CN104722288A - Method for immobilizing titanium dioxide photocatalyst on aluminum alloy net - Google Patents
Method for immobilizing titanium dioxide photocatalyst on aluminum alloy net Download PDFInfo
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- CN104722288A CN104722288A CN201510066606.XA CN201510066606A CN104722288A CN 104722288 A CN104722288 A CN 104722288A CN 201510066606 A CN201510066606 A CN 201510066606A CN 104722288 A CN104722288 A CN 104722288A
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Abstract
The invention provides a method for immobilizing a titanium dioxide photocatalyst on an aluminum alloy net. The method comprises the following steps: (1) performing sand pre-processing on the surface of the aluminum alloy net; (2) spraying an adhesive aqueous solution on the pre-processed aluminum alloy net; (3) preparing a titanium dioxide suspension grout and uniformly spraying the titanium dioxide suspension grout on the adhesive; and (4) drying. Compared with the prior art, the method has the beneficial effects that the process is simple and practical, the firmness is good, the degrading effects are good, the loss rate is only 3.83% which is obviously superior to those of a direct coating method and a gel-sol method, the degradation rate can reach 100% within 4 hours and is obviously superior to those of a common adhesive method and the gel-sol method.
Description
Technical field
The present invention relates to a kind of method at the immobilized titanium deoxide catalyst of aluminium alloy net, be applied to the gas pollutant process of environmental area, especially the process of volatile organic matter (VOCs).
Background technology
More and more serious along with atmosphere pollution, people more pay close attention to the improvement to atmosphere pollution.TiO
2photocatalysis technology is high, cheap and easy to get with its chemical stability, environmental friendliness, to organic pollutant degraded non-selectivity, degradation of organic substances end product be CO
2and H
2the plurality of advantages such as O are considered to the environment protection novel of most application prospect.
Numerous research shows, no matter in liquid phase or gas-phase photocatalysis degradation of organic substances, and TiO
2all there is good photocatalytic activity.But, nano-TiO in the liquid phase
2unsuitable sedimentation, is difficult to realize separation and recovery of catalyst; In the gas phase, in the larger situation of wind speed, nano-TiO
2easily be blown away and cause catalyst loss, this causes TiO
2photocatalysis technology is difficult to be widely used.Thus, TiO
2photochemical catalyst is immobilized is the key point promoting this technology extensive use.
But there is following technical problem in prior art:
Generally, TiO
2the immobilized method of photochemical catalyst can be divided into two kinds: 1. indirect method, by TiO
2precursor be carried on carrier, then high-temperature heating formed TiO
2; 2. direct method, by nano-TiO
2powder is directly carried on carrier.
Indirect method common are chemical vapour deposition technique, liquid phase deposition, sol-gel process etc.Chemical vapour deposition technique is evaporated by predecessor, then does carrier gas with nitrogen and take on the substrate of preheating by steam, and fully hydrolysis is final in the form of the oxide at deposition on substrate on substrate to make steam.Liquid phase deposition is raw material mainly with inorganic metal salt, adds and reaction can be made to generation oxide side to the material of movement, make reactant on substrate, complexation reaction occur and be deposited on substrate.The basic step of sol-gel process first prepares sol-gel solution, then by methods such as dip-coating method, rotation semar technique and injection coating methods, sol solution is fixed on carrier, finally by coated carrier drying roasting, one deck TiO can be formed at carrier surface
2film.In these methods, it take wire netting as carrier, the technology adopting the immobilized titanium dioxide optical catalyst of sol-gel process that prior art CN103127934 A provides a kind of, but the immobilized TiO of sol-gel process
2preparation process complicated, difficulty is high and be difficult to actual popularization.
Direct method comprises compound electric plating method, bonding agent method etc.Compound electric plating method is under applied voltage effect, with a kind of metal for matrix metal, by the method for electro-deposition by TiO
2particulate is attached in the coat of metal.Bonding agent method is with nano-TiO
2powder is raw material, prepares the good supported titanium of bond strength with immobilized bonding agent
2photochemical catalyst.In these methods, compound electric plating method can obtain high, the wear-resisting supported titanium of film hardness
2photochemical catalyst, but plating solution formula is complicated, and difficulty is high, and compared with compound electric plating method, bonding agent method is because method is simple, operating condition requires low and is easy to control and has application prospect more widely.
Prior art CN1256170A provide a kind of using cement as bonding agent by method immobilized for titanium dioxide.E Lei is carrier using water miscible polyacrylamide as bonding agent, with sheet glass, by bonding agent method, by TiO
2the fully mixed merga pass of powder and bonding agent regulates each parameter to prepare the loaded photocatalyst with high light catalytic activity.Yan Chunfang etc. for bonding agent, are crosslinking agent with PIC with waterborne organic silicon resin, take sheet glass as carrier, with the standby solid-carrying type TiO of bonding agent legal system
2photochemical catalyst, bonding agent mass fraction be 42%, crosslinking agent mass fraction is 7%, TiO
2under the condition of mass fraction 5%, obtained TiO
2photochemical catalyst.But existing bonding method is all by TiO
2immobilized after powder mixes with bonding agent, bonding agent can cover TiO significantly
2active sites.
Summary of the invention
In view of the technical problem that prior art exists, the invention provides a kind of method at the online immobilized titanium dioxide optical catalyst of aluminium alloy.
Particularly, the present invention is realized by following scheme, and a kind of method at the online immobilized titanium dioxide optical catalyst of aluminium alloy, comprising:
(1), the sand pretreatment of aluminium alloy net surface;
(2). the online spraying and adhesive bonding agent of the aluminium alloy after the pre-treatment aqueous solution;
(3), preparing titanium dioxide suspension slurry, then titanium dioxide suspension slurry is uniformly sprayed on bonding agent;
(4), dry.
Wherein, by great many of experiments, described bonding agent is preferably waterborne silicone-acrylate resin, and wherein bonding agent dissolves or suspends in water and obtains adhesive solution, and wherein bonding agent mass fraction is 10%, and bonding agent mass fraction is 90%.Adhesive solution is obtained as 45g bonding agent dissolves in 5g water.
Described titanium dioxide suspension slurry refers to that titanium dioxide suspending is in water, and consider that titanium dioxide concentration is too low, very little, photocatalysis effect is poor for the amount of spraying; Titanium dioxide concentration is too high, easily reunites, and thus in titanium dioxide suspension slurry, titanium dioxide mass fraction is preferably 10%-30%, and particularly preferably 20%.As 10g titanium dioxide joins in 40g distilled water, namely mass fraction is 20%.
In preferred version, also have dispersant in described titanium dioxide suspension slurry, dispersant is preferably polyethylene glycol, sodium metasilicate, or calgon, particularly preferably calgon.Consider dispersion dosage very little, dispersion effect is bad, and dispersion dosage is too large, and titanium dioxide can be reunited again again.Thus the quality (g) of preferred dispersants and the 1%-5% of titanium dioxide quality (g), particularly preferably 2%.
Described titanium dioxide is preferably P25 titanium dioxide, and P25 titanium dioxide refers to the fumed nano grade titanium dioxide of a kind of high degree of dispersion of aerosil explained hereafter, can by commercially available acquisition.
Highly preferred scheme comprises:
(1), the sand pretreatment of aluminium alloy net surface
(1.1) NaOH solution of aluminium alloy net 80g/L processes 1min at 30 DEG C, rear 20%HNO
3solution processes 5s at ambient temperature with clean carrier surface, removes oil stain and other impurity;
(1.2) pretreated aluminium alloy net is put into the FeCl of 1.0mol/L
3at 30 DEG C, process 6min in solution, make FeCl
3displacement reaction is there is with the Al of aluminum alloy surface, and then by aluminum alloy surface sand; Use the NaOH solution process 20s of 240g/L again, make its sandization more obvious, remove the reaction residue of carrier surface simultaneously;
(1.3) finally the carrier distilled water of process is cleaned, dry 30 minutes for 100 DEG C.
(2), in 45g waterborne silicone-acrylate resin add 5g distilled water, stir 2min, obtain bonding agent liquid, with spray gun by online for the bonding agent liquid even application aluminium alloy after treatment of spraying.
(3), by 10g titanium dioxide join in 40g distilled water, magnetic agitation 5min, then add calgon 0.2g, magnetic agitation 4h, ultrasonic 30min, obtains titanium dioxide suspension slurry, then is uniformly sprayed on waterborne silicone-acrylate resin by titanium dioxide suspension slurry.
(4), dry 30min under baking oven 100 DEG C of conditions.
Preparation method of the present invention is using the aluminium alloy net through surperficial sand process as carrier; Wire netting surface uniform sprays one deck bonding agent; P25 titanium dioxide suspension slurry is sprayed again at bonding agent skin, wherein in titanium dioxide suspension slurry, add dispersant, select bonding method, there is the advantage of bonding agent method and directly painting method simultaneously, namely nano TiO 2 particles is firmly immobilized under the effect of bonding agent, catalyst not easily runs off, and directly contacts with pollutant simultaneously.
The present invention is evaluated by following method and technology:
The evaluation of catalyst firmness: under 5m/s gas flow rate, catalyst loss rate is evaluated; Immobilized rear catalyst gross mass is m1, and purging rear catalyst gross mass is m2, turnover rate η=(m1-m2)/m1.
Catalyst effect is evaluated: utilize the degradation rate closing photo catalysis reactor degraded butyraldehyde to evaluate photocatalysis effect, in closed reactor, butyraldehyde concentration is 50ppm, O
2concentration is 21%, and 4h is carried out in reaction, and sampling should be carried out for every 20min.The computing formula of degradation rate is:
η in formula---degradation rate (%);
C
0 butyraldehyde---butyraldehyde initial concentration (ppm);
C
butyraldehyde---butyraldehyde concentration (ppm) during molecular balance
The beneficial effect of hinge structure of the present invention comprises: features simple and practical process, and fastness is good, good degrading effect; Turnover rate is only 3.83%, is obviously better than directly painting method and sol-gel process; In 4h, degradation rate can arrive 100%, is obviously better than general bonding agent method and sol-gel process.
Accompanying drawing explanation
Carrier pattern before and after accompanying drawing 1 pretreatment
The immobilized photochemical catalyst schematic diagram of accompanying drawing 2 bonding method
The curve map of immobilized photocatalyst for degrading butyraldehyde under the different dispersant of accompanying drawing 3
Immobilized photocatalyst surface shape appearance figure under the different dispersant of accompanying drawing 4
Immobilized photocatalyst surface shape appearance figure under accompanying drawing 5 difference dispersion dosage
Under accompanying drawing 6 difference dispersion dosage, immobilized photochemical catalyst is to the degradation curve figure of butyraldehyde
Immobilized photocatalyst surface shape appearance figure under accompanying drawing 7 different titanium dioxide amount
Under accompanying drawing 8 different titanium dioxide amount, immobilized photochemical catalyst is to the degradation curve figure of butyraldehyde
The degraded butyraldehyde curve map of immobilized photochemical catalyst under the different solid support method of accompanying drawing 9
Detailed description of the invention
Below in conjunction with concrete example and accompanying drawing, the present invention is described in further detail, but content of the present invention is not limited to embodiment.
Embodiment 1
Aluminium alloy net physical property is good, and corrosion resistance is strong.But aluminum alloy surface is smooth, be unfavorable for the immobilized of catalyst, thus, sand process will be carried out to aluminum alloy surface.
Preferred version detailed process is as follows: the NaOH solution of aluminium alloy net 80g/L processes 1min at 30 DEG C, rear 20%HNO
3solution processes 5s at ambient temperature with clean carrier surface; Pretreated aluminium alloy net is put into the FeCl of 1.0mol/L
3at 30 DEG C, process 6min in solution, make aluminum alloy surface sand; Use the NaOH solution process 20s of 240g/L again, make its sandization more obvious, remove the reaction residue of carrier surface simultaneously; Finally the carrier distilled water of process is cleaned, dry.Carry out observation contrast after being amplified 50 times, can find that surface is obviously coarse, be conducive to the bonding of the fixative on surface, as shown in Figure 1.
Embodiment 2
Flow process such as Fig. 2 of bonding method shows, adopts spray gun at carrier surface first even application one deck bonding agent, then adopts spray gun on bonding agent, spray one deck TiO at once
2suspension slurry.
Preferred version is specially: bonding agent is preferably waterborne silicone-acrylate resin, and wherein bonding agent dissolves or suspends in water and obtains adhesive solution, and wherein bonding agent mass fraction is 90%.
Embodiment 3
Preparing titanium dioxide suspension slurry, then titanium dioxide suspension slurry is uniformly sprayed on bonding agent.
In preferred version, described titanium dioxide suspension slurry refers to that titanium dioxide suspending is in water, and in preferred titanium dioxide suspension slurry, the ratio of titanium dioxide quality (g) and water volume (mL) is 10%-30%, particularly preferably 20%.
In preferred version, described titanium dioxide suspension slurry also has dispersant, and dispersant is preferably polyethylene glycol, sodium metasilicate, calgon, and wherein the quality (g) of dispersant and the ratio of water volume (mL) are 1%-5%, particularly preferably 2%.
Described titanium dioxide is preferably P25 titanium dioxide.
Specifically preferred scheme is: the distilled water measuring certain volume, the dispersant (calgon, sodium metasilicate and polyethylene glycol (PEG)) of 2% (accounting for the mass fraction of P25) is added after adding the P25 titanium dioxide mix and blend 5min of 20%, magnetic agitation 2h, then ultrasonic 30min, P25 is fully disperseed, makes TiO
2suspension.By TiO
2uniform suspension is sprayed on and is sprayed with on the carrier of bonding agent by the flow process of bonding method, dries the i.e. obtained photochemical catalyst containing different dispersant.
Closed photo catalysis reactor is utilized to evaluate photocatalysis effect, butyraldehyde concentration 50ppm, O in closed reactor
2concentration 21%, 4h is carried out in reaction.Accompanying drawing 3 is use the photochemical catalyst containing different dispersant to the butyraldehyde degradation rate after the degradation curve of butyraldehyde and stable reaction respectively.From accompanying drawing 3, add the photocatalysis effect of dispersant to butyraldehyde and have certain facilitation, wherein the weak effect of three kinds of dispersants is apart from little, and after molecular balance, degradation rate is respectively calgon > sodium metasilicate > polyethylene glycol from high to low.As can be seen from the characterization result of metallographic microscope also, when utilizing calgon as dispersant, TiO
2dispersion effect better.As shown in Figure 4.
Embodiment 4
Adding the sodium hexametaphosphate dispersant (1%, 2%, 3%, 4%, 5%) of different amount respectively, make TiO
2suspension, and use TiO
2bonding method makes photochemical catalyst.With its surface topography map of microscopic examination, as shown in Figure 5.In calgon amount, to be 2% be that titanium dioxide is comparatively even, and effect is best.Butyraldehyde is degraded simultaneously.As shown in Figure 6, from accompanying drawing 6, dispersant is 2% make degradation effect best to result.
Embodiment 5
Keep TiO
2dispersant and TiO in suspension
2ratio be 2% constant, investigate change in concentration (10%, 15%, 20%, 25%, the 30%) impact on catalyst activity of P25 in suspension.Different Ti O when accompanying drawing is Kaolinite Preparation of Catalyst
2the catalyst surface shape appearance figure that content is corresponding, can obviously find out, along with TiO from Fig. 7
2the increase of concentration, carrier surface TiO
2density constantly increases.
Again respectively to use containing different Ti O
2the photochemical catalyst of content is degraded to butyraldehyde, and result as shown in Figure 8.From accompanying drawing 8, with TiO
2the increase of amount, there is the trend of first increases and then decreases in butyraldehyde degradation rate, and works as TiO
2tiO in suspension
2when concentration is 20%, photocatalysis effect is significantly better than other situations.This is mainly because work as TiO
2time concentration is lower, TiO
2(be can be observed by the pattern of accompanying drawing 7) very little, cause photocatalysis effect poor; Work as TiO
2time concentration is greater than 20%, with TiO
2the increase of concentration, the effect of dispersant diminishes, as can be seen from accompanying drawing 7, a large amount of TiO
2particle agglomeration together, not only cannot improve TiO
2exposed surface area, has stopped some light-catalysed avtive spots on the contrary, and catalyst photocatalytic activity is reduced.
Embodiment 6
(1), the sand pretreatment of aluminium alloy net surface
(1.1) NaOH solution of aluminium alloy net 80g/L processes 1min at 30 DEG C, rear 20%HNO
3solution processes 5s at ambient temperature with clean carrier surface, removes oil stain and other impurity;
(1.2) pretreated aluminium alloy net is put into the FeCl of 1.0mol/L
3at 30 DEG C, process 6min in solution, make FeCl
3displacement reaction is there is with the Al of aluminum alloy surface, and then by aluminum alloy surface sand; Use the NaOH solution process 20s of 240g/L again, make its sandization more obvious, remove the reaction residue of carrier surface simultaneously;
(1.3) finally the carrier distilled water of process is cleaned, dry 30 minutes for 100 DEG C.
(2). with spray gun by online for the waterborne silicone-acrylate resin even application aluminium alloy after treatment of moisture 10%.
(3), preparing titanium dioxide mass fraction is 20%, calgon mass fraction is 2% (accounting for the percentage of titanium dioxide) titanium dioxide suspension slurry, then titanium dioxide suspension slurry to be uniformly sprayed on waterborne silicone-acrylate resin.
(4), dry 30min under baking oven 100 DEG C of conditions.
Embodiment 7 contrast experiment and technology assessment
Because directly painting method, sol-gel process, these three kinds of methods of bonding agent method are relatively simply skillful, the solid support method of these three kinds of catalyst of initial option contrasts.Immobilized complete after, with hair-dryer simulation high temperature and high speed air-flow to the immobilized evaluation carrying out firmness.
The present invention is evaluated by following method and technology:
The evaluation of catalyst firmness: be 5m/s in gas velocity, temperature is evaluated catalyst loss rate under being approximately 80 DEG C of conditions; Catalyst plane is vertical with airflow direction, uses gas flow purging 2h, and weighs the quality before and after purging, and immobilized rear catalyst gross mass is m1, and purging rear catalyst gross mass is m2, turnover rate η=(m1-m2)/m1.
Catalyst effect is evaluated: utilize the degradation rate closing photo catalysis reactor degraded butyraldehyde to evaluate photocatalysis effect, in closed reactor, butyraldehyde concentration is 50ppm, O
2concentration is 21%, and 4h is carried out in reaction, and sampling should be carried out for every 20min.The computing formula of degradation rate is:
η in formula---degradation rate (%);
C
0 butyraldehyde---butyraldehyde initial concentration (ppm);
C
butyraldehyde---butyraldehyde concentration (ppm) during molecular balance
Distinct methods photochemical catalyst turnover rate is as following table 1, and the effect of catalytic degradation butyraldehyde is as accompanying drawing 9.
Photochemical catalyst turnover rate prepared by table 1 distinct methods
Good from the immobilized titanium dioxide fastness of the visible the present invention of upper table (such as the scheme of embodiment 6) hinge structure, good degrading effect; Turnover rate is only 3.83%, is obviously better than directly painting method and sol-gel process; In 4h, degradation rate can arrive 100%, is obviously better than general bonding agent method and sol-gel process.
Above content is in conjunction with concrete preferred embodiment further description made for the present invention, can not assert that specific embodiment of the invention is confined to these explanations.For general technical staff of the technical field of the invention, without departing from the inventive concept of the premise, some simple deduction or replace can also be made, all should be considered as belonging to protection scope of the present invention.
Claims (8)
1., in a method for the online immobilized titanium dioxide optical catalyst of aluminium alloy, it is characterized in that, comprising:
(1), the sand pretreatment of aluminium alloy net surface;
(2), the aluminium alloy online spraying and adhesive bonding agent aqueous solution after the pre-treatment;
(3), preparing titanium dioxide suspension slurry, then titanium dioxide suspension slurry is uniformly sprayed on bonding agent;
(4), dry.
2. method according to claim 1, is characterized in that, described bonding agent is preferably waterborne silicone-acrylate resin, and wherein bonding agent mass fraction is 90%.
3. method according to claim 1, is characterized in that, described titanium dioxide suspension slurry refers to that titanium dioxide suspending is in water, and wherein in titanium dioxide suspension slurry, titanium dioxide mass fraction is 20%.
4. method according to claim 3, is characterized in that, also have dispersant in described titanium dioxide suspension slurry, dispersant preferably includes polyethylene glycol, sodium metasilicate, or calgon.
5. method according to claim 4, is characterized in that described dispersant quality is the 1%-5% of titanium dioxide quality.
6. method according to claim 5, is characterized in that, described wherein preferred dispersants quality is 2% of titanium dioxide quality.
7. method according to claim 1, is characterized in that, described titanium dioxide is preferably P25 titanium dioxide.
8. method according to claim 1, is characterized in that, comprising:
(1), the sand pretreatment of aluminium alloy net surface
(1.1) NaOH solution of aluminium alloy net 80g/L processes 1min at 30 DEG C, rear 20%HNO
3solution processes 5s at ambient temperature with clean carrier surface, removes oil stain and other impurity;
(1.2) pretreated aluminium alloy net is put into the FeCl of 1.0mol/L
3at 30 DEG C, process 6min in solution, make FeCl
3displacement reaction is there is with the Al of aluminum alloy surface, and then by aluminum alloy surface sand; Use the NaOH solution process 20s of 240g/L again, make its sandization more obvious, remove the reaction residue of carrier surface simultaneously;
(1.3) finally the carrier distilled water of process is cleaned, dry 30 minutes for 100 DEG C.
(2), in 45g waterborne silicone-acrylate resin add 5g distilled water, stir 2min, obtain bonding agent liquid, with spray gun by online for the bonding agent liquid even application aluminium alloy after treatment of spraying.
(3), by 10g titanium dioxide join in 40g distilled water, magnetic agitation 5min, then add calgon 0.2g, magnetic agitation 4h, ultrasonic 30min, obtains titanium dioxide suspension slurry, then is uniformly sprayed on waterborne silicone-acrylate resin by titanium dioxide suspension slurry.
(4), dry 30min under baking oven 100 DEG C of conditions.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111097541A (en) * | 2018-10-25 | 2020-05-05 | 中国科学院上海硅酸盐研究所 | Dye-sensitized black titanium dioxide and preparation method and application thereof |
| CN112246239A (en) * | 2020-10-23 | 2021-01-22 | 南京国豪环保材料科技有限公司 | Catalytic material and cork board with formaldehyde decomposition function |
| CN113083171A (en) * | 2021-03-10 | 2021-07-09 | 叁素(浙江)新材料科技有限责任公司 | ClO of composite photocatalyst2Method for preparing sustained-release gel |
| CN116272933A (en) * | 2021-12-06 | 2023-06-23 | 陕西青朗万城环保科技有限公司 | Carrier catalyst and preparation method thereof |
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| CN101485974A (en) * | 2009-02-23 | 2009-07-22 | 东南大学 | Method for supporting nano titanic oxide on surface of carrier material |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111097541A (en) * | 2018-10-25 | 2020-05-05 | 中国科学院上海硅酸盐研究所 | Dye-sensitized black titanium dioxide and preparation method and application thereof |
| CN112246239A (en) * | 2020-10-23 | 2021-01-22 | 南京国豪环保材料科技有限公司 | Catalytic material and cork board with formaldehyde decomposition function |
| CN112246239B (en) * | 2020-10-23 | 2023-05-05 | 南京国豪环保材料科技有限公司 | Catalytic material and cork board with formaldehyde decomposition function |
| CN113083171A (en) * | 2021-03-10 | 2021-07-09 | 叁素(浙江)新材料科技有限责任公司 | ClO of composite photocatalyst2Method for preparing sustained-release gel |
| CN116272933A (en) * | 2021-12-06 | 2023-06-23 | 陕西青朗万城环保科技有限公司 | Carrier catalyst and preparation method thereof |
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Application publication date: 20150624 |