CN102266774A - Semiconductor nano photocatalysis material and preparation method thereof - Google Patents
Semiconductor nano photocatalysis material and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a semiconductor nano photocatalysis material and a preparation method thereof. The semiconductor nano photocatalysis material comprises a carrier and a semiconductor nano photocatalyst layer loaded on the surface of the carrier and is characterized in that: the carrier is made from a multihole foam material. The preparation method comprises the following steps of: taking the multihole foam material as the carrier; performing surface treatment on the carrier and fixing a semiconductor nano photocatalyst on the surface of the carrier by a loading method, wherein the semiconductor nano photocatalyst accounts for 1 to 20 weight percent of the carrier; and preparing the target product by vacuum drying. Compared with the prior art, the photocatalysis material has large specific surface area, high bonding strength and high capacity, and the photocatalysis active efficiency and the photocatalysis stability are improved. The preparation method is simple, easy to operate and suitable for industrialized manufacturing.
Description
Technical field
The present invention relates to a kind of catalysis material, especially a kind of semiconductor nano catalysis material and preparation method thereof.
Background technology
Along with problem of environmental pollution is day by day seriously changed, make and improve the living environment that runs down by human clean, safe, the economic chemical technology on exploitation one species ecology of being badly in need of.Photocatalysis is a kind of emerging depollution of environment technology.For example, nano-TiO
2Photochemical catalyst can decompose effectively and is adsorbed on its surperficial toxic gas molecule, suppresses or eliminates harmful microorganism, and harmful larger molecular organics can be decomposed into harmless small-molecule substance such as carbon dioxide and water, does not have secondary pollution.Because nano-TiO
2Have anti-chemistry and photoetch, stable performance, nontoxic, catalytic activity is high, advantage such as inexpensive and enjoy attention, is a kind of environment-friendly type catalyst that DEVELOPMENT PROSPECT is arranged very much.But nano-TiO
2Be a kind of powder, its photocatalysis need be fixed and need certain contact area and reaction time, thereby how it is loaded to and make its photocatalysis efficiency the best become one of key issue that this technology need solve on the appropriate carriers.Common carrier material foam-expelling metal also has active carbon, zeolite, expanded perlite, silica gel, aluminium oxide, lucite, optical fiber, natural clay, extra large sand, resin etc. outward.Utilize that these carrier loaded photochemical catalysts exist that light-receiving area is little, specific area is little, vapour lock is big, shortcoming such as not high, the easy fragmentation of mechanical strength and load capacity are little.
Summary of the invention
For overcoming above technological deficiency, the invention provides a kind of semiconductor nano catalysis material, and further disclose its preparation method.This material is a matrix with the perforated foams, has enlarged the photochemical catalyst specific area, thereby photocatalysis efficiency is significantly improved.
The present invention also further discloses the preparation method of above-mentioned semiconductor nano catalysis material.
The present invention is achieved by following technical solution:
Catalysis material of the present invention comprises the perforated foams carrier and is carried on the semiconductor nano photocatalyst layer of carrier surface.
The carrier voidage of described perforated foams〉96%, thickness 2-5mm, aperture 100 μ m-2mm.
Described perforated foams is a kind of in foam copper, nickel foam, foam iron, foamed aluminium or the foamed plastics;
The photochemical catalyst of described semiconductor light-catalyst layer is to be selected from Co
3O
4, NiO, Cu
2O, TiO
2, ZnO, CdS, Fe
2O
3, SnO
2, WO
3Or Nb
2O
5In one or both.The particle diameter of the photochemical catalyst of described semiconductor nano photocatalyst layer is 10-50nm, and coverage rate is 50%, and load capacity is 20-50g/m
2
The preparation method of catalysis material of the present invention is to be matrix with the perforated foams, in conjunction with corresponding load technology such as composite plating, Ni-P and dip-coating method even load nano-TiO
2The preparation catalysis material.
Before the load, at first two kinds of dissimilar material foam metal and Foam Plastic Surface are handled respectively.Wherein, the foam metal surface treatment step: through oil removing, washing, pickling, washing, activation dries up after the washing.Foam Plastic Surface treatment step: after destressing, oil removing, washing, alligatoring, neutralization, reduction, washing, sensitization, activation, washing, dry up.
Degreaser in the described foam metal surface treatment deoiling step is a 10-30%NaOH solution, and temperature is 50-60 ℃, and the time of deoiling is 1-10min; Mordant in the described acid pickling step is the sulfuric acid solution of 10-20%, and temperature is 50-60 ℃, and the pickling time is 1-10min; Activator in the described activation step is the AgNO of 1-5%
3Solution, soak time are 5-10min;
Described Foam Plastic Surface handle destressing agent in the destressing step by acetone and water by acetone: the ratio of water=0.2 ~ 1:1 is prepared, and the destressing time is 20-40min; Degreaser in the described deoiling step is 10 ~ 30%NaOH solution, and temperature is 50 ~ 60 ℃, and the oil removing time is 1-10min; Alligatoring agent in the described alligatoring step is by the CrO of 15 ~ 25g/L
3With the concentrated sulfuric acid preparation of 600mL/L, temperature is 70 ~ 75 ℃, and coarsening time is 5-15min; Sensitizer in the described sensitization step is by 30 ~ 40mL/LHCl and 15 ~ 20g/LSnCl
2Preparation, sensitization time is 5-10min; Activator in the described activation step is 1 ~ 5% AgNO
3Solution, soak time are 5-10min.
Behind process of surface treatment, with foamed plastics with Ni
2+Carry out composite plating in the corresponding plating bath for main body, Ni-P makes the support type catalysis material; Or foam metal flooded in the colloidal sol that with the butyl titanate is presoma lift, drying, heat treatment and make then.The TiO of institute's load
2Photocatalytic activity component maximum can be near 20% of photocatalysis screen pack gross weight.
The carrying method that adopts is a kind of in composite plating, Ni-P and the dip-coating method; foamed material of different nature carries out load through being positioned over after the different surface treatments in corresponding colloidal sol or the plating bath; drying then, the dip-coating method load of foam metal also must make through logical nitrogen protection or the heat treatment in vacuum tube furnace.Baking temperature wherein is 90 ~ 100 ℃, time 10 ~ 20min.Heat treatment temperature is 300 ~ 350 ℃, time 60 ~ 120min.These carrying methods are simple to operate, just can obtain uniformly within a short period of time, efficiently, with the well behaved nano-TiO of matrix bond mechanics
2Coating, thus photocatalysis stability and photocatalytic activity improved significantly.
Composite plating of the present invention, Ni-P and three kinds of carrying methods of dip-coating method prepare catalysis material, can make by following three kinds of modes:
(1) prescription of composite plating plating bath is: the NiSO of 250 ~ 300g/L
46H
2The NiCl of O, 30 ~ 40g/L
26H
2The H of O, 40g/L
3BO
3And the TiO of the SDBS of 0.5 ~ 1g/L, 5-10g/L
2, cathode-current density is 20 ~ 40 mA
Cm
-2, pH is transferred to 3.5 ~ 4.5; Medium stir speed (S.S.), plating 30 ~ 60min under 40 ~ 50 ℃ temperature.
(2) being formulated as of Ni-P plating bath: (concentration is inferior sodium phosphate: 20-28g/L), Ni
2+(concentration is: 87-93g/L), Pb
2+(concentration is: 0.7-1.5ppm), (concentration is lactic acid: 25-30g/L), (concentration is propionic acid: 1-5g/L), (concentration is SDBS: 0.5-1g/L), TiO
2(concentration is: 5-10g/L), plating bath pH is adjusted to 4-5; Medium stir speed (S.S.), plating 30-60min under 90-94 ℃ the temperature;
(3) be the infusion process of presoma with the butyl titanate: under the room temperature, the 30-40mL butyl titanate is mixed with the absolute ethyl alcohol of 75-85mL, slowly splash into the mixed liquor of forming by the absolute ethyl alcohol of 10-15mL glacial acetic acid, 4-8mL deionized water and 75-85mL then, or in above-mentioned mixed liquor, add the salting liquid that contains the semiconductor alloy element of 10-20mL10g/L again, constantly stir, after forming colloidal sol before the gel with the surface treated foam metal matrix dipping wherein behind 5 ~ 10min in 90 ~ 100 ℃ vacuum drying chamber dry 10 ~ 20min, so circulate 3 ~ 5 times; Be heat treatment 60 ~ 120min in 300 ~ 350 ℃ of vacuum tube furnaces or in the tube furnace of logical nitrogen deoxygenation in temperature then.
With respect to prior art, catalysis material specific area of the present invention is big, adhesion good, load capacity is big, has improved photocatalytic activity efficient and photocatalysis stability.By disposing suitable ultraviolet source, can degrade effectively to the harmful microorganism in the air or in the water, poisonous organic molecule, thereby play the effect that purifies air with water quality.The simple easy operating of its preparation method, and suitable industrialization production.
Description of drawings
Fig. 1 is the structural representation of the load device of composite plating method of the present invention.
Fig. 2 is the structural representation of the load device of Ni-P of the present invention and dip-coating method.
Fig. 3 is the material that the present invention adopts the different loads mode to make, and to the degraded that the dye activity of difficulty decomposition is deceived GR, its percent of decolourization is curve map over time.
The specific embodiment
Now the present invention is described further in conjunction with the accompanying drawings and embodiments.
Embodiment 1: the composite plating carrying method
Present embodiment adopts special composite plating device.This device comprises that the constant temperature that is filled with isothermal liquid 5 stirs water tank 2 and is located at constant temperature and stirs coating bath 4 in the water tank 2 as shown in Figure 1, fills composite plating baths 3 in the coating bath 4, and the bottom of coating bath 4 also is provided with magnetic agitation mechanism 7.And in coating bath 4, be provided with the fixed bar 8 that is used for fixing foamed material net 6.Respectively be provided with an electronickelling plate 1 in the both sides of fixed bar 8, described two blocks of electronickelling plates 1 join with the positive pole of external power source, and described foamed material net 6 joins with the negative pole of external power source; Be that described two blocks of electronickelling plates 1 form electroplanting device as positive pole of electroplating and negative pole respectively with foamed material net 8.Concrete steps are:
1. the pre-treatment on nickel foam surface: oil removing (10%NaOH, 50 ℃, 100min) → washing → pickling (10% sulfuric acid, 50 ℃, 10min) → washing → activation (2% AgNO3,5min) → wash → dry up.
2. the configuration of composite plating plating bath: the NiSO that takes by weighing 250g
46H
2The NiCl of O, 40g
26H
2The H of O, 40g
3BO
3In the beaker of 1000mL, add deionized water and make its dissolving, the pH of above-mentioned solution is adjusted to 4.0 and continue to add deionized water to graduation mark, add SDBS, the 5gTiO of 0.5g then
2, constantly stirring or employing ultrasonic wave disperse 24h standby.
3. nickel foam and nickel plate are immersed in the above-mentioned plating bath, as negative electrode and the anode electroplated, current density transfers to 30mA respectively
Cm
-2, in stirring water tank, stirs constant temperature, and with adjustment to 40 ℃ and keep constant, plating 30min is then with sample dry 10min in 90 ℃ vacuum drying chamber.
4. the above-mentioned foam nickel screen that will electroplate in the stove of logical nitrogen or in the vacuum tube furnace in 350 ℃ of heat treatment 60min, thereby make nano-TiO
2The catalysis material good with the nickel foam adhesion.The photocatalysis experiment shows that this catalyst material can make the percent of decolourization of reactive black reach more than 90% under the irradiation of uviol lamp in 4 hours.
Embodiment 2: the Ni-P carrying method
Present embodiment adopts special chemically composited plating appts, and as shown in Figure 2, this device is not established electronickelling plate 1 in coating bath 4, and concrete steps are:
1. the pre-treatment on nickel foam surface: oil removing (10%NaOH, 50 ℃, 10min) → washing → pickling (10% sulfuric acid, 50 ℃, 10min) → washing → activation (2% AgNO3,5min) → wash → dry up.
2. the configuration of chemical plating bath: add deionized water to 1/2 of 1000mL beaker, then respectively to the Pb of the nickel salt solution 50mL of the inferior sodium phosphate that wherein adds 24g, 90g/L, 30g lactic acid, 3g propionic acid, 0.7-1.5ppm
2+, add deionized water to graduation mark after pH is adjusted to 4.6, add the SDBS of 0.5g, the TiO of 5-10g then
2, constantly stirring or employing ultrasonic wave disperse 24h standby.
3. above-mentioned plating bath is stirred in constant temperature stirs water tank, be warming up to 92 ℃ and keep constant, the foam nickel screen of the treated mistake in surface is immersed 30min in the chemical plating fluid, then sample is taken out and dry 10min in 90 ℃ baking oven.
With above-mentioned foam nickel screen in the stove of logical nitrogen or in the vacuum tube furnace in 350 ℃ of heat treatment 60min, thereby make nano-TiO
2The photocatalysis net good with the nickel foam adhesion.The photocatalysis experiment shows that this catalyst material can make the percent of decolourization of reactive black reach more than 90% under the irradiation of uviol lamp in 4 hours.
Embodiment 3: dipping lifts the load method
The load device of present embodiment adopts device shown in Figure 2, can be without the operation down of water-bath normal temperature.Concrete steps are:
1. the pre-treatment on nickel foam surface: oil removing (10%NaOH, 50 ℃, 10min) → washing → pickling (10% sulfuric acid, 50 ℃, 10min) → wash → dry up.
2. be the colloidal sol of presoma with the butyl titanate: under the room temperature, the butyl titanate of 34mL (0.1mol) mixed with the absolute ethyl alcohol of 80mL place beaker, to move in the buret by the mixed liquor that 10mL glacial acetic acid, 4mL deionized water and 80mL absolute ethyl alcohol are formed then and slowly splash into, and constantly stir liquid in the beaker.
3. before the gel, above-mentioned surface-treated metal foam nickel screen be impregnated in wherein after forming colloidal sol, lift taking-up with the speed of 5mm/s, dry 10min in drying box repeats aforesaid operations three times then.
4. the sample that will flood drying after three times in the stove of logical nitrogen or in the vacuum tube furnace in 350 ℃ of heat treatment 120min, thereby make nano-TiO
2The photocatalysis net good with the nickel foam adhesion.The photocatalysis experiment shows that this catalyst material can make the percent of decolourization of reactive black reach more than 80% under the irradiation of uviol lamp in 4 hours.
Embodiment 4:
1. the surface treatment of foamed plastics: destressing (acetone: water=1:3,30min) → oil removing (20%NaOH, 50 ℃, 20min) → washing → alligatoring (CrO of 20g/L
3With the concentrated sulfuric acid of 600mL/L, 70 ~ 75 ℃, 5-15min) → neutralization → reduction → washing → sensitization (40mL/LHCl+20g/LSnCl
2, 5min) → and activation (2% AgNO3,5min) → wash → dry up.
2. the configuration of chemical plating nickel-plating liquid: add deionized water to 1/2 of 1000mL beaker, then, add deionized water then to scale respectively to the nickel salt solution 50mL of the inferior sodium phosphate that wherein adds 24g, 90g/L.
3. the configuration of composite plating plating bath: the NiSO that takes by weighing 250g
46H
2The NiCl of O, 40g
26H
2The H of O, 40g
3BO
3In the beaker of 1000mL, add deionized water and make its dissolving, the pH of above-mentioned solution is adjusted to 4.0 and continue to add deionized water to graduation mark, add the SDBS of 0.5g, the TiO of 5-10g then
2, constantly stirring or employing ultrasonic wave disperse 24h standby.
4. the foamed plastics that the surface is treated places 85 ℃ chemical plating nickel-plating liquid, and the oven dry of plating 10min after washing can be conducted electricity it.As negative electrode, in the above-mentioned electroplate liquid for preparing, current density transfers to 30mA to the nickel plate as anode pickling with this sample
Cm
-2, in stirring water tank, stirs constant temperature, and with adjustment to 40 ℃ and keep constant, plating 30min promptly makes photocatalysis net with sample dry 10min in 90 ℃ baking oven then.The photocatalysis experiment shows that this catalyst material can make the percent of decolourization of reactive black reach more than 90% under the irradiation of uviol lamp in 6 hours.
Embodiment 5:
1. the surface treatment of foamed plastics: destressing (acetone: water=1:3,30min) → oil removing (20%NaOH, 50 ℃, 20min) → washing → alligatoring (CrO of 20g/L
3With the concentrated sulfuric acid of 600mL/L, 70 ~ 75 ℃, 5-15min) → neutralization → reduction → washing → sensitization (40mL/LHCl+20g/LSnCl
2, 5min) → and activation (2% AgNO3,5min) → wash → dry up.
2. the configuration of chemical plating bath: add deionized water to 1/2 of 1000mL beaker, then respectively to the Pb of the nickel salt solution 50mL of the inferior sodium phosphate that wherein adds 24g, 90g/L, 30g lactic acid, 3g propionic acid, 0.7-1.5ppm
2+, add deionized water to graduation mark after pH is adjusted to 4.6, add the SDBS of 0.5g, the TiO of 5-10g then
2, constantly stirring or employing ultrasonic wave disperse 24h standby.
3. above-mentioned plating bath is stirred in constant temperature stirs water tank, be warming up to 92 ℃ and keep constant, the foam nickel screen of the treated mistake in surface is immersed 30min in the chemical plating fluid, then sample is taken out and dry 10min and make photocatalysis net in 90 ℃ baking oven.The photocatalysis experiment shows that this catalyst material can make the percent of decolourization of reactive black reach more than 80% under the irradiation of uviol lamp in 6 hours.
Embodiment 6:
1. the pre-treatment on foam copper surface: oil removing (10%NaOH, 50 ℃, 10min) → washing → pickling (10% sulfuric acid, 50 ℃, 10min) → wash → dry up.
2. in the beaker of 250mL, add after 34mL (0.1mo1) butyl titanate and 80mL absolute ethyl alcohol mix, under agitation splash into the mixed liquor of forming by the ammonium tungstate solution of 10mL glacial acetic acid, 4mL distilled water, 80mL absolute ethyl alcohol and 15mL10g/L, stir with keeping.
3. before the gel, above-mentioned surface-treated metal foam copper mesh be impregnated in wherein after forming colloidal sol, lift taking-up with the speed of 5mm/s, dry 10min in drying box repeats aforesaid operations five times then.
4. the sample that will flood drying after five times in the stove of logical nitrogen or in the vacuum tube furnace in 350 ℃ of heat treatment 120min, thereby make TiO
2/ WO
3Photocatalysis composite coating, this coating and foam copper basal body binding force are good.The photocatalysis experiment shows that this catalyst material can make the percent of decolourization of reactive black reach more than 90% under the irradiation of uviol lamp in 4 hours; The percent of decolourization of reactive black is reached more than 80%.
Embodiment 7:
1. the pre-treatment on foamed aluminium surface: oil removing (10%NaOH, 50 ℃, 5min) → washing → pickling (10% sulfuric acid, 50 ℃, 2min) → wash → dry up.
2. after adding 30mL butyl titanate and 75mL absolute ethyl alcohol mix in the beaker of 250mL, under agitation splash into the mixed liquor of forming by 13mL glacial acetic acid, 4mL distilled water, 75mL absolute ethyl alcohol and 3.95g zinc nitrate, drip the about 2mL/min of speed, stir with keeping.
3. before the gel, above-mentioned surface-treated metal foamed aluminium net be impregnated in wherein after forming colloidal sol, lift taking-up with the speed of 5mm/s, dry 10min in drying box repeats aforesaid operations five times then.
4. the sample that will flood drying after five times in the stove of logical nitrogen or in the vacuum tube furnace in 350 ℃ of heat treatment 120min, thereby make TiO
2/ ZnO photocatalysis composite coating, this coating and foamed aluminium matrix adhesion are good.The photocatalysis experiment shows that this catalyst material all can make the percent of decolourization of reactive black reach more than 80% under the irradiation of uviol lamp or fluorescent lamp in 4 hours.
Embodiment 8:
1. the ironing surface pre-treatment of foam: oil removing (10%NaOH, 50 ℃, 5min) → washing → pickling (10% sulfuric acid, 50 ℃, 2min) → wash → dry up.
2. after adding 34mL butyl titanate and 80mL absolute ethyl alcohol mix in the beaker of 250mL, under agitation splash into the mixed liquor of forming by 12mL glacial acetic acid, 4mL distilled water, 80mL absolute ethyl alcohol and niobium oxalate solution (wt (Nb)=1.39%), then this mixed liquor is joined in the ammoniacal liquor of 6mol/L, stir with keeping.
3. before the gel, above-mentioned surface-treated metal foam iron net be impregnated in wherein after forming colloidal sol, lift taking-up with the speed of 5mm/s, dry 10min in drying box repeats aforesaid operations five times then.
4. the sample that will flood drying after five times in the stove of logical nitrogen or in the vacuum tube furnace in 350 ℃ of heat treatment 120min, thereby make TiO
2/ Nb
2O
5Photocatalysis composite coating, this coating and foam iron base body adhesion are good.The photocatalysis experiment shows that this catalyst material all can make the percent of decolourization of reactive black reach more than 80% under the irradiation of uviol lamp or fluorescent lamp in 4 hours.
The statistics of data by experiment, we have drawn the material that adopts the different loads mode to make, the degraded of the black GR of dye activity that difficulty is decomposed, its percent of decolourization is curve map (as shown in Figure 3) over time.
Claims (10)
1. a semiconductor nano catalysis material comprises carrier and the semiconductor nano photocatalyst layer that is carried on carrier surface, and it is characterized in that: described carrier is a perforated foams.
2. catalysis material as claimed in claim 1 is characterized in that: the carrier voidage of described perforated foams〉96%, thickness is 2-5mm, the aperture is 100 μ m-2mm.
3. catalysis material as claimed in claim 1 is characterized in that: described perforated foams is a kind of in foam copper, nickel foam, foam iron, foamed aluminium or the foamed plastics; The photochemical catalyst of described semiconductor light-catalyst layer is to be selected from Co
3O
4, NiO, Cu
2O, TiO
2, ZnO, CdS, Fe
2O
3, SnO
2, WO
3Or Nb
2O
5In one or both.
4. catalysis material as claimed in claim 1 is characterized in that: the particle diameter of the photochemical catalyst of described semiconductor nano photocatalyst layer is 10-50nm, and coverage rate is 50%, and load capacity is 20-50g/m
2
5. the preparation method of catalysis material as claimed in claim 1 is characterized in that may further comprise the steps:
A. with the perforated foams carrier;
B. carrier surface is handled;
C. by carrying method the semiconductor nano photochemical catalyst is fixed in described carrier surface, wherein the semiconductor nano photochemical catalyst accounts for the 1%-20% of total weight of carrier;
D. vacuum drying gets target product; Wherein, be that the carrier catalysis material also is included in makes target product in nitrogen protection or the vacuum tube furnace behind heat treatment step with the foam metal.
6. preparation method as claimed in claim 5 is characterized in that, described perforated foams is selected from a kind of in foam metal or the foamed plastics; Described semiconductor nano photochemical catalyst is selected from Co
3O
4, NiO, Cu
2O, TiO
2, ZnO, CdS, Fe
2O
3, SnO
2, WO
3Or Nb
2O
5In one or both.
7. preparation method as claimed in claim 5 is characterized in that, described carrier surface treatment step is specially:
The foam metal surface treatment step: through oil removing, washing, pickling, washing, activation dries up after the washing;
Foam Plastic Surface treatment step: after destressing, oil removing, washing, alligatoring, neutralization, reduction, washing, sensitization, activation, washing, dry up.
8. preparation method as claimed in claim 7 is characterized in that:
Degreaser in the described foam metal surface treatment deoiling step is a 10-30%NaOH solution, and temperature is 50-60 ℃, and the time of deoiling is 1-10min; Mordant in the described acid pickling step is the sulfuric acid solution of 10-20%, and temperature is 50-60 ℃, and the pickling time is 1-10min; Activator in the described activation step is the AgNO of 1-5%
3Solution, soak time are 5-10min;
Described Foam Plastic Surface handle destressing agent in the destressing step by acetone and water by acetone: the ratio of water=0.2 ~ 1:1 is prepared, and the destressing time is 20-40min; Degreaser in the described deoiling step is 10 ~ 30%NaOH solution, and temperature is 50 ~ 60 ℃, and the oil removing time is 1-10min; Alligatoring agent in the described alligatoring step is by the CrO of 15 ~ 25g/L
3With the concentrated sulfuric acid preparation of 600mL/L, temperature is 70 ~ 75 ℃, and coarsening time is 5-15min; Sensitizer in the described sensitization step is by 30 ~ 40mL/LHCl and 15 ~ 20g/LSnCl
2Preparation, sensitization time is 5-10min; Activator in the described activation step is 1 ~ 5% AgNO
3Solution, soak time are 5-10min.
9. preparation method as claimed in claim 5 is characterized in that: described carrying method comprises composite plating method, Ni-P method or dip-coating method;
Described composite plating method is specially: the prescription of composite plating plating bath comprises that concentration is the NiSO of 250-300g/L
46H
2The NiCl of O, 30-40g/L
26H
2The H of O, 40g/L
3BO
3And the TiO of the SDBS of 0.5-1g/L, 5-10g/L
2; Described perforated foams and nickel plate are immersed in the above-mentioned plating bath, respectively as negative electrode and the anode electroplated; Cathode-current density is 20-40mA
Cm
-2Bath pH value is 3.5-4.5; Stir plating 30-60min under 40-50 ℃ constant temperature;
Described Ni-P method is specially: the prescription of Ni-P plating bath comprises: concentration is the inferior sodium phosphate of 20-28g/L, the Ni of 87-93g/L
2+, 0.7-1.5ppm Pb
2+, the lactic acid of 25-30g/L, the propionic acid of 1-5g/L, the SDBS of 0.5-1g/L, the TiO of 5-10g/L
2Plating bath pH is 4-5; Described perforated foams is immersed in the above-mentioned plating bath, stir plating 30-60min under 90-94 ℃ the temperature;
Described dip-coating method is specially: be presoma with the butyl titanate, under the room temperature, the 30-40mL butyl titanate is mixed with the absolute ethyl alcohol of 75-85mL, slowly splash into by 5-10mL glacial acetic acid then, the mixed liquor that the absolute ethyl alcohol of 4-8mL deionized water and 75-85mL is formed, or in above-mentioned mixed liquor, add the salting liquid that contains the semiconductor alloy element of 10-20mL10g/L again, constantly stir, after forming colloidal sol before the gel with the surface treated foam metal matrix dipping wherein behind 5 ~ 10min in 90 ~ 100 ℃ vacuum drying chamber dry 10 ~ 20min, so circulate 3 ~ 5 times.
10. preparation method as claimed in claim 5 is characterized in that: the described vacuum drying time is 10-20min, and temperature is 90-100 ℃; Described heat treatment temperature is 300-350 ℃, and the time is 60-120min.
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| CN102941129A (en) * | 2012-11-06 | 2013-02-27 | 中国科学院广州地球化学研究所 | Supported photocatalyst as well as preparation method and application thereof |
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| CN110902939A (en) * | 2019-11-11 | 2020-03-24 | 南京信息工程大学 | Sewage treatment system |
| CN112892535A (en) * | 2021-03-05 | 2021-06-04 | 内蒙古大学 | Cu for VOC purificationxPreparation of O/Cu trans-photocatalytic material |
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| CN114377682A (en) * | 2020-10-22 | 2022-04-22 | 陕西科技大学 | Self-supporting electro-catalytic material and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1486785A (en) * | 2003-08-12 | 2004-04-07 | 上海交通大学 | Prepn process of photocatalytic filtering net of foamed metal carrying nano Tio2 |
| CN1537978A (en) * | 2003-10-22 | 2004-10-20 | 顺德市凯纳方实业有限公司 | Production method of composite photo catalytic antibacterial foamed metal |
| CN2686718Y (en) * | 2003-12-19 | 2005-03-23 | 佛山市顺德区凯纳方实业有限公司 | Composite photocatalytic antibacterial foam metal |
-
2011
- 2011-06-07 CN CN2011101504295A patent/CN102266774A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1486785A (en) * | 2003-08-12 | 2004-04-07 | 上海交通大学 | Prepn process of photocatalytic filtering net of foamed metal carrying nano Tio2 |
| CN1537978A (en) * | 2003-10-22 | 2004-10-20 | 顺德市凯纳方实业有限公司 | Production method of composite photo catalytic antibacterial foamed metal |
| CN2686718Y (en) * | 2003-12-19 | 2005-03-23 | 佛山市顺德区凯纳方实业有限公司 | Composite photocatalytic antibacterial foam metal |
Non-Patent Citations (2)
| Title |
|---|
| 孙彤等: "化学复合镀法制备多孔光催化材料及其光催化性能", 《过程工程学报》, vol. 06, no. 04, 31 August 2006 (2006-08-31), pages 639 - 644 * |
| 杨承昭等: "复合电沉积制备纳米TiO2/泡沫镍及其光催化性能研究", 《2009年全国电子电镀及表面处理学术交流会论文集》, 31 December 2009 (2009-12-31), pages 213 - 216 * |
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