CN102220619B - Preparation method of nano platinum-nickel duplex metal/titanium dioxide nanotube array composition material - Google Patents
Preparation method of nano platinum-nickel duplex metal/titanium dioxide nanotube array composition material Download PDFInfo
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Abstract
The invention provides a preparation method of a nano platinum-nickel duplex metal/titanium dioxide nanotube array composition material. The method comprises the steps of: a, preprocessing titanium plates; b, preparing a titanium dioxide nano tubular array; c, roasting at the high temperature; and d, loading nano platinum-nickel duplex metal. In the invention, the nano platinum-nickel duplex metal is loaded on the titanium dioxide nano tubular array to form the platinum-nickel duplex metal/titanium dioxide nanotube array composition material by adopting a multi-current (or multi-potential) pulse step change method; and the platinum-nickel duplex metal/titanium dioxide nanotube array composition material prepared by adopting the method can realize that nano platinum-nickel particles are loaded uniformly on the titanium dioxide nanotube array uniformly and has the advantages of controllable particle size of nano platinum-nickel, high dispersion degree, strong generality, and the like.
Description
Technical field
The present invention relates to a kind of preparation method of nano metal carried titanium dioxide nanotube array composite material, particularly a kind of preparation method of nanometer platinum nickel bimetal carried titanium dioxide nanotube array composite material.
Background technology
Nano composite material has great application prospect at environment protection, new energy development and high sensor aspect preparing because of having particular performances, so the preparation of nano composite material becomes one of focus of current nano materials research.Platinum is a kind of catalytic performance excellent noble metal catalyst, especially nano-platinum particle organism such as catalysis methanol, ethanol effectively, is catalyzer the most frequently used in the present alcohol fuel battery.But discover that the platinum surface is prone to adsorb the intermediate product that produces in some catalytic processs and cause poisoning of catalyst, thereby influence its catalytic activity.Simultaneously,, cause the alcohol fuel battery cost higher, limit its range of application owing to the platinum scarcity of resources, cost an arm and a leg.Therefore, improve the anti-poisoning performance and its consumption of minimizing of nanometer platinum, seek the major objective that cheap catalyzer becomes present research.People (Applied Catalysis B:Environmental 63 (2006) 137 – 149) such as Ermete Antolini discover when platinum and two kinds of metal composite of nickel form bimetallic alloy together; The anti-poisoning performance of platinum can not only be improved effectively, its catalytic performance can also be improved simultaneously.
Titanium oxide (TiO2) nanotube is the nano material of a kind of stable performance and environmental protection; Particularly the Nano tube array of titanium dioxide prepared of anonizing has structure, favorable linearity electronic transmission performance and the big specific surface area of high orientation, is a kind of support of the catalyst of excellence.Nano tube array of titanium dioxide has than sensitive photoelectric response ability in addition, when catalyst cupport is on Nano tube array of titanium dioxide, can make full use of its photoelectric response ability, improves the catalytic performance of catalyzer.People (Electrochemistry Communications 9 (2007) 1578 – 1581) such as Kyung-Won Park discover that platinum loads on the Nano tube array of titanium dioxide under the irradiation of UV-light, improve a lot under the dark attitude of the performance of platinum catalysis methanol.
In sum, nanometer platinum nickel bimetal carried titanium dioxide nanotube array composite material is a kind of catalyzer of using future that has very much.But because the sedimentation potential of platinum and nickel differs bigger; Wherein,
;
Make two kinds of metals codeposition and go out the comparison difficulty from its aqueous solution; The platinum-nickel alloy that existing simultaneously electro-deposition method is prepared can not be controlled both patterns and dispersiveness effectively, and disposable to prepare controlled and the finely disseminated platinum-nickel alloy of pattern just more difficult through galvanic deposit on this nanotube-shaped material of Nano tube array of titanium dioxide.
Summary of the invention
To above-mentioned technical barrier; The present invention introduces multiple current (or many current potentials) pulse step method the preparation field of nanometer platinum nickel bimetal carried titanium dioxide nanotube array composite material; The cardinal principle of this method is: utilize the pulse step of multiple current (or many current potentials) to strengthen the electrochemical polarization of negative electrode and reduce concentration polarization, realize the codeposition of two kinds of metals through the electric currents (or current potential) that a plurality of different sizes are set.When electric current (or current potential) was in greatly, cathode drop was higher, promoted fully deposition of the bigger metal (nickel) of electronegativity; When electric current (or current potential) is in constantly lessly, promote fully deposition of the bigger metal (platinum) of positive polarity.When electric current (or current potential) is in zero, can make negative electrode ionic concn on every side return to starting point concentration.Periodic so continuous repetition multiple current (or many current potentials) pulse step is reduced the metal platinum nickel ion.Realize the accurate control of metal size through control deposition current size and depositing time length, thereby two kinds of metals are loaded on inside and outside the Nano tube array of titanium dioxide equably.
In view of this; The objective of the invention is to propose a kind of preparation method of nanometer platinum nickel bimetal carried titanium dioxide nanotube array composite material; Make two kinds of metal particle diameter controlled amount, be evenly distributed, load is stable, thereby make nanometer platinum nickel bimetal carried titanium dioxide nanotube array composite material.
The objective of the invention is to realize through following technical scheme: a kind of preparation method of nanometer platinum nickel bimetal carried titanium dioxide nanotube array composite material may further comprise the steps:
A, the pre-treatment of titanium sheet: with titanium sheet difference ultrasonic cleaning 10～20min in absolute ethyl alcohol, hydrochloric acid, absolute ethyl alcohol and zero(ppm) water successively; The massfraction of said hydrochloric acid is 20%;
B, preparation Nano tube array of titanium dioxide: the titanium sheet after cleaning dried is as anode, and platinized platinum places the HF solution of 0.2～0.5M as negative electrode, and normal-temperature reaction 1～3h makes Nano tube array of titanium dioxide under the voltage of 10～30V;
C, high-temperature roasting: with Nano tube array of titanium dioxide roasting 1～5h in nitrogen or air atmosphere of b step gained, maturing temperature is 350～500 ℃;
D, loaded with nano platinum nickel bimetal: the NiSO that consists of 100～300g/L at solute
46H
2The NiCl of O, 15～45g/L
2, 15～45g/L H
3BO
3H with 1～10g/L
2PtCl
66H
2In the O aqueous solution; Will be in c the Nano tube array of titanium dioxide after the roasting as working electrode; Platinized platinum is as supporting electrode; Silver/silver chloride electrode adopts multiple current (or many current potentials) pulse step method that nanometer platinum nickel bimetal is deposited on and makes nanometer platinum nickel bimetal particulate load Nano tube array of titanium dioxide matrix material on the Nano tube array of titanium dioxide as reference electrode.
Further, multiple current among the said d (or many current potentials) pulse step method adopts the multiple current master mode, and bigger cathode current density is-350～-650mA/cm
2, less cathode current density is-5～-20mA/cm
2, the cathodic current time is respectively 5～20ms, and the electric current turn-off time is 0.08～1s, and the multiple current pulse step cycle is 50～400;
Further; Multiple current among the said d (or many current potentials) pulse step method adopts many control of Electric potentials pattern; Bigger cathode potential is-2.5～-4.5V, less cathode potential is-0.2～-0.4V, the cathode potential time is respectively 5～20ms; The current potential turn-off time is 0.08～1s, and many potential pulse step cycle is 20～200;
Further, the temperature of reaction the during galvanic deposit of multiple current among the d (or many current potentials) pulse step is controlled at 35～65 ℃, constantly stirs in the reaction process, and stirring velocity is 20～40 commentaries on classics/s.
The invention has the beneficial effects as follows: the present invention is used to prepare nanometer platinum nickel bimetal carried titanium dioxide nanotube array composite material with multiple current (or many current potentials) pulse step method first; This method not only can realize the load equably on Nano tube array of titanium dioxide of two kinds of metals; Two kinds of nano metal particle diameters are controlled; Dispersity is high, advantages such as highly versatile.The nano composite material that present method obtained is expected in many fields such as photoelectrocatalysis, sensor material and environment protection important use is arranged.
Description of drawings
Below in conjunction with accompanying drawing and embodiment the present invention is further described;
Accompanying drawing 1 is the X-ray diffractogram of the nanometer platinum nickel bimetal carried titanium dioxide nanotube array composite material of embodiment 1 preparation;
Accompanying drawing 2 is the X-ray energy spectrum analysis of the nanometer platinum nickel bimetal carried titanium dioxide nanotube array composite material of embodiment 1 preparation;
Accompanying drawing 3 is the field emission microscope photo of the Nano tube array of titanium dioxide material of the not loaded with nano metal of preparation among the embodiment 2;
Accompanying drawing 4 is the field emission microscope photo of embodiment 1 resulting nanometer platinum nickel bimetal carried titanium dioxide nanotube array composite material;
Accompanying drawing 5 is the field emission microscope photo of embodiment 3 resulting nanometer platinum nickel bimetal carried titanium dioxide nanotube array composite materials;
Accompanying drawing 6 is the field emission microscope photo of embodiment 4 resulting nanometer platinum nickel bimetal carried titanium dioxide nanotube array composite materials;
Accompanying drawing 7 is the field emission microscope photo of embodiment 6 resulting nanometer platinum nickel bimetal carried titanium dioxide nanotube array composite materials.
Embodiment
The preparation method of nanometer platinum nickel bimetal carried titanium dioxide nanotube array composite material of the present invention may further comprise the steps:
A, the pre-treatment of titanium sheet: purity is removed the oxide compound on surface more than or equal to 99.6% titanium sheet through abrasive paper for metallograph polishing, is ultrasonic cleaning 10～20min respectively in 20% hydrochloric acid, absolute ethyl alcohol and the zero(ppm) water at absolute ethyl alcohol, massfraction then successively; With further removal oxide on surface;
B, preparation Nano tube array of titanium dioxide: the titanium sheet after cleaning dried is as anode, and platinized platinum places the HF solution of 0.2M～0.5M (M is mol/L) as negative electrode, normal-temperature reaction 1.0h～3.0h under the voltage of 10V～30V; Make the Nano tube array of titanium dioxide of caliber 40～110nm, pipe range 100～500nm;
C, high-temperature roasting: with Nano tube array of titanium dioxide roasting 1～5h in nitrogen or air atmosphere of b step gained, maturing temperature is 350～500 ℃; Optimizing temperature is 400～450 ℃; The heat treated purpose of this step is to make Nano tube array of titanium dioxide be converted into anatase octahedrite from amorphous state, improves its electroconductibility;
D, loaded with nano platinum nickel bimetal: the NiSO that consists of 100～300g/L at solute
46H
2The NiCl of O, 15～45g/L
2, 15～45g/L H
3BO
3H with 1～10g/L
2PtCl
66H
2In the aqueous solution of O; Will be in c the Nano tube array of titanium dioxide after the roasting as working electrode; Platinized platinum is as supporting electrode; Silver/silver chloride electrode adopts multiple current (or many current potentials) pulse step method that nanometer platinum nickel bimetal is carried on and makes nanometer platinum nickel bimetal carried titanium dioxide nanotube array composite material on the Nano tube array of titanium dioxide as reference electrode.
After the oxide compound on surface was removed in the abrasive paper for metallograph polishing, ultrasonic cleaning 10min respectively in absolute ethyl alcohol, 20% hydrochloric acid, absolute ethyl alcohol, the second distillation aqueous solution respectively was with further removal oxide on surface with the titanium sheet of purity 99.6%; Titanium sheet after cleaning dried is as anode, and platinized platinum is the HF solution that negative electrode places 0.2M, and under the voltage of 30V, normal-temperature reaction 1h forms Nano tube array of titanium dioxide; Follow roasting 5h in 350 ℃ air; Consist of the NiSO of 100g/L at solute
46H
2The NiCl of O, 45g/L
2, 10g/L H
3BO
3H with 1g/L
2PtCl
66H
2In the aqueous solution of O; With the Nano tube array of titanium dioxide after the roasting as working electrode, platinized platinum as supporting electrode; Silver/silver chloride electrode under the multiple current master mode, adopts following experiment parameter as reference electrode: bigger cathode current density is-350mA/cm
2, less cathode current density is-20mA/cm
2The cathodic current time is respectively 5ms, electric current turn-off time 0.08s, and the multiple current pulse step cycle is 400; Temperature of reaction is controlled at 35 ℃, and stirring velocity is 20 commentaries on classics/s, can make nanometer platinum nickel bimetal carried titanium dioxide nanotube array composite material of the present invention.
After the oxide compound on surface was removed in the abrasive paper for metallograph polishing, ultrasonic cleaning 15min respectively in absolute ethyl alcohol, 20% hydrochloric acid, absolute ethyl alcohol, the second distillation aqueous solution respectively was with further removal oxide on surface with the titanium sheet of purity 99.6%.Titanium sheet after cleaning dried is as anode, and platinized platinum is the HF solution that negative electrode places 0.3M, and under the voltage of 20V, normal-temperature reaction 2h forms Nano tube array of titanium dioxide; Follow 450 ℃ of roasting 3h in nitrogen.Consist of the NiSO of 200g/L at solute
46H
2The NiCl of O, 30g/L
2, 35g/L H
3BO
3H with 5g/L
2PtCl
66H
2In the aqueous solution of O with the Nano tube array of titanium dioxide after the roasting as working electrode, platinized platinum as supporting electrode; Silver/silver chloride electrode is as reference electrode; Under the multiple current master mode, adopt following experiment parameter: bigger cathode current density is-450mA/cm
2, less cathode current density is-10mA/cm
2The cathodic current time is respectively 10ms, electric current turn-off time 1s, and the multiple current pulse step cycle is 100; Temperature of reaction is controlled at 50 ℃, and stirring velocity is 30 commentaries on classics/s, can make nanometer platinum nickel bimetal carried titanium dioxide nanotube array composite material of the present invention.
After the oxide compound on surface was removed in the abrasive paper for metallograph polishing, ultrasonic cleaning 20min respectively in absolute ethyl alcohol, 20% hydrochloric acid, absolute ethyl alcohol, the second distillation aqueous solution respectively was with further removal oxide on surface with the titanium sheet of purity 99.6%.Titanium sheet after cleaning dried is as anode, and platinized platinum is the HF solution that negative electrode places 0.5M, and under the voltage of 10V, normal-temperature reaction 3h forms Nano tube array of titanium dioxide; Follow 500 ℃ of roasting 1h in nitrogen.Consist of the NiSO of 300g/L at solute
46H
2The NiCl of O, 15g/L
2, 45g/L H
3BO
3H with 10g/L
2PtCl
66H
2In the aqueous solution of O with the Nano tube array of titanium dioxide after the roasting as working electrode, platinized platinum as supporting electrode; Silver/silver chloride electrode is as reference electrode; Under the multiple current master mode, adopt following experiment parameter: bigger cathode current density is-650mA/cm
2, less cathode current density is-5mA/cm
2The cathodic current time is respectively 20ms, electric current turn-off time 1s, and the multiple current pulse step cycle is 50; Temperature of reaction is controlled at 65 ℃, and stirring velocity is 40 commentaries on classics/s, can make nanometer platinum nickel bimetal carried titanium dioxide nanotube array composite material of the present invention.
After the oxide compound on surface was removed in the abrasive paper for metallograph polishing, ultrasonic cleaning 10min respectively in absolute ethyl alcohol, 20% hydrochloric acid, absolute ethyl alcohol, the second distillation aqueous solution respectively was with further removal oxide on surface with the titanium sheet of purity 99.6%.Titanium sheet after cleaning dried is as anode, and platinized platinum is the HF solution that negative electrode places 0.5M, and under the voltage of 10V, normal-temperature reaction 3h forms Nano tube array of titanium dioxide; Follow 500 ℃ of roasting 1h in nitrogen; Consist of the NiSO of 300g/L at solute
46H
2The NiCl of O, 15g/L
2, 45g/L H
3BO
3H with 1g/L
2PtCl
66H
2O; With the Nano tube array of titanium dioxide after the roasting as working electrode, platinized platinum as supporting electrode, silver/silver chloride electrode is as reference electrode, under many control of Electric potentials pattern; Adopt following experiment parameter: bigger cathode potential is-4.5V that less cathode potential is-0.2V.The cathode potential time is respectively 20ms, and the current potential turn-off time is 1s, and many potential pulse step cycle is 20; Temperature of reaction is controlled at 65 ℃, and stirring velocity is 40 commentaries on classics/s, can make nanometer platinum nickel bimetal carried titanium dioxide nanotube array composite material of the present invention.
Embodiment 5
After the oxide compound on surface was removed in the abrasive paper for metallograph polishing, ultrasonic cleaning 15min respectively in absolute ethyl alcohol, 20% hydrochloric acid, absolute ethyl alcohol, the second distillation aqueous solution respectively was with further removal oxide on surface with the titanium sheet of purity 99.6%; Titanium sheet after cleaning dried is as anode, and platinized platinum is the HF solution that negative electrode places 0.3M, and under the voltage of 20V, normal-temperature reaction 2h forms Nano tube array of titanium dioxide; Follow roasting 3h in 450 ℃ air; Consist of the NiSO of 200g/L at solute
46H
2The NiCl of O, 30g/L
2, 30g/L H
3BO
3H with 4g/L
2PtCl
66H
2O; With the Nano tube array of titanium dioxide after the roasting as working electrode, platinized platinum as supporting electrode, silver/silver chloride electrode is as reference electrode, under many control of Electric potentials pattern; Adopt following experiment parameter: bigger cathode potential is-3.5V that less cathode potential is-0.3V.The cathode potential time is respectively 10ms, and the current potential turn-off time is 0.08s, and many potential pulse step cycle is 50; Temperature of reaction is controlled at 50 ℃, and stirring velocity is 30 commentaries on classics/s, can make nanometer platinum nickel bimetal carried titanium dioxide nanotube array composite material of the present invention.
Embodiment 6
After the oxide compound on surface was removed in the abrasive paper for metallograph polishing, ultrasonic cleaning 20min respectively in absolute ethyl alcohol, 20% hydrochloric acid, absolute ethyl alcohol, the second distillation aqueous solution respectively was with further removal oxide on surface with the titanium sheet of purity 99.6%; Titanium sheet after cleaning dried is as anode, and platinized platinum is the HF solution that negative electrode places 0.2M, and under the voltage of 30V, normal-temperature reaction 1h forms Nano tube array of titanium dioxide; Follow roasting 5h in 350 ℃ nitrogen; Consist of the NiSO of 100g/L at solute
46H
2The NiCl of O, 45g/L
2, 15g/L H
3BO
3H with 10g/L
2PtCl
66H
2O; With the Nano tube array of titanium dioxide after the roasting as working electrode, platinized platinum as supporting electrode, silver/silver chloride electrode is as reference electrode, under many control of Electric potentials pattern; Adopt following experiment parameter: bigger cathode potential is-2.5V that less cathode potential is-0.4V.The cathode potential time is respectively 5ms, and the current potential turn-off time is 0.08s, and many potential pulse step cycle is 200; Temperature of reaction is controlled at 35 ℃, and stirring velocity is 20 commentaries on classics/s, can make nanometer platinum nickel bimetal carried titanium dioxide nanotube array composite material of the present invention.
As shown in the figure: accompanying drawing 1 is that the X-ray diffractogram of nanometer platinum nickel bimetal carried titanium dioxide nanotube array composite material of embodiment 1 preparation is as shown in the figure; 2 θ equal 25.27o among the figure; 52.09o be respectively (101) that belong to anatase octahedrite, the diffraction peak of (105) crystal face; 2 θ equal 39.9 ° among the figure, 46.7 ° and the 67.9 ° characteristic diffraction peaks that are respectively metal platinum (111) (200) (220); 2 θ equal 44.5 ° and are the characteristic diffraction peak of metallic nickel (111), and to sum up the result can explain that the metal of load on the Nano tube array of titanium dioxide is two kinds of metals of nanometer platinum nickel.
Accompanying drawing 2 is the X-ray energy spectrum analysis of the nanometer platinum nickel bimetal carried titanium dioxide nanotube array composite material of embodiment 6 preparation, and the relative mass that from figure, can calculate various elements is respectively: O content is 9.96%, Ti content is 16.22%, Pt content is 46.18%, Ni content is 27.64%.
Accompanying drawing 3 is the field emission microscope photo of the Nano tube array of titanium dioxide material of the not loaded with nano platinum nickel bimetal of preparation in the embodiment 2; Accompanying drawing 4 is the field emission microscope photo of the nanometer platinum nickel bimetal carried titanium dioxide nanotube array composite material of embodiment 1 preparation; Accompanying drawing 5 is the field emission microscope photo of embodiment 3 resulting nanometer platinum nickel bimetal carried titanium dioxide nanotube array composite materials; Accompanying drawing 6 is the field emission microscope photo of embodiment 4 resulting nanometer platinum nickel bimetal carried titanium dioxide nanotube array composite materials.Accompanying drawing 7 is the field emission microscope photo of embodiment 6 resulting nanometer platinum nickel bimetal carried titanium dioxide nanotube array composite materials.Accompanying drawing 3 is in accompanying drawing 6; White particle is the nanometer platinum nickel particle of load; Through comparing with accompanying drawing 3; Obviously can find out the nanometer platinum nickel bimetal carried titanium dioxide nanotube array composite material that adopts method of the present invention to make, the surface is uniformly distributed with nanometer platinum nickel bimetal particle, and the different dispersity of size are higher; Can also control the size of particle diameter in addition through the length of control electrodeposition time, satisfy the demand of different-grain diameter.
Explanation is at last; Above embodiment is only unrestricted in order to technical scheme of the present invention to be described; Although with reference to preferred embodiment the present invention is specified, those of ordinary skill in the art should be appreciated that and can make amendment or be equal to replacement technical scheme of the present invention; And not breaking away from the aim and the scope of technical scheme of the present invention, it all should be encompassed in the middle of the power claimed range of the present invention.
Claims (5)
1. the preparation method of nanometer platinum nickel bimetal/Nano tube array of titanium dioxide matrix material is characterized in that: may further comprise the steps:
A, the pre-treatment of titanium sheet: with titanium sheet difference ultrasonic cleaning 10～20min in absolute ethyl alcohol, hydrochloric acid, absolute ethyl alcohol and zero(ppm) water successively; The massfraction of said hydrochloric acid is 20%;
B, preparation Nano tube array of titanium dioxide: the titanium sheet after pre-treatment dried is as anode, and platinized platinum places the HF solution of 0.2～0.5M as negative electrode, and normal-temperature reaction 1～3h makes Nano tube array of titanium dioxide under the voltage of 10～30V;
C, high-temperature roasting: with Nano tube array of titanium dioxide roasting 1～5h in nitrogen or air atmosphere of b step gained, maturing temperature is 350～500 ℃;
D, uniform loading nanometer platinum nickel bimetal particle: the NiSO that consists of 100～300g/L at solute
46H
2The NiCl of O, 15～45g/L
2, 15～45g/L H
3BO
3H with 1～10g/L
2PtCl
66H
2In the O aqueous solution; Will be through the Nano tube array of titanium dioxide after the c roasting as working electrode; Platinized platinum is as supporting electrode; Silver/silver chloride electrode adopts multiple current or many potential pulse step method that nanometer platinum nickel bimetal particulate load is made nanometer platinum nickel bimetal/Nano tube array of titanium dioxide matrix material on Nano tube array of titanium dioxide as reference electrode.
2. the preparation method of nanometer platinum nickel bimetal according to claim 1/Nano tube array of titanium dioxide matrix material; It is characterized in that: multiple current or many potential pulse step method adopt the multiple current master mode among the said d, and bigger cathode current density is-350～-650mA/cm
2, less cathode current density is-5～-20mA/cm
2, the cathodic current time is respectively 5～20ms, and the electric current turn-off time is 0.08～1s, and the multiple current pulse step cycle is 50～400.
3. the preparation method of nanometer platinum nickel bimetal according to claim 1/Nano tube array of titanium dioxide matrix material; It is characterized in that: multiple current or many potential pulse step method adopt many control of Electric potentials pattern among the said d; Bigger cathode potential is-2.5～-4.5V, less cathode potential is-0.2～-0.4V, the cathode potential time is respectively 5～20ms; The current potential turn-off time is 0.08～1s, and many potential pulse step cycle is 20～200.
4. according to the preparation method of claim 1,2 or 3 described nanometer platinum nickel bimetal/Nano tube array of titanium dioxide matrix materials; It is characterized in that: the temperature of reaction among the d during galvanic deposit of multiple current or many potential pulse step is controlled at 10～65 ℃; Constantly stir in the reaction process, stirring velocity is 10～60 commentaries on classics/s.
5. the preparation method of nanometer platinum nickel bimetal according to claim 4/Nano tube array of titanium dioxide matrix material; It is characterized in that: the temperature of reaction among the d during galvanic deposit of multiple current or many potential pulse step is controlled at 35～65 ℃; Constantly stir in the reaction process, stirring velocity is 20～40 commentaries on classics/s.
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| CN102703942B (en) * | 2012-06-20 | 2015-04-29 | 北京工业大学 | Method for preparing nano-platinum/palladium titanium dioxide nanotube composite electrode by pulse electrodeposition |
| CN102828219A (en) * | 2012-07-13 | 2012-12-19 | 湖南大学 | Ternary nanocomposite Au/RGO-TiO2 nanotube array as well as preparation method and application thereof |
| CN102942215A (en) * | 2012-09-10 | 2013-02-27 | 重庆大学 | Three-dimensional SnO2 nano flower-like material grown on titanium substrate and preparation method thereof |
| CN105297107B (en) * | 2015-07-27 | 2017-12-01 | 北京工业大学 | A kind of method of cyclic voltammetric electrodeposited nanocrystalline platinum nickel/titanium dioxide nanotube electrode |
| CN105603492B (en) * | 2016-01-29 | 2018-10-09 | 武汉理工大学 | A method of the electrochemical deposition silver nano-grain in Nano tube array of titanium dioxide |
| CN106191945A (en) * | 2016-07-01 | 2016-12-07 | 北京工业大学 | A kind of pulse electrodeposition prepares the method for titania nanotube immobilized platinum nickel bimetal combination electrode |
| CN107604380B (en) * | 2017-08-14 | 2019-10-29 | 浙江工业大学 | Pb/foamed nickel electrode and preparation method and application thereof |
| CN108330524B (en) * | 2018-01-08 | 2019-11-08 | 武汉科技大学 | Nano nickel titanium dioxide nanotube array perforated membrane and preparation method thereof |
| CN108145175A (en) * | 2018-01-10 | 2018-06-12 | 云南大学 | A kind of preparation method of Au/Ni double bases nano particle molectronics electrod-array |
| CN109411244A (en) * | 2018-10-12 | 2019-03-01 | 中国矿业大学 | A kind of preparation method of titanium dioxide/double-metal hydroxide combination electrode |
| CN110820035B (en) * | 2019-11-12 | 2021-12-10 | 盐城工学院 | Cobalt hydroxide/foamed nickel composite electrode prepared based on multi-potential cyclic step method and method |
| CN110988074B (en) * | 2019-12-20 | 2021-12-21 | 肇庆学院 | CoCu @ cubic Ia3d structure mesoporous carbon electrochemical sensor and application thereof in detection of trace cyadox |
| CN114392753A (en) * | 2021-11-30 | 2022-04-26 | 盐城工学院 | Ag and NiO co-doped TiO2Method for preparing nanotube array |
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