CN101613080B - Method for preparing composite material for nanometer nickel/titanium dioxide nanotube array - Google Patents
Method for preparing composite material for nanometer nickel/titanium dioxide nanotube array Download PDFInfo
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- CN101613080B CN101613080B CN2009101044186A CN200910104418A CN101613080B CN 101613080 B CN101613080 B CN 101613080B CN 2009101044186 A CN2009101044186 A CN 2009101044186A CN 200910104418 A CN200910104418 A CN 200910104418A CN 101613080 B CN101613080 B CN 101613080B
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Abstract
The invention relates to a method for preparing a composite material for a nanometer nickel/titanium dioxide nanotube array by means of loading nickel nanometer grains on a titanium dioxide tube array through pulse electrodeposition. Firstly, metal titanium is used as a base; the highly-orderly nanometer titanium dioxide tube array is prepared by utilizing an anodic oxidation method; the properties of a titanium dioxide semiconductor, as well as surface electronic transmission capability, are improved after roasting; then the nickel nanometer grains are uniformly loaded on the TiO2 nanotube array by means of the pulse electrodeposition; wherein the grain diameters are controllable, the grains are uniform in terms of size, and the load capacity can also be controlled. The composite material for the Ni/TiO2 nanotube array, which is prepared according to the method, cannot only be applied in a super-capacitor but also be applied in the aspects such as photocatalysis for hydrogen generation, catalysts, magnetic materials, etc.
Description
Technical field
The present invention relates to a kind of nano metal/zinc/titanium dioxide nanotube array compound materials preparation method, especially utilize the pulse electrodeposition method, accurately control the nano metal microscopic appearance, the method for nickel-loaded nano particle on titanium dioxide nanotube array.
Background technology
Titanium dioxide (TiO
2) because of its unique physics, chemistry, photoelectric properties, have broad application prospects at solar cell, sensor, lithium ion battery, the hydrogen manufacturing of photodestruciton water and aspects such as photocatalytic degradation atmosphere and water pollutant, be subjected to paying close attention to widely.Particularly the titanium dioxide nanotube array prepared of anodizing has the structure of high orientation, big specific area and very strong ion-exchange or nano particle and embeds ability.But as a kind of environmentally friendly material, also there are some defectives in titanium dioxide, mainly shows: (1) greater band gap (3.2eV); (2) photo-quantum efficiency is very low; (3) poorly conductive.For overcoming these shortcomings, many in recent years scientific researches group forms composite and improves the functional character of titanium dioxide nanotube array and enlarge its range of application by titanium dioxide nanotube array and heavy metal, noble metal.
The method of being reported at present for preparing nano metal/titania nanotube composite mainly contains chemical reduction method and light deposition method.(1) chemical reduction method is to utilize methods such as gas reduction, organic matter reduction and metal replacement reduction, makes the reduction of solution metal ion and is deposited on substrate surface.But the crystal grain that is to use the preparation of this method is difficult to realize the nanometer on the three-dimensional dimension.(2) the light deposition method is that titania nanotube is immersed in the solution that contains metal, utilizes UV-irradiation to deposit metal in the titania nanotube surface then.Comparatively speaking size, shape and the decentralization that the pulse electrodeposition method can more effective regulation and control electro-deposition crystal grain, therefore the metal nanoparticle that can obtain to be evenly distributed, and employing pulse electrodeposition can obtain load stabilized nano metal/titanium dioxide nanotube composite construction.Pulse electrodeposition can be saved raw material, especially has very big potentiality and important meaning aspect the saving noble metal.Its operation principle mainly is: utilize the relaxation of electric current (or voltage) pulse to increase the activation polarization of negative electrode and reduce concentration polarization.When current lead-through, be deposited fully near the metal ion of negative electrode; When electric current turn-offed, the discharge ion around the negative electrode returned to initial concentration.Like this, the continuous repetition pulse electric current in cycle is mainly used in reduction of metal ion, thereby improves the physical and chemical performance of base material.
Ni/TiO
2Composite has potential using value and more and more is subjected to people's attention in catalysis and photoelectrocatalysis field owing to it.At present, in more external documents relevant for nickel with the compound report of titanium dioxide granule, researchers have also realized nickel-loaded nano particle on titanium dioxide nanoparticle by certain methods, but existing method is difficult to accurately control metallic nickel granular size, exist distribution of particles inhomogeneous, and titanium dioxide nanoparticle is the non-directional structure, and interplanar contact is unfavorable for effective transmission of electronics.
Summary of the invention
At existing the problems referred to above that the method for nickel-loaded nano particle exists on nano titanium oxide, the objective of the invention is to propose a kind of granular size controlled, be evenly distributed, the preparation method of a kind of novel nano nickel/titanium dioxide nanotube array composite that load is stable.
The present invention prepares the method for composite material for nanometer nickel/titanium dioxide nanotube array, the steps include:
1) with titanium foil sheet (purity is more than or equal to 99.6%) ultrasonic cleaning 5～15min respectively in 15～30% hydrochloric acid, absolute ethyl alcohol, distilled water successively, removes its oxide on surface;
2) titanium foil sheet after cleaning is dried is as anode, and platinized platinum places the HF solution of 0.05～0.3M, normal-temperature reaction 0.5～5h under the voltage of 5～30V as negative electrode; Form titanium dioxide nanotube array by this step;
3) with the 2nd) titanium dioxide nanotube array (TiO of step reaction gained
2/ Ti) roasting 1～5h in nitrogen or air atmosphere, sintering temperature is 300～600 ℃, optimizing temperature is 400～450 ℃;
4) consist of the NiSO of 250～350g/L at solute
46H
2The H of O and 30～45g/L
3BO
3The aqueous solution in, earlier the pH value of solution value is adjusted into 3～5, again with the 3rd) titanium dioxide nanotube array (TiO behind the one-step baking
2/ Ti) as working electrode, the nickel plate adopts the pulse electrodeposition method that nano nickel particles is carried on and obtains the nanometer nickel/titanium dioxide nanotube composite on the titania nanotube as auxiliary electrode (promptly adopting two electrode systems); The pulse electrodeposition method adopt current control mode, pulse cathode current density be-30～-300mA/cm
2, pulse anode current density is 30～300mA/cm
2, negative electrode and anodic current density equate, cathode pulse ON time 8～14ms, anodic pulse ON time 1～4ms, turn-off time 0.1～1.5s, electrodeposition time 15～100min.
Further, the 4th) can also comprise the solute NiCl that concentration is 30～60g/L in Bu the aqueous solution
26H
2O.
The 4th) reaction temperature during the pace pulse electro-deposition is controlled at 35～45 ℃, constantly stirs in the course of reaction, and mixing speed is 40～60 commentaries on classics/s.
The 4th) also can adopt three-electrode system during the pace pulse electro-deposition, remove and continue with the 3rd) titanium dioxide nanotube array (TiO behind the one-step baking
2/ Ti) as working electrode, the nickel plate is as outside the auxiliary electrode, also with Ag/AgCl as reference electrode.
The present invention has proposed the method for nickel-loaded nano particle on the titanium dioxide nanotube array that anodizing is prepared first, this method not only can be implemented on the titanium dioxide nanotube array nickel-loaded nano particle equably, controlled (the diameter 20～90nm) of the particle diameter of nano particle, the decentralization height, and has an economical with materials, advantages such as highly versatile, the nano composite material that this method obtained are expected in many high-tech areas such as high performance catalyst, magnetic material, ultracapacitor, photoelectrocatalysis important use is arranged.
Description of drawings
Fig. 1 (a, b)-electric current and voltage responsive signal under the embodiment of the invention 5 pulse current control models;
The Ni/TiO of Fig. 2-the present invention's preparation
2The X diffraction pattern of nanotube array composite.
The field emission microscope photo of the composite material for nanometer nickel/titanium dioxide nanotube array that Fig. 3-embodiment 2 obtains.
The field emission microscope photo of the composite material for nanometer nickel/titanium dioxide nanotube array that Fig. 4-embodiment 5 obtains.
The specific embodiment
Below in conjunction with the drawings and specific embodiments the present invention is described in further detail.
Method for preparing composite material for nanometer nickel/titanium dioxide nanotube array of the present invention, its preparation process is:
1) titanium foil sheet (purity is more than or equal to 99.6%) is removed the oxide on surface through abrasive paper for metallograph polishing, ultrasonic cleaning 5～15min respectively in 15～30% hydrochloric acid, absolute ethyl alcohol, distilled water successively then is with further removal oxide on surface;
2) titanium foil sheet after cleaning is dried is as anode, and platinized platinum places the HF solution of 0.05～0.3M (M is mol/L) as negative electrode, normal-temperature reaction 0.5～5h under the voltage of 5～30V; Form titanium dioxide nanotube array on the microcosmic, caliber 40～110nm, pipe range 100～500nm;
3) with the 2nd) step reaction gained titanium dioxide nanotube array (TiO
2/ Ti) roasting 1～5h in nitrogen or air atmosphere, sintering temperature is 300～600 ℃, optimizing temperature is 400～450 ℃; The heat treated purpose of this step is to improve TiO
2The pipe semiconductor property improves its electric conductivity;
4) consist of the NiSO of 250～350g/L at solute
46H
2The H of O and 30～45g/L
3BO
3(H
3BO
3Except that occuping buffering effect, can also make the nano composite structure crystallization careful, be difficult for burning.When adopting the high current density operation, boric acid content should be high) the aqueous solution in, utilize NaOH, KOH etc. that the pH value of solution value is adjusted into 3～5 earlier, adopt the pulse electrodeposition method that nano nickel particles is carried on again and obtain composite material for nanometer nickel/titanium dioxide nanotube array on the titanium dioxide nanotube array; Pulse electrodeposition both can adopt three-electrode system (to go on foot the TiO that obtains with the 3rd
2As auxiliary electrode, Ag/AgCl is as reference electrode as working electrode, Ni plate for/Ti), also can adopt two electrode system (TiO
2/ Ti is as working electrode, and the nickel plate is as auxiliary electrode); The pulse electrodeposition method adopt current control mode, pulse cathode current density be-30～-300mA/cm
2, pulse anode current density is 30～300mA/cm
2, negative electrode and anodic current density equate, cathode pulse ON time 8～14ms, anodic pulse ON time 1～4ms, turn-off time 0.1～1.5s, electrodeposition time 15～100min.Reaction temperature during pulse electrodeposition is controlled at 35～45 ℃, constantly stirs in the course of reaction, and mixing speed is 40～60 commentaries on classics/s.The pulse electrodeposition method is a prior art, and key of the present invention is to have chosen different parameter values, particularly current density, pulse ON time and turn-off time.
The 4th) can also add the NiCl that concentration is 30～60g/L in Bu the aqueous solution
26H
2O.NiCl
26H
2The effect of O: chlorion can be used as the anode depolarizing agent on the one hand, and nickel ion can be used as the source of supply of nickel on the other hand, and the both is an active ingredient.Experiment shows, NiCl
26H
2The O also NaCl of available 7～10g/L replaces.
Embodiment 1
After titanium foil sheet (purity 99.6%) removed the oxide on surface through abrasive paper for metallograph polishing, ultrasonic 10min respectively in 18% hydrochloric acid, absolute ethyl alcohol, the second distillation aqueous solution respectively was with further removal oxide on surface.Titanium foil sheet after cleaning dried is as anode, and platinized platinum is the HF solution that negative electrode places 0.15M, and under the voltage of 20V, normal-temperature reaction 2h forms titanium dioxide nanotube array.Follow 400 ℃ of roasting 3h in nitrogen.Consist of 300g/L NiSO at solute
46H
2O, 45g/LNiCl
26H
2O, 37g/L H
3BO
3The aqueous solution in, utilize NaOH with pH value of solution modulation 4.4.With the titanium dioxide nanotube array after the roasting as working electrode, Ni plate as auxiliary electrode, Ag/AgCl under current control mode, adopts following pulse electrodeposition parameter: pulse cathode current density-70mA/cm as reference electrode
2, pulse anode current density 70mA/cm
2, cathode pulse ON time 8ms, anodic pulse ON time 2ms, turn-off time 1s, electrodeposition time are 20min.Reaction temperature is controlled at 40 ℃, and mixing speed is 40 commentaries on classics/s, promptly gets composite material for nanometer nickel/titanium dioxide nanotube array.
After titanium foil sheet (purity 99.6%) removed the oxide on surface through abrasive paper for metallograph polishing, ultrasonic 10min respectively in 18% hydrochloric acid, absolute ethyl alcohol, the second distillation aqueous solution respectively was with further removal oxide on surface.Titanium foil sheet after cleaning dried is as anode, and platinized platinum is the HF solution that negative electrode places 0.15M, and under the voltage of 20V, normal-temperature reaction 2h forms titanium dioxide nanotube array.Follow 400 ℃ of roasting 3h in nitrogen.Consist of 300g/L NiSO at solute
46H
2O, 45g/LNiCl
26H
2O, 37g/L H
3BO
3The aqueous solution in, utilize NaOH with pH value of solution modulation 4.4.With the titanium dioxide nanotube array after the roasting as working electrode, Ni plate as auxiliary electrode, Ag/AgCl is as reference electrode.Under current control mode, adopt following pulse electrodeposition parameter: pulse cathode current density-70mA/cm
2, pulse anode current density 70mA/cm
2, cathode pulse ON time 8ms, anodic pulse ON time 2ms, turn-off time 1s, electrodeposition time are 25min.Reaction temperature is controlled at 40 ℃, and mixing speed is 40 commentaries on classics/s, promptly gets composite material for nanometer nickel/titanium dioxide nanotube array.The field emission microscope photo of the composite material for nanometer nickel/titanium dioxide nanotube array that Fig. 3 obtains for present embodiment, as seen from the figure, the Ni nano particle is evenly distributed, after tested its particle size average out to 43nm.
Embodiment 3
Cathode pulse ON time among the embodiment 2 is set to 12ms, and the constant Ni of the making nano particle of other conditions diminishes.
Embodiment 4
Turn-off time among the embodiment 2 is set to 0.1s, and the constant meeting of other conditions causes the Ni nano particle to become big.
Embodiment 5
Pulse cathode current density among the embodiment 2 is set to 160mA/cm
2, the constant thinner Ni nano particle of particle that obtains of other conditions.The field emission microscope photo of the composite material for nanometer nickel/titanium dioxide nanotube array that Fig. 4 obtains for present embodiment, as seen from the figure, the Ni nano particle is evenly distributed, after tested its particle size average out to 22nm.Electric current under the present embodiment pulse current control model and voltage responsive signal are seen Fig. 1 a and Fig. 1 b.
Embodiment 6
Sintering temperature is set to 550 ℃ among the embodiment 2, and the constant meeting of other conditions causes the Ni nano particle to become big.
The different preparation parameters of table 1. (embodiment 1-6) obtain the Ni nano particle load TiO of different sizes
2Nanotube array
| Embodiment | Sintering temperature (℃) | Pulse current density (mA/cm 2) | Cathode pulse ON time (ms) | Anodic pulse ON time (ms) | Turn-off time (s) | Sedimentation time (min) | Ni particle mean size (nm) |
| 1 | 400 | ±70 | 8 | 2 | 1 | 20 | 28 |
| 2 | 400 | ±70 | 8 | 2 | 1 | 25 | 43 |
| 3 | 400 | ±70 | 12 | 2 | 1 | 25 | 20 |
| 4 | 400 | ±70 | 8 | 2 | 0.1 | 25 | 84 |
| 5 | 400 | ±160 | 8 | 2 | 1 | 25 | 22 |
| 6 | 550 | ±70 | 8 | 2 | 1 | 25 | 90 |
Fig. 2 is the Ni/TiO of the present invention's preparation
2The X diffraction pattern of nanotube array composite, 2 θ equal 44.5 ° and 51.8 ° and are nano metal Ni characteristic diffraction peak among the figure, and what load be described is the Ni nano particle.
Claims (5)
1. method for preparing composite material for nanometer nickel/titanium dioxide nanotube array is characterized in that its preparation process is:
1) with titanium foil sheet ultrasonic cleaning 5～15min respectively in 15～30% hydrochloric acid, absolute ethyl alcohol, distilled water successively, to remove its oxide on surface;
2) titanium foil sheet after cleaning is dried is as anode, and platinized platinum places the HF solution of 0.05～0.3M as negative electrode, and normal-temperature reaction 0.5～5h under the voltage of 5～30V forms titanium dioxide nanotube array;
3) with the 2nd) step reaction gained titanium dioxide nanotube array roasting 1～5h in nitrogen or air atmosphere, sintering temperature is 300～600 ℃;
4) consist of the NiSO of 250～350g/L at solute
46H
2The H of O and 30～45g/L
3BO
3The aqueous solution in, earlier the pH value of solution value is adjusted into 3～5, again with the 3rd) titanium dioxide nanotube array behind the one-step baking is as working electrode, the nickel plate adopts the pulse electrodeposition method that nano nickel particles is carried on and obtains composite material for nanometer nickel/titanium dioxide nanotube array on the titanium dioxide nanotube array as auxiliary electrode; The pulse electrodeposition method adopt current control mode, pulse cathode current density be-70～-160mA/cm
2, pulse anode current density is 70～160mA/cm
2, negative electrode and anodic current density absolute value equate, cathode pulse ON time 8～14ms, anodic pulse ON time 2ms, turn-off time 0.1～1.5s, electrodeposition time 20～25min.
2. method for preparing composite material for nanometer nickel/titanium dioxide nanotube array as claimed in claim 1 is characterized in that: the 3rd) Bu sintering temperature is 400～450 ℃.
3. method for preparing composite material for nanometer nickel/titanium dioxide nanotube array as claimed in claim 1 or 2 is characterized in that: the 4th) also comprise the solute NiCl that concentration is 30～60g/L in Bu the aqueous solution
26H
2O.
4. method for preparing composite material for nanometer nickel/titanium dioxide nanotube array as claimed in claim 3 is characterized in that: the 4th) reaction temperature during the pace pulse electro-deposition is 35～45 ℃, constantly stirs in the course of reaction, and mixing speed is 40～60 commentaries on classics/s.
5. method for preparing composite material for nanometer nickel/titanium dioxide nanotube array as claimed in claim 4, it is characterized in that: the 4th) adopt three-electrode system during the pace pulse electro-deposition, with the 3rd) titanium dioxide nanotube array behind the one-step baking is as working electrode, the nickel plate is as auxiliary electrode, and Ag/AgCl is as reference electrode.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101905863A (en) * | 2010-07-09 | 2010-12-08 | 重庆大学 | Method for preparing nanometer zinc/titanium dioxide nanotube array compound materials |
| CN101955665A (en) * | 2010-08-18 | 2011-01-26 | 重庆大学 | Method for preparing composite material of polypyrrole granules and titanium dioxide nanotube array |
| CN102464382B (en) * | 2010-11-05 | 2013-10-23 | 同济大学 | High oxygen evolution potential and electrode preparation method for treating fluorine containing organic waste water |
| CN102220619B (en) * | 2011-06-01 | 2012-12-26 | 重庆大学 | Preparation method of nano platinum-nickel duplex metal/titanium dioxide nanotube array composition material |
| CN102491263B (en) * | 2011-12-30 | 2014-02-26 | 乔正阳 | Method for preparing new vanadium pentoxide nanoparticle-loaded one-dimensional nano titanium dioxide tube array material |
| CN102534726A (en) * | 2012-01-12 | 2012-07-04 | 天津大学 | Titanium dioxide (TiO2) nanotube composite material and method for depositing SnSe/Ag nanoparticles |
| 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 |
| CN102820137A (en) * | 2012-09-11 | 2012-12-12 | 天津市贝特瑞新能源科技有限公司 | High-activity TiO2 nanometer pipe/ intermediate phase carbon microsphere composite material 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 |
| CN109300702B (en) * | 2018-10-26 | 2020-09-08 | 辽宁工程技术大学 | Co (OH)2/TiO2 nanotube array composite material and preparation method thereof |
| CN111632602A (en) * | 2019-03-01 | 2020-09-08 | 南京理工大学 | Preparation method of nanoparticle/nanotube composite material |
| CN111816456B (en) * | 2020-06-30 | 2021-08-13 | 西安交通大学 | Electrode manufacturing method capable of enhancing conductivity of supercapacitor electrode and inhibiting falling of active substances |
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