottom of the cooling box 2, a plurality of placing grooves 32 for placing titanium sheets are arranged on the upper surface of the cooling plates 3 at equal intervals, a drainage groove 33 is arranged at one end of the placing groove 32 opposite to the baffling cooling circuit, cooling paint is coated on the surface of the drainage groove 33, and the cooling paint is formed by mixing the following components: the high-molecular-weight high-strength glass comprises 11 parts of high-molecular acrylic resin liquid, 3 parts of ceramic powder, 1 part of vacuum glass beads, 0.8 part of bentonite and 0.2 part of dispersing agent by weight; the bottom of the placing groove 32 is provided with a plurality of through holes, the inner walls of the two sides of the cooling box 2 are provided with sliding grooves 23, the bottom of the front surface of the cooling box 2 is provided with a fixed plate 4, the top of the fixed plate 4 is provided with a limit sealing groove 41, a movable sealing plate 5 is arranged above the fixed plate 4, the movable sealing plate 5 is in sliding connection with the sliding grooves 23, the bottom of the movable sealing plate 5 is clamped with the limit sealing groove 41, a water return port 22 is connected with a water storage tank 11 positioned in the water tank 1, one side of the water storage tank 11 is provided with a temperature controller 12, the temperature controller 12 is a commercial power temperature controller, one side of the temperature controller 12 is provided with a water suction pump 13, the water suction pump 13 is an internal structure of the water tank 1 after the structural shape of the commercial water suction pump is adjusted, and the water suction pump 13 is connected with a water outlet 21;
working principle of the flow cooling device: when the titanium sheet cooling device is used, a titanium sheet is placed in the placing groove 32, then the bottom of the movable sealing plate 5 is clamped with the limiting sealing groove 41 through the sliding groove 23, the water outlet 21 is opened to enable cooling water to sequentially realize continuous cooling of the titanium sheet through the baffling loop, auxiliary cooling can be performed through cooling coating coated on the surface of the titanium sheet when water flows through the drainage groove 33, the bottom of the titanium sheet in the placing groove 32 can be cooled through the through hole when water flows through the next layer, the cooling effect is good, water circulation can be fully utilized, and the water flow speed is controllable and cannot damage the nano structure on the surface of the titanium sheet;
s5, annealing treatment: airing the titanium sheet at the dark room temperature, then placing the titanium sheet in a muffle furnace for heating treatment, heating to 450 ℃ at the heating rate of 10 ℃/min, then carrying out heat treatment for 1h, and cooling to obtain the titanium sheet with the surface coated with TiO 2 The titanium sheet-based photocatalyst of the nanowire array film has the room temperature of 26 ℃, and the cooling process of annealing treatment comprises the following steps of slow cooling in a furnace and quenching outside the furnace:
s5-1, slow cooling in the furnace: after the heat treatment is finished, the temperature in the furnace is reduced to 34 ℃ at a cooling speed of 25 ℃/min, and then the titanium sheet is naturally cooled in the furnace for 38min;
s5-2, quenching outside the furnace: taking the titanium sheet out of the furnace, quenching and cooling the surface of the titanium sheet by using an atomized liquid nitrogen quenching and cooling mode, wherein 6 cooling points are arranged on the surface of the titanium sheet, the cooling points are annular, 3 liquid nitrogen spraying points are correspondingly arranged at the same time, one cooling point is separated between every two adjacent liquid nitrogen spraying points, the liquid nitrogen spraying points sequentially and synchronously move after cooling of one cooling point is completed, the residence time of the liquid nitrogen spraying points at the cooling point is 2s, the spraying amount is 0.05ml/s, and the surface temperature of the titanium sheet is reduced to 19 ℃.
Example 2
This embodiment differs from embodiment 1 in that: the ultrasonic cleaning parameters in step S1 are different.
S1, ultrasonic cleaning: taking titanium sheets with purity of more than 99.8%, respectively, wherein the length, width and height of the titanium sheets are 40mm, 40mm and 0.1mm, putting the titanium sheets into an acetone solution for ultrasonic cleaning for 15min, putting the titanium sheets into an ethanol solution for ultrasonic cleaning for 10min, putting the titanium sheets into deionized water for ultrasonic cleaning for 10min, wherein the mass concentration of substances in the acetone solution is 11mol/L, the mass concentration of the ethanol solution is 40%, the volumes of the acetone solution, the ethanol solution and the deionized water are all 30 times that of the titanium sheets, and the ultrasonic frequency of ultrasonic cleaning is 40kHz to remove greasy dirt on the surfaces of the titanium sheets.
Example 3
This embodiment differs from embodiment 1 in that: the ultrasonic cleaning parameters in step S1 are different.
S1, ultrasonic cleaning: taking titanium sheets with purity of more than 99.8%, respectively placing the titanium sheets into an acetone solution for ultrasonic cleaning for 20min, placing the titanium sheets into an ethanol solution for ultrasonic cleaning for 15min, placing the titanium sheets into deionized water for ultrasonic cleaning for 15min, wherein the mass concentration of substances in the acetone solution is 13.5mol/L, the mass concentration of the ethanol solution is 40%, the volumes of the acetone solution, the ethanol solution and the deionized water are 40 times that of the titanium sheets, and the ultrasonic frequency of ultrasonic cleaning is 40kHz to remove greasy dirt on the surface of the titanium sheets.
Example 4
This embodiment differs from embodiment 1 in that: the parameters of the pickling in step S2 are different.
S2, acid washing: immersing the titanium sheet after ultrasonic cleaning in a cleaning solution, wherein the cleaning solution comprises hydrofluoric acid solution, nitric acid solution and deionized water according to a proportion of 1:3:6, mixing the titanium sheet with the solution of hydrofluoric acid with the mass concentration of 40%, the solution of nitric acid with the mass concentration of 70% and the soaking time of 2min, taking out the titanium sheet, and repeating the process of the step S1.
Example 5
This embodiment differs from embodiment 1 in that: and step S3, the parameters of the deepening process are different.
S3, deepening: immersing the pickled titanium sheet into 50 weight parts of the titanium sheet with the mass concentrationH with a degree of 30% 2 O 2 And then adding 18 parts by weight of melamine into the solution, continuously stirring for 30min at the stirring speed of 120r/min, dropwise adding 1 part by weight of nitric acid solution with the mass concentration of 60% into the solution at the dropping speed of 1ml/s, and putting the titanium sheet and the mixed solution into an oven together after the dropwise adding is finished to react for 72h at the temperature of 80 ℃.
Example 6
This embodiment differs from embodiment 1 in that: and step S3, the parameters of the deepening process are different.
S3, deepening: immersing the pickled titanium sheet in 52 parts by weight of H with the mass concentration of 30% 2 O 2 And then adding 22 parts by weight of melamine into the solution, continuously stirring for 30min at the stirring speed of 140r/min, dropwise adding 2 parts by weight of a nitric acid solution with the mass concentration of 63% into the solution at the dropping speed of 2ml/s, and putting the titanium sheet and the mixed solution into an oven together after the dropwise adding is finished to react for 72h at the temperature of 80 ℃.
Example 7
This embodiment differs from embodiment 1 in that: the parameters of the cooling wash in step S4 are different.
S4, cooling and cleaning: taking out the titanium sheet after deepening treatment, carrying out flow cooling on deionized water, reducing the temperature of the surface of the titanium sheet to 12 ℃, then putting the titanium sheet into deionized water for ultrasonic cleaning for 2min, wherein the ultrasonic frequency of ultrasonic cleaning is 40kHz, the temperature of the deionized water for flow cooling is 8 ℃, and the flow speed of the deionized water on the surface of the titanium sheet is 5ml/cm 2 ·s；
The flow cooling device for flow cooling comprises a water tank 1 and a cooling box 2 positioned on one side of the water tank 1, a plurality of cooling plates 3 are arranged in the cooling box 2, all the cooling plates 3 are mutually communicated to form a baffling cooling circuit, a water outlet 21 is arranged on one side of the top of the cooling box 2, water passing holes 31 are formed in the tail end of the baffling cooling circuit of each group of cooling plates 3, water return ports 22 are formed in the tail end of the baffling cooling circuit at the bottom of the cooling box 2, a plurality of placing grooves 32 used for placing titanium sheets are arranged on the upper surface of the cooling plates 3 in an equidistant manner, a drainage groove 33 is formed in one end of the placing groove 32 opposite to the baffling cooling circuit, cooling paint is coated on the surface of the drainage groove 33, and the cooling paint is formed by mixing the following components: the high-molecular-weight high-strength glass comprises, by weight, 10 parts of high-molecular acrylic resin liquid, 3 parts of ceramic powder, 1 part of vacuum glass beads, 0.5 part of bentonite and 0.2 part of dispersing agent; the standing groove 32 bottom is equipped with a plurality of through-holes, cooling tank 2 both sides inner wall is equipped with spout 23, cooling tank 2 openly bottom is equipped with fixed plate 4, fixed plate 4 top is equipped with spacing seal groove 41, fixed plate 4 top is equipped with movable closing plate 5, movable closing plate 5 and spout 23 sliding connection, movable closing plate 5 bottom and spacing seal groove 41 joint, return water mouth 22 is connected and is located the inside water storage tank 11 of water tank 1, water storage tank 11 one side is equipped with temperature controller 12, temperature controller 12 one side is equipped with suction pump 13, suction pump 13 is connected with delivery port 21.
Example 8
This embodiment differs from embodiment 1 in that: the parameters of the cooling wash in step S4 are different.
S4, cooling and cleaning: taking out the titanium sheet after deepening treatment, carrying out flow cooling on deionized water, reducing the temperature of the surface of the titanium sheet to 16 ℃, then putting the titanium sheet into deionized water for ultrasonic cleaning for 1min, wherein the ultrasonic frequency of ultrasonic cleaning is 40kHz, the temperature of the deionized water for flow cooling is 10 ℃, and the flow speed of the deionized water on the surface of the titanium sheet is 6ml/cm 2 ·s；
The flow cooling device for flow cooling comprises a water tank 1 and a cooling box 2 positioned on one side of the water tank 1, a plurality of cooling plates 3 are arranged in the cooling box 2, all the cooling plates 3 are mutually communicated to form a baffling cooling circuit, a water outlet 21 is arranged on one side of the top of the cooling box 2, water passing holes 31 are formed in the tail end of the baffling cooling circuit of each group of cooling plates 3, water return ports 22 are formed in the tail end of the baffling cooling circuit at the bottom of the cooling box 2, a plurality of placing grooves 32 used for placing titanium sheets are arranged on the upper surface of the cooling plates 3 in an equidistant manner, a drainage groove 33 is formed in one end of the placing groove 32 opposite to the baffling cooling circuit, cooling paint is coated on the surface of the drainage groove 33, and the cooling paint is formed by mixing the following components: the high-molecular-weight ceramic powder comprises 12 parts of high-molecular acrylic resin liquid, 4 parts of ceramic powder, 2 parts of vacuum glass beads, 0.8 part of bentonite and 0.2 part of dispersing agent by weight; the standing groove 32 bottom is equipped with a plurality of through-holes, cooling tank 2 both sides inner wall is equipped with spout 23, cooling tank 2 openly bottom is equipped with fixed plate 4, fixed plate 4 top is equipped with spacing seal groove 41, fixed plate 4 top is equipped with movable closing plate 5, movable closing plate 5 and spout 23 sliding connection, movable closing plate 5 bottom and spacing seal groove 41 joint, return water mouth 22 is connected and is located the inside water storage tank 11 of water tank 1, water storage tank 11 one side is equipped with temperature controller 12, temperature controller 12 one side is equipped with suction pump 13, suction pump 13 is connected with delivery port 21.
Example 9
This embodiment differs from embodiment 1 in that: the annealing process in step S5 is different in parameters.
S5, annealing treatment: airing the titanium sheet at the dark room temperature, then placing the titanium sheet in a muffle furnace for heating treatment, heating to 440 ℃ at the heating rate of 10 ℃/min, then carrying out heat treatment for 1h, and cooling to obtain the titanium sheet with the surface coated with TiO 2 The cooling process of the titanium sheet-based photocatalyst of the nanowire array film comprises the following steps of slow cooling in a furnace and quenching outside the furnace, wherein the room temperature is 25 ℃, and the cooling process of annealing treatment comprises the following steps of:
s5-1, slow cooling in the furnace: after the heat treatment is finished, the temperature in the furnace is reduced to 33 ℃ at a cooling speed of 20 ℃/min, and then the titanium sheet is naturally cooled in the furnace for 30min;
s5-2, quenching outside the furnace: taking out the titanium sheet from the furnace, quenching and cooling the surface of the titanium sheet by using an atomized liquid nitrogen quenching and cooling mode, wherein 8 cooling points are arranged on the surface of the titanium sheet, the cooling points are annular, 4 liquid nitrogen spraying points are correspondingly arranged at the same time, one cooling point is separated between every two adjacent liquid nitrogen spraying points, the liquid nitrogen spraying points sequentially and synchronously move after cooling of one cooling point is completed, the residence time of the liquid nitrogen spraying points at the cooling point is 3s, the spraying amount is 0.06ml/s, and the surface temperature of the titanium sheet is reduced to 21 ℃.
Example 10
This embodiment differs from embodiment 1 in that: the annealing process in step S5 is different in parameters.
S5, annealing treatment: airing the titanium sheet at the dark room temperature, and then placing the titanium sheet in a muffle furnace for heating treatment toHeating to 460 ℃ at a heating rate of 10 ℃/min, then heat-treating for 1h, and cooling to obtain the TiO coated surface 2 The titanium sheet-based photocatalyst of the nanowire array film has the room temperature of 27 ℃, and the cooling process of annealing treatment comprises the following steps of slow cooling in a furnace and quenching outside the furnace:
s5-1, slow cooling in the furnace: after the heat treatment is finished, the temperature in the furnace is reduced to 35 ℃ at a cooling speed of 30 ℃/min, and then the titanium sheet is naturally cooled in the furnace for 45min;
s5-2, quenching outside the furnace: taking the titanium sheet out of the furnace, quenching and cooling the surface of the titanium sheet by using an atomized liquid nitrogen quenching and cooling mode, wherein 8 cooling points are arranged on the surface of the titanium sheet, the cooling points are annular, 4 liquid nitrogen spraying points are correspondingly arranged at the same time, one cooling point is separated between every two adjacent liquid nitrogen spraying points, the liquid nitrogen spraying points sequentially and synchronously move after cooling of one cooling point is completed, the residence time of the liquid nitrogen spraying points at the cooling point is 2s, the spraying amount is 0.035ml/s, and the surface temperature of the titanium sheet is reduced to 18 ℃.
Experimental example 1
Observing the morphology and crystal form of the surface nano titanium substrate photocatalyst prepared by the preparation method in the example 1, as shown in fig. 8, the microstructure of the film prepared by the preparation method of the invention is TiO 2 An array of nanowires. As shown in fig. 9, a porous layer of about 1.9 μm thickness was first formed on the surface of the metallic titanium sheet, and a nanowire structure of about 1.5 μm was grown on the porous layer. TiO (titanium dioxide) 2 The critical thickness of the coating layer which effectively utilizes ultraviolet light as a semiconductor catalyst is 1 mu m, and the TiO which is prepared at present and has the thickness of more than 1 mu m 2 The nanowire film has better photocatalytic activity. FIG. 10 is a diagram of TiO 2 XRD patterns of the films revealed that the films produced were pure anatase phases, containing only a very small amount of the perovskite phase (labeled S). FIG. 11 is a diagram of the prepared TiO 2 The drawing shows isothermal desorption of nitrogen from the thin film scraped nanowire powder. It was found by calculation that the specific surface area of the film was 52.6m at a relative pressure of 0.3 or less 2 Per g, average film size of 17.8nm, total pore volume of 0.24cm 3 /g。
Experimental example 2
The surface nano titanium substrate photocatalyst prepared by the preparation method in the example 1 is subjected to a recycling experiment, as shown in fig. 12, until the fifth cycle, the titanium sheet-based catalyst can still keep good and stable photocatalytic performance, and can degrade 64% of RhB after 2 hours of reaction.

Claims (5)

1. The preparation method of the surface nano titanium substrate photocatalyst is characterized by comprising the following steps of:
s1, ultrasonic cleaning: taking titanium sheets with purity of more than 99.8%, placing the titanium sheets into an acetone solution for ultrasonic cleaning for 15-20min, placing the titanium sheets into an ethanol solution for ultrasonic cleaning for 10-15min, placing the titanium sheets into deionized water for ultrasonic cleaning for 10-15min, and removing greasy dirt on the surfaces of the titanium sheets;
s2, acid washing: immersing the titanium sheet after ultrasonic cleaning in a cleaning solution, wherein the cleaning solution comprises hydrofluoric acid solution, nitric acid solution and deionized water according to a proportion of 1:3:6, mixing the titanium sheets in a volume ratio, wherein the soaking time is 1-2min, and then taking out the titanium sheets and repeating the process of the step S1;
s3, deepening: immersing the pickled titanium sheet into 50-52 parts by weight of H with the mass concentration of 30% 2 O 2 Adding 18-22 parts by weight of melamine into the solution, continuously stirring for 30min, dropwise adding 1-2 parts by weight of nitric acid solution with the mass concentration of 60-63%, and putting the titanium sheet and the mixed solution into an oven together after the dropwise adding is finished to react for 72h at 80 ℃;
in the step S3, the stirring speed is 120-140r/min, and the dropping speed of the nitric acid solution is 1-2ml/S;
s4, cooling and cleaning: taking out the titanium sheet after the deepening treatment, performing deionized water flowing cooling, reducing the temperature of the surface of the titanium sheet to 12-16 ℃, and then placing the titanium sheet into deionized water for ultrasonic cleaning for 1-2min;
in the step S4, the temperature of the deionized water for flow cooling is 8-10 ℃, and the flow speed of the deionized water on the surface of the titanium sheet is 5-6ml/cm 2 ·s；
The mobile cooling device for mobile cooling comprises a water tank (1) and a cooling box (2) positioned at one side of the water tank (1), wherein a plurality of cooling plates (3) are arranged inside the cooling box (2), all the cooling plates (3) are mutually communicated to form a baffling cooling loop, a water outlet (21) is arranged at one side of the top of the cooling box (2), water passing holes (31) are arranged at the tail end of the baffling cooling loop of each group of cooling plates (3), water return ports (22) are arranged at the tail end of the baffling cooling loop of the bottom of the cooling box (2), a plurality of placing grooves (32) for placing titanium sheets are arranged on the upper surface of the cooling plates (3) at equal intervals, a drainage groove (33) is arranged at one end of the opposite baffling cooling loop, cooling paint is coated on the surface of the drainage groove (33), a plurality of through holes are formed in the bottom of the placing groove (32), sliding grooves (23) are formed in the inner walls of two sides of the cooling box (2), a fixed plate (4) are arranged at the bottom of the front of the cooling box (2), a limiting sealing groove (41) is arranged at the top of the fixed plate (4), a movable sealing plate (5) is arranged above the fixed plate (4), the movable sealing plate (5) is connected with the sliding sealing plate (41) in a sliding mode, the water return port (22) is connected with a water storage tank (11) positioned in the water tank (1), one side of the water storage tank (11) is provided with a temperature controller (12), one side of the temperature controller (12) is provided with a water suction pump (13), and the water suction pump (13) is connected with the water outlet (21);
s5, annealing treatment: airing the titanium sheet at the dark room temperature, then placing the titanium sheet in a muffle furnace for heating treatment, heating to 440-460 ℃ at the heating rate of 10 ℃/min, then carrying out heat treatment for 1h, and cooling to obtain the titanium sheet with the surface coated with TiO 2 Titanium plate-based photocatalyst of nanowire array film;
in the step S5, the room temperature is 25-27 ℃, and the cooling process of annealing treatment is divided into slow cooling in a furnace and quenching outside the furnace, wherein the steps of slow cooling in the furnace and quenching outside the furnace are as follows:
s5-1, slow cooling in the furnace: after the heat treatment is finished, the temperature in the furnace is reduced to 33-35 ℃ at a cooling speed of 20-30 ℃/min, and then the titanium sheet is naturally cooled in the furnace for 30-45min;
s5-2, quenching outside the furnace: taking out the titanium sheet from the furnace, quenching and cooling the surface of the titanium sheet by using an atomized liquid nitrogen quenching and cooling mode, setting 6 or 8 cooling points on the surface of the titanium sheet, setting the cooling points in a ring shape, correspondingly setting 3 or 4 liquid nitrogen spraying points at the same time, separating one cooling point between every two adjacent liquid nitrogen spraying points, and sequentially and synchronously moving the liquid nitrogen spraying points after cooling of one cooling point is completed, wherein the residence time of the liquid nitrogen spraying points at the cooling points is 2-3s, the spraying amount is 0.035-0.06ml/s, and the surface temperature of the titanium sheet is reduced to 18-21 ℃.
2. The method for preparing a surface nano titanium substrate photocatalyst according to claim 1, wherein the length, width and height of the titanium sheet in the step S1 are 40mm, 40mm and 0.1mm, respectively.
3. The method for preparing the surface nano titanium substrate photocatalyst according to claim 1, wherein the mass concentration of the acetone solution in the step S1 is 11-13.5mol/L, the mass concentration of the ethanol solution is 40%, the volumes of the acetone solution, the ethanol solution and the deionized water are all 30-40 times of that of the titanium sheet, and the ultrasonic frequency of ultrasonic cleaning in the step S1 and the step S4 is 40kHz.
4. The method for preparing a surface nano titanium substrate photocatalyst according to claim 1, wherein the mass concentration of the hydrofluoric acid solution in the step S2 is 40% and the mass concentration of the nitric acid solution is 70%.
5. The method for preparing the surface nano titanium substrate photocatalyst according to claim 1, wherein the cooling coating is prepared by mixing the following components: the high-molecular acrylic resin comprises, by weight, 10-12 parts of high-molecular acrylic resin liquid, 3-4 parts of ceramic powder, 1-2 parts of vacuum glass beads, 0.5-0.8 part of bentonite and 0.2 part of dispersing agent.
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CN101508463A (en) * 2009-03-19 2009-08-19 浙江大学 Method for producing nano-wire array film of titanium dioxide
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