CN101476122B - Method for solid support of modified nano titanium dioxide by chemically plating nickel-zinc-phosphor alloy - Google Patents
Method for solid support of modified nano titanium dioxide by chemically plating nickel-zinc-phosphor alloy Download PDFInfo
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- CN101476122B CN101476122B CN2009101161777A CN200910116177A CN101476122B CN 101476122 B CN101476122 B CN 101476122B CN 2009101161777 A CN2009101161777 A CN 2009101161777A CN 200910116177 A CN200910116177 A CN 200910116177A CN 101476122 B CN101476122 B CN 101476122B
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- nickel
- titanium dioxide
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- zinc
- nano titanium
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Abstract
The invention relates to a method for modifying nano titanium dioxide supported on chemical nickel plating zinc phosphorus alloy which can make modifying nano TiO2 content in a compound plating layer reach to above 60wt%, the compound plating layer combines with metallic matrix well, and can be used for light-catalyzed reaction processed in solution. A special technique is that: firstly, confecting acet solution containing 6-12 g/L modifying TiO2, depositing a modifying nano TiO2 grain layer on the copper or nickle matrix by using electrophoresis technique, then placing the copper sheet or nickel sheet or plating nickel plastic sheet doping the nano TiO2 layer into the chemical plating nickel zinc phosphorus alloy solution and leaving period of time, then preparing a nickel zinc phosphorus alloy /modifying nano TiO2 compound plating layer and realizing supporting on modifying nano TiO2. The method can realize supporting on nano TiO2 granule, and increase nano TiO2 content in the depositing layer.
Description
Technical field
The present invention relates to the nano material preparation technology, be specially and adopt electrophoresis and electroless plating compounding method, the solution modified nano-titanium dioxide is the immobilized problem during photochemical catalysis in solution.
Background technology
In conductor photocatalysis material, titanium dioxide TiO
2Have good biological and chemical inertia, stronger oxidation susceptibility, characteristics such as with low cost.Generally just can have photocatalytic activity, studies show that, at nano titanium oxide TiO in the UV-light zone
2Elements such as middle doping carbon, sulphur, nitrogen can make titanium dioxide TiO
2The red shift of photochemical catalysis response spectrum can have photocatalytic activity in visible-range.
Under occasions such as sewage disposal, need in solution, carry out light-catalyzed reaction, nano titanium oxide directly is suspended in the solution, titanium dioxide be difficult for to reclaim, and nano-powder reunites easily, need be to nano titanium oxide TiO
2Carry out immobilized.In existing technology, polymer support itself can be by titanium dioxide TiO
2Photodegradation can only short-term be used; Though various glass carrier light transmissions are good, there is the problem of adhesion property difference; The ceramic monolith light transmission is poor, and aperture and the difficult coupling of catalyst particle size; Fe when stainless steel is done carrier
3+, Cr
3+Ion enters titanium dioxide TiO easily
2Layer destroys its lattice, reduces catalytic activity, and titanium dioxide TiO
2Bonding properties is relatively poor between layer and metallic carrier.In the Ni-based alloy electroplating bath of electroless plating, add titanium dioxide TiO
2Particle makes nickel-base alloy and titanium dioxide TiO
2Particle is co-deposited on metal or the nonmetal basal body, is to solve titanium dioxide TiO
2Immobilized important channel, but titanium dioxide TiO in the co-deposited layer that this method obtains
2Shared volume ratio is generally less than 40%, and content is lower, has influenced result of use.
The present invention utilizes at first deposition layer of titanium dioxide TiO on metallic matrix of electrophoresis process
2, allow chemically plating nickel-zinc-phosphor alloy solution then at titanium dioxide TiO
2Particle reacts between the slit, realizes nano titanium oxide TiO
2Particulate is immobilized, and improves titanium dioxide TiO in the co-deposited layer
2Content.
Summary of the invention
In order to make modified nano-titanium dioxide TiO in the composite deposite
2Content reach more than the 60wt%, combine well between composite deposite and metallic matrix, can be applicable to the light-catalyzed reaction carried out in the solution, the invention provides a kind of method that adopts the chemically plating nickel-zinc-phosphor alloy solid support of modified nano titanium dioxide.
The technical solution that realizes above-mentioned purpose is as follows:
Adopt the method for chemically plating nickel-zinc-phosphor alloy solid support of modified nano titanium dioxide to comprise following operation steps:
A, get copper sheet or nickel sheet or nickel plating plastic sheet, ultrasonic cleaning is 5 minutes in acetone, takes out at room temperature at air drying;
B, be averaged the doped nano titanium dioxide 3-8 gram that particle diameter is 15-25nm, add in 500 milliliters of acetone, ultrasonic stirring 30 minutes makes solution 1;
C, Graphite Electrodes and copper sheet or nickel sheet or nickel plating plastic sheet are immersed in the glassware that solution 1 is housed, do anode with graphite, and make copper sheet or nickel sheet or nickel plating plastic sheet parallel with graphite, at inter-electrode voltage is 50-70V/cm, electrophoresis is 1 minute under the electric current 0.5-1mA condition, obtains the doped nano titanium dioxide coating on copper sheet or nickel sheet or nickel plating plastic sheet;
D, preparation chemically plating nickel-zinc-phosphor alloy solution: get single nickel salt 15～25 grams per liters, zinc sulfate 5～10 grams per liters, inferior sodium phosphate 10～40 grams per liters, trisodium citrate 30～50 grams per liters, sodium acetate 10～30 grams per liters, regulate pH value to 5.0-7.5;
E, nickel zinc-phosphor alloy solution solution is heated to 30-50 ℃, put into nickel zinc-phosphor alloy solution with applying the copper sheet of doped nano titanium dioxide coating or nickel sheet or nickel plating plastic sheet, 3-4 hour, promptly on copper sheet or nickel sheet or nickel plating plastic sheet, obtain the immobilized doped nano titanium dioxide composite deposite of nickel zinc-phosphor alloy;
Described doped nano titanium dioxide is carbon-doped nano titanium deoxid or sulfur doping nano titanium oxide or nitrogen-doped nanometer titanium dioxide.
Inventive method realizes on the one hand to nano titanium oxide TiO
2Particulate is immobilized, improves titanium dioxide TiO in the co-deposited layer on the other hand
2Content.
One of principle of the present invention is, in colloidal solution, and modified Nano TiO
2Particle has positive charge.Under electric field action, modified nano-titanium dioxide TiO
2Particle moves to negative electrode, and discharges electric charge at negative electrode, thereby deposits on cathode sample.
Two of principle of the present invention is, has on the surface of autocatalysis, and inferior sodium phosphate can be reduced into metallic nickel with nickel ion, and inferior sodium phosphate can decomposite phosphorus in this process, and zine ion also can be reduced into metallic zinc simultaneously, forms the sosoloid of nickel.When depositing modified nano-titanium dioxide TiO
2When the particulate metallic matrix was inserted in the chemically plating nickel-zinc-phosphor alloy solution, solution can pass through modified nano-titanium dioxide TiO
2The particulate space contacts with metallic matrix, and produce self-catalyzed reaction and generate the nickel zinc-phosphor alloy, because nickel zinc-phosphor alloy itself also has self-catalysis, thus sustainable the carrying out of reaction, generation nickel zinc-phosphor alloy/modified nano-titanium dioxide TiO
2Composite deposite realizes that the nickel zinc-phosphor alloy is to modified nano-titanium dioxide TiO
2Particulate is immobilized.
The invention has the beneficial effects as follows:
1. utilize electrophoresis process on matrix, to obtain uniform modified nano-titanium dioxide TiO
2Settled layer adopts chemically plating nickel-zinc phosphorus technology to realize modified nano-titanium dioxide TiO
2Immobilized, be easy to control.
2. the present invention is fit to various modified nano-titanium dioxide TiO
2, as carbon-doped nano titanium deoxid TiO
2, nitrogen-doped nanometer titanium dioxide TiO
2, sulfur doping nano titanium oxide TiO
2Immobilized, or the adulterated nano titanium oxide TiO of above-mentioned elements compounding
2, applied widely.
3. modified nano-titanium dioxide TiO in the composite deposite of the inventive method preparation
2Content reaches more than the 60wt%, combines good between composite deposite and metallic matrix.Because nickel zinc-phosphor alloy solidity to corrosion is better, the photodegradation in solution of immobilized back is effective; Through UV-irradiation 2 hours, the sample that utilizes present method to make reached 50～60% to the methyl orange solution photocatalytic degradation rate that 10mg/ rises.
Embodiment
Below in conjunction with embodiment the present invention is further described.
Embodiment 1:
Adopt the method for chemically plating nickel-zinc-phosphor alloy solid support of modified nano titanium dioxide to comprise following operation steps:
To be of a size of 20 * 30 * 1.5mm copper sheet with sand papering after, ultrasonic cleaning is 5 minutes in acetone, takes out at room temperature at air drying.Copper sheet was put into 1% stannous chloride solution dipping 1 minute, after the water flushing, immersed in 0.1% the palladium chloride solution 30 seconds, dry standby after the washing.
Taking by weighing median size is 20nm nitrogen-doped nanometer titanium dioxide 3 grams, adds in 500 milliliters of acetone, and ultrasonic stirring 30 minutes makes solution A.
Graphite Electrodes and copper sheet are immersed in the glassware that solution A is housed, do anode with graphite, copper sheet is done negative electrode, and makes copper sheet parallel with graphite, is 65V/cm at inter-electrode voltage, and electrophoresis is 1 minute under the electric current 1mA condition, obtains the nitrogen-doped nanometer titanium dioxide coating.
Preparation chemically plating nickel-zinc-phosphor alloy solution, single nickel salt 25 grams per liters; Zinc sulfate 10 grams per liters; Inferior sodium phosphate 40 grams per liters; Trisodium citrate 50 grams per liters; Sodium acetate 30 grams per liters are regulated pH value to 5.0.Solution is heated to 30 ℃.The copper sheet that applies the nitrogen-doped nanometer titanium dioxide coating is put into chemically plating nickel-zinc-phosphor alloy solution, after 4 hours, promptly obtain the immobilized nitrogen-doped nanometer titanium dioxide composite deposite of nickel zinc-phosphor alloy.
Embodiment 2
To be of a size of 20 * 30 * 2mm nickel sheet with sand papering after, ultrasonic cleaning is 5 minutes in acetone, takes out at room temperature at air drying.
Taking by weighing median size is 25nm carbon-doped nano titanium deoxid 8 grams, adds in 500 milliliters of acetone, and ultrasonic stirring 30 minutes makes solution B.
Graphite Electrodes and nickel sheet are immersed in the glassware that solution B is housed, do anode, do negative electrode with the nickel sheet with graphite, and make the nickel sheet parallel with graphite, at inter-electrode voltage is 50V/cm, and electrophoresis is 1 minute under the electric current 0.5mA condition, obtains the carbon-doped nano titanium deoxid settled layer.
Preparation chemically plating nickel-zinc-phosphor alloy solution, single nickel salt 15 grams per liters; Zinc sulfate 5 grams per liters; Inferior sodium phosphate 10 grams per liters; Trisodium citrate 30 grams per liters; Sodium acetate 25 grams per liters, pH value is adjusted to 7.5.Nickel zinc-phosphor alloy solution is heated to 50 ℃, the nickel sheet of carbon coating doped nano titanium dioxide settled layer is put into chemically plating nickel-zinc-phosphor alloy solution, 3 hours, promptly obtain the immobilized carbon-doped nano titanium deoxid composite deposite of nickel zinc-phosphor alloy.
Embodiment 3
The plastic sample that will be of a size of 20 * 30 * 1.5mm was put into 1% tin chloride solution dipping 1 minute, after the water flushing, immersed in 0.1% the palladium chloride solution 30 seconds, inserted chemical nickel-plating solution after the washing.Consisting of of chemical plating nickel-phosphorus alloy solution: single nickel salt 30 grams per liters; Inferior sodium phosphate 25 grams per liters; Trisodium citrate 45 grams per liters; Zinc sulfate 25 grams per liters; Sodium acetate 30 grams per liters are regulated pH value to 4.5.Solution is heated to 80 ℃, 30 minutes, obtains the nickel plating plastic sample.
Taking by weighing median size is 20nm nitrogen-doped nanometer titanium dioxide 3 grams, adds in 500 milliliters of acetone, and ultrasonic stirring 30 minutes makes solution C.
Graphite Electrodes and nickel plating plastic sheet are immersed in the glassware that solution C is housed, doing anode with graphite, and make the nickel plating plastic sheet parallel with graphite, is 70V/cm at inter-electrode voltage, electrophoresis is 1 minute under the electric current 0.5mA condition, obtains the nitrogen-doped nanometer titanium dioxide coating.
Preparation chemically plating nickel-zinc-phosphor alloy solution, single nickel salt 25 grams per liters; Zinc sulfate 10 grams per liters; Inferior sodium phosphate 40 grams per liters; Trisodium citrate 50 grams per liters; Sodium acetate 30 grams per liters are regulated pH value to 6.5.Solution is heated to 45 ℃.The nickel plating plastic sheet that applies the nitrogen-doped nanometer titanium dioxide coating is put into chemically plating nickel-zinc-phosphor alloy solution, 3 hours, promptly obtain the immobilized nitrogen-doped nanometer titanium dioxide composite deposite of nickel zinc-phosphor alloy.
Embodiment 4
Difference from Example 2 is that adopting median size is the sulfur doping nano-titanium dioxide powder of 15nm.Preparation chemically plating nickel-zinc-phosphor alloy solution, single nickel salt 15 grams per liters; Zinc sulfate 10 grams per liters; Inferior sodium phosphate 30 grams per liters; Trisodium citrate 40 grams per liters; Sodium acetate 10 grams per liters are regulated pH value to 6.0.Nickel zinc-phosphor alloy solution is heated to 50 ℃.The nickel sheet that applies sulfur doping nano titanium oxide settled layer is put into chemically plating nickel-zinc-phosphor alloy solution, after 3 hours, promptly obtain the immobilized sulfur doping nano titanium oxide composite deposite of nickel zinc-phosphor alloy.
Claims (1)
1. adopt the method for chemically plating nickel-zinc-phosphor alloy solid support of modified nano titanium dioxide, it is characterized in that comprising following operation steps:
A, get copper sheet or nickel sheet or nickel plating plastic sheet, ultrasonic cleaning is 5 minutes in acetone, takes out at room temperature at air drying;
B, be averaged the doped nano titanium dioxide 3-8 gram that particle diameter is 15-25nm, add in 500 milliliters of acetone, ultrasonic stirring 30 minutes makes solution 1;
C, Graphite Electrodes and copper sheet or nickel sheet or nickel plating plastic sheet are immersed in the glassware that solution 1 is housed, do anode with graphite, and make copper sheet or nickel sheet or nickel plating plastic sheet parallel with graphite, at inter-electrode voltage is 50-70V/cm, electrophoresis is 1 minute under the electric current 0.5-1mA condition, obtains the doped nano titanium dioxide coating on copper sheet or nickel sheet or nickel plating plastic sheet;
D, preparation chemically plating nickel-zinc-phosphor alloy solution: get single nickel salt 15～25 grams per liters, zinc sulfate 5～10 grams per liters, inferior sodium phosphate 10～40 grams per liters, trisodium citrate 30～50 grams per liters, sodium acetate 10～30 grams per liters, regulate pH value to 5.0-7.5;
E, nickel zinc-phosphor alloy solution solution is heated to 30-50 ℃, put into nickel zinc-phosphor alloy solution with applying the copper sheet of doped nano titanium dioxide coating or nickel sheet or nickel plating plastic sheet, 3-4 hour, promptly on copper sheet or nickel sheet or nickel plating plastic sheet, obtain the immobilized doped nano titanium dioxide composite deposite of nickel zinc-phosphor alloy;
Described doped nano titanium dioxide is carbon-doped nano titanium deoxid or sulfur doping nano titanium oxide or nitrogen-doped nanometer titanium dioxide.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009101161777A CN101476122B (en) | 2009-02-06 | 2009-02-06 | Method for solid support of modified nano titanium dioxide by chemically plating nickel-zinc-phosphor alloy |
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|---|---|---|---|
| CN2009101161777A CN101476122B (en) | 2009-02-06 | 2009-02-06 | Method for solid support of modified nano titanium dioxide by chemically plating nickel-zinc-phosphor alloy |
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| CN101476122B true CN101476122B (en) | 2010-10-13 |
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| CN102580709A (en) * | 2012-01-14 | 2012-07-18 | 天津大学 | Amorphous anatase nano titanium dioxide material and preparation method thereof |
| CN103436737B (en) * | 2013-06-19 | 2015-12-09 | 常州大学 | A kind of preparation method of zinc-phosphor alloy |
| CN109030594B (en) * | 2018-09-10 | 2020-09-08 | 合肥工业大学 | Preparation method and application of silver bismuthate-silver-titanium dioxide nanotube array |
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