CN102605369A - Amorphous nano porous titanium dioxide composite material and method thereof for depositing cadmium sulfide - Google Patents
Amorphous nano porous titanium dioxide composite material and method thereof for depositing cadmium sulfide Download PDFInfo
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- CN102605369A CN102605369A CN2012100108290A CN201210010829A CN102605369A CN 102605369 A CN102605369 A CN 102605369A CN 2012100108290 A CN2012100108290 A CN 2012100108290A CN 201210010829 A CN201210010829 A CN 201210010829A CN 102605369 A CN102605369 A CN 102605369A
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Abstract
The invention discloses an amorphous nano porous titanium dioxide composite material and a method thereof for depositing cadmium sulfide. The method comprises the following steps: preparing nano porous titanium dioxide by electrochemical dealloying, depositing CdS in the amorphous nano porous titanium dioxide, and finally, carrying out annealing treatment. The invention implements uniform distribution of cadmium sulfide nanoparticles, enhances the photocurrent of the porous titanium dioxide, and has the advantages of simple preparation process and low environmental pollution.
Description
Technical field
The present invention relates to a kind of nano material and method of modifying thereof, more particularly, relate to a kind of nano material and utilize the method for hydrothermal method modified Nano material.
Background technology
The titanium oxide of nanostructure is because its huge specific surface area and excellent photoelectric performance, in recent years, in photochemical catalysis, solar cell, research aspects such as photolysis water hydrogen have received concern widely.Take off alloyage and make one of important method of the bigger nanometer titania of preparation specific surface area.It is meant that in alloy, eroding comparatively active element through certain method stays inactive element and form vesicular structure.In Oxidant, the surface of porous metal can form zone of oxidation, thereby can be used to prepare the nano porous titanium dioxide material.With respect to crystal alloy, amorphous alloy is because its homogeneity at other composition of Subnano-class and tissue is more suitable for the initial alloy that alloyage is taken off in conduct.In addition, because the energy gap broad, the photoabsorption of titanium oxide is interval takes out ultraviolet band, and the energy of this wave band only accounts for 4～5% of solar energy total amount, so people are doing a large amount of research aspect the photosensitization of titanium oxide.Method commonly used is compound with a kind of energy gap narrower semi-conductor and titanium oxide, widen material to the responding range of light to visible region, improve the utilization ratio of catalytic efficiency (or solar energy then.CdS is a kind of photosensitizer relatively more commonly used, has good effect aspect the photoresponse of widening titanium oxide.But traditional preparation method generally all will be used ammoniacal liquor, and the ammonia that evaporates can cause adverse influence to atmospheric environment.
Summary of the invention
The objective of the invention is to overcome deficiency of the prior art; A kind of porous nano titanium oxide and cadmium sulfide nano particulate matrix material and preparation method thereof are provided; Realize cadmium sulfide nano particulate uniform distribution and the photoelectric current that improves poriferous titanium dioxide; This preparation process is simple, and environmental pollution is less.
The object of the invention is achieved through following technical scheme:
(be that step 1) is utilized electrochemistry to take off alloyage to prepare nano porous titanium dioxide: with the amorphous CTB alloy as working electrode at first; As reference electrode, as supporting electrode, electrolytic solution is aqueous nitric acid with platinum guaze or platinized platinum or Graphite Electrodes with SCE; Concentration is 3-8mol/L; With respect to open circuit potential constant potential pressurization 0.75～1.5V, the electrochemistry of in 50～80 ℃ water-bath, carrying out 1～4 hour is taken off alloy reaction, can make the amorphous nano poriferous titanium dioxide
(being step 2) places the CdS deposit fluid to deposit 8～30 minutes 50～90 ℃ of water-baths the amorphous nano poriferous titanium dioxide of step (1) preparation then, and said CdS deposit fluid is the aqueous solution, by 0.001～0.01mol/L CdCl
2, 0.002～0.015mol/L sodium nitrilo triacetate (Na
3NTA) and 0.001～0.015mol/L thiocarbamide form, the pH value of solution is adjusted to 9.5～11.5 by alkali lye
(step 3) was annealed prepared Cadmium Sulfide composite Nano poriferous titanium dioxide material thermal treatment 0.5-3 hour under 180-220 ℃ temperature, to improve the bonding force of Cadmium Sulfide and vesicular structure at last
In the wherein said step (1), the atomic molar of Ti and Cu is than being (2～5) in the amorphous CTB alloy of use: (8～5), the atomic molar ratio of preferred Ti and Cu is 3: 7.
In the said step (1), aqueous nitric acid concentration is preferably 3.38～7.55mol/L, is more preferably 5.36mol/L.
In the said step (1), be preferably 1-1.25V with respect to the constant voltage of open circuit potential, the time that feeds voltage is preferably 1.5-2h.
In the said step (1), bath temperature is 60-70 ℃.
Connate water bath temperature in the said step (2) is preferably 60-75 ℃, is more preferably 70 ℃; The preferred 10-20 of depositing time minute, be more preferably 12 minutes.
In the said step (2), CdCl in the CdS deposit fluid
2Concentration be preferably 0.004～0.006mol/L, 0.005mol/L more preferably, Na
3The concentration of NTA is preferably 0.007～0.01mol/L, and more preferably the concentration of 0.0075mol/L and thiocarbamide is preferably 0.005～0.0065mol/L, more preferably 0.00625mol/L.
Annealing temperature in the said step (3) is preferably 190-200 ℃, and the time is preferably 1-2 hour.
Method of the present invention is easy and simple to handle; Consuming time shorter, compare with the traditional preparation process method, mainly contain following advantage: (1) has solved the characteristics of particle agglomeration; Make that (shown in accompanying drawing 1, ESEM is S4800 on its nano-porous structure that is evenly distributed on titanium oxide; Hitachi, Japan); (2) reaction times shortens greatly, and simple to operate; (3) can effectively control the size of nano particle; (4) securely on the nano-porous structure attached to titanium oxide; (5) do not use ammoniacal liquor in the reaction process, thereby can not impact environment because of reaction process produces ammonia.Can know that through X-ray photoelectron spectroscopic analysis (XPS is the AXIS Ultra xps energy spectrum appearance of Britain Kratos company) (a) middle bound energy is at 464.3eV and 458.7eV; Proved that Ti is+4 valencys, (b) middle bound energy has proved that at 530.0eV O is-divalent; (c) bound energy has proved that at 411.8eV and 405.0eV Cd is+divalent in, and (d) middle bound energy is at 161.2eV and 162.3eV; Proved that S is-divalent, fully proved to generate titanium oxide and deposited the CdS nano particle.Use electrochemical workstation Gamry Ref600 to carry out the photoelectric current PT.Ionogen is the mixing solutions of S-WAT and sodium sulphite, and its concentration is respectively 0.05mol/L and 0.1mol/L.By the Cadmium Sulfide composite Nano poriferous titanium dioxide material light anode after the thermal treatment at 130mW/cm
2Xenon source illumination under, obtainable current density can reach 2.5mA/cm
2(shown in accompanying drawing 3) has a good application prospect at solar cell and photocatalysis field.
Description of drawings
The Nano cadmium sulphide granule-morphology photo (sem) that Fig. 1 obtains on amorphous nano poriferous titanium dioxide surface.
Fig. 2 X-ray photoelectron spectroscopic analysis spectrogram (XPS is the AXIS Ultra xps energy spectrum appearance of Britain Kratos company), wherein (a) figure is Ti, and (b) figure is O, and (c) figure is Cd, and (d) figure is S
The photoelectric current curve of Fig. 3 Cadmium Sulfide composite Nano poriferous titanium dioxide material light anode under xenon lamp shines.
Embodiment
Below in conjunction with specific embodiment further specify technical scheme of the present invention wherein galvanostatic method utilize Gamry Ref600 electrochemical workstation; Adopt three-electrode system; Be gauze platinum electrode as supporting electrode, SCE is as reference electrode, non-crystalline state Ti-Cu alloy is a working electrode; Wherein supporting electrode also can adopt platinized platinum or graphite, regulates the alkali lye of pH value and selects for use the sodium hydroxide of 10wt% or potassium hydroxide aqueous solution to get final product.
(1) selects Ti for use
30Cu
70AMORPHOUS ALLOY RIBBONS is a working electrode, and electrolytic solution is 5.36mol/L HNO
3Solution, 70 ℃ of bath temperatures, reference electrode constant potential pressurization 1V, makes the amorphous nano poriferous titanium dioxide at 1.5 hours time length relatively.
(2) place the Cadmium Sulfide deposit fluid 70 ℃ of water-bath deposit 12 minutes the nano porous titanium dioxide of step (1) preparation, in the said Cadmium Sulfide deposit fluid, CdCl
2Concentration be 0.005mol/L, Na
3The concentration of NTA is that the concentration of 0.0075mol/L and thiocarbamide is 0.00625mol/L, and the pH value is adjusted to 11.0
(3) the Cadmium Sulfide composite Nano poriferous titanium dioxide that step (2) is obtained was annealed 2 hours at 200 ℃.
(1) selects Ti for use
20Cu
80AMORPHOUS ALLOY RIBBONS is a working electrode, and electrolytic solution is 3.38mol/LHNO
3Solution, 60 ℃ of bath temperatures, reference electrode constant potential pressurization 1.5V, makes the amorphous nano poriferous titanium dioxide at 1 hour time length relatively.
(2) place the Cadmium Sulfide deposit fluid 90 ℃ of water-bath deposit 8 minutes the nano porous titanium dioxide of step (1) preparation, in the said Cadmium Sulfide deposit fluid, CdCl
2Concentration be 0.001mol/L, Na
3The concentration of NTA is that the concentration of 0.007mol/L and thiocarbamide is 0.001mol/L, and the pH value is adjusted to 11.5
(3) the Cadmium Sulfide composite Nano poriferous titanium dioxide that step (2) is obtained was annealed 2.5 hours at 190 ℃.
(1) selects Ti for use
50Cu
50AMORPHOUS ALLOY RIBBONS is a working electrode, and electrolytic solution is 8mol/LHNO
3Solution, 80 ℃ of bath temperatures, reference electrode constant potential pressurization 1.25V, makes the amorphous nano poriferous titanium dioxide at 4 hours time length relatively.
(2) place the Cadmium Sulfide deposit fluid 75 ℃ of water-bath deposit 20 minutes the nano porous titanium dioxide of step (1) preparation, in the said Cadmium Sulfide deposit fluid, CdCl
2Concentration be 0.004mol/L, Na
3The concentration of NTA is that the concentration of 0.007mol/L and thiocarbamide is 0.0065mol/L, and the pH value is adjusted to 9.5
(3) the Cadmium Sulfide composite Nano poriferous titanium dioxide that step (2) is obtained was annealed 0.5 hour at 220 ℃.
Embodiment 4
(1) selects Ti for use
40Cu
60AMORPHOUS ALLOY RIBBONS is a working electrode, and electrolytic solution is 7.55mol/LHNO
3Solution, 50 ℃ of bath temperatures, reference electrode constant potential pressurization 0.75V, makes the amorphous nano poriferous titanium dioxide at 2 hours time length relatively.
(2) place the Cadmium Sulfide deposit fluid 50 ℃ of water-bath deposit 30 minutes the nano porous titanium dioxide of step (1) preparation, in the said Cadmium Sulfide deposit fluid, CdCl
2Concentration be 0.01mol/L, Na
3The concentration of NTA is that the concentration of 0.015mol/L and thiocarbamide is 0.015mol/L, and the pH value is adjusted to 10
(3) the Cadmium Sulfide composite Nano poriferous titanium dioxide that step (2) is obtained was annealed 1 hour at 180 ℃.
Embodiment 5
(1) selects Ti for use
40Cu
60AMORPHOUS ALLOY RIBBONS is a working electrode, and electrolytic solution is 3mol/LHNO
3Solution, 65 ℃ of bath temperatures, reference electrode constant potential pressurization 1V, makes the amorphous nano poriferous titanium dioxide at 3 hours time length relatively.
(2) place the Cadmium Sulfide deposit fluid 60 ℃ of water-bath deposit 10 minutes the nano porous titanium dioxide of step (1) preparation, in the said Cadmium Sulfide deposit fluid, CdCl
2Concentration be 0.006mol/L, Na
3The concentration of NTA is that the concentration of 0.01mol/L and thiocarbamide is 0.015mol/L, and the pH value is adjusted to 11.0
(3) the Cadmium Sulfide composite Nano poriferous titanium dioxide that step (2) is obtained was annealed 0.5 hour at 200 ℃.
Embodiment 6
(1) selects Ti for use
30Cu
70AMORPHOUS ALLOY RIBBONS is a working electrode, and electrolytic solution is 6mol/LHNO
3Solution, 75 ℃ of bath temperatures, reference electrode constant potential pressurization 1.5V, makes the amorphous nano poriferous titanium dioxide at 2.5 hours time length relatively.
(2) place the Cadmium Sulfide deposit fluid 80 ℃ of water-bath deposit 15 minutes the nano porous titanium dioxide of step (1) preparation, in the said Cadmium Sulfide deposit fluid, CdCl
2Concentration be 0.008mol/L, Na
3The concentration of NTA is that the concentration of 0.002mol/L and thiocarbamide is 0.005mol/L, and the pH value is adjusted to 11.0
(3) the Cadmium Sulfide composite Nano poriferous titanium dioxide that step (2) is obtained was annealed 1 hour at 210 ℃.
Embodiment 7
(1) selects Ti for use
30Cu
70AMORPHOUS ALLOY RIBBONS is a working electrode, and electrolytic solution is 5mol/LHNO
3Solution, 55 ℃ of bath temperatures, reference electrode constant potential pressurization 1V, makes the amorphous nano poriferous titanium dioxide at 4 hours time length relatively.
(2) place the Cadmium Sulfide deposit fluid 65 ℃ of water-bath deposit 25 minutes the nano porous titanium dioxide of step (1) preparation, in the said Cadmium Sulfide deposit fluid, CdCl
2Concentration be 0.002mol/L, Na
3The concentration of NTA is that the concentration of 0.005mol/L and thiocarbamide is 0.008mol/L, and the pH value is adjusted to 11.5
(3) the Cadmium Sulfide composite Nano poriferous titanium dioxide that step (2) is obtained was annealed 2 hours at 200 ℃.
Embodiment 8
(1) selects Ti for use
30Cu
70AMORPHOUS ALLOY RIBBONS is a working electrode, and electrolytic solution is 4mol/LHNO
3Solution, 75 ℃ of bath temperatures, reference electrode constant potential pressurization 1V, makes the amorphous nano poriferous titanium dioxide at 3.5 hours time length relatively.
(2) place the Cadmium Sulfide deposit fluid 85 ℃ of water-bath deposit 12 minutes the nano porous titanium dioxide of step (1) preparation, in the said Cadmium Sulfide deposit fluid, CdCl
2Concentration be 0.007mol/L, Na
3The concentration of NTA is that the concentration of 0.008mol/L and thiocarbamide is 0.012mol/L, and the pH value is adjusted to 9.5
(3) the Cadmium Sulfide composite Nano poriferous titanium dioxide that step (2) is obtained was annealed 1.5 hours at 200 ℃.
More than the present invention has been done exemplary description; Should be noted that; Under the situation that does not break away from core of the present invention, the replacement that is equal to that any simple distortion, modification or other those skilled in the art can not spend creative work all falls into protection scope of the present invention.
Claims (10)
1. an amorphous nano poriferous titanium dioxide matrix material is characterized in that, in the titanium oxide structure of nanoporous, deposits Cadmium Sulfide, prepares according to following step:
Step (1) is utilized electrochemistry to take off alloyage to prepare nano porous titanium dioxide: with the amorphous CTB alloy as working electrode; As reference electrode, as supporting electrode, electrolytic solution is aqueous nitric acid with platinum guaze or platinized platinum or Graphite Electrodes with SCE; Concentration is 3-8mol/L; With respect to open circuit potential constant potential pressurization 0.75～1.5V, the electrochemistry of in 50～80 ℃ water-bath, carrying out 1～4 hour is taken off alloy reaction, can make the amorphous nano poriferous titanium dioxide
Step (2) places the CdS deposit fluid to deposit 8～30 minutes 50～90 ℃ of water-baths the amorphous nano poriferous titanium dioxide of step (1) preparation, and said CdS deposit fluid is the aqueous solution, by 0.001～0.01mol/L CdCl
2, 0.002～0.015mol/L sodium nitrilo triacetate and 0.001～0.015mol/L thiocarbamide are formed, and the pH value of solution is adjusted to 9.5～11.5 by alkali lye
Step (3) was annealed prepared Cadmium Sulfide composite Nano poriferous titanium dioxide material thermal treatment 0.5-3 hour under 180-220 ℃ temperature, to improve the bonding force of Cadmium Sulfide and vesicular structure.
2. a kind of amorphous nano poriferous titanium dioxide matrix material according to claim 1; It is characterized in that; In the said step (1), the atomic molar of Ti and Cu is than being (2～5) in the amorphous CTB alloy of use: (8～5), the atomic molar ratio of preferred Ti and Cu is 3: 7.
3. a kind of amorphous nano poriferous titanium dioxide matrix material according to claim 1 is characterized in that in the said step (1), aqueous nitric acid concentration is preferably 3.38～7.55mol/L, is more preferably 5.36mol/L; Constant voltage with respect to open circuit potential is preferably 1-1.25V, and the time that feeds voltage is preferably 1.5-2h; In the said step (1), bath temperature is 60-70 ℃.
4. a kind of amorphous nano poriferous titanium dioxide matrix material according to claim 1 is characterized in that the connate water bath temperature in the said step (2) is preferably 60-75 ℃, is more preferably 70 ℃; The preferred 10-20 of depositing time minute, be more preferably 12 minutes; In the said step (2), CdCl in the CdS deposit fluid
2Concentration be preferably 0.004～0.006mol/L, 0.005mol/L more preferably, Na
3The concentration of NTA is preferably 0.007～0.01mol/L, and more preferably the concentration of 0.0075mol/L and thiocarbamide is preferably 0.005～0.0065mol/L, more preferably 0.00625mol/L.
5. a kind of amorphous nano poriferous titanium dioxide matrix material according to claim 1 is characterized in that the annealing temperature in the said step (3) is preferably 190-200 ℃, and the time is preferably 1-2 hour.
6. a deposition cadmium sulfide nano particulate method in the titanium oxide structure of nanoporous is characterized in that, prepares according to following step:
Step (1) is utilized electrochemistry to take off alloyage to prepare nano porous titanium dioxide: with the amorphous CTB alloy as working electrode; As reference electrode, as supporting electrode, electrolytic solution is aqueous nitric acid with platinum guaze or platinized platinum or Graphite Electrodes with SCE; Concentration is 3-8mol/L; With respect to open circuit potential constant potential pressurization 0.75～1.5V, the electrochemistry of in 50～80 ℃ water-bath, carrying out 1～4 hour is taken off alloy reaction, can make the amorphous nano poriferous titanium dioxide
Step (2) places the CdS deposit fluid to deposit 8～30 minutes 50～90 ℃ of water-baths the amorphous nano poriferous titanium dioxide of step (1) preparation, and said CdS deposit fluid is the aqueous solution, by 0.001～0.01mol/L CdCl
2, 0.002～0.015mol/L sodium nitrilo triacetate and 0.001～0.015mol/L thiocarbamide are formed, and the pH value of solution is adjusted to 9.5～11.5 by alkali lye
Step (3) was annealed prepared Cadmium Sulfide composite Nano poriferous titanium dioxide material thermal treatment 0.5-3 hour under 180-220 ℃ temperature, to improve the bonding force of Cadmium Sulfide and vesicular structure.
7. a kind of cadmium sulfide nano particulate method that in the titanium oxide structure of nanoporous, deposits according to claim 6; It is characterized in that; In the said step (1); The atomic molar of Ti and Cu is than being (2～5) in the amorphous CTB alloy that uses: (8～5), the atomic molar ratio of preferred Ti and Cu is 3: 7.
8. a kind of cadmium sulfide nano particulate method that in the titanium oxide structure of nanoporous, deposits according to claim 6 is characterized in that in the said step (1), aqueous nitric acid concentration is preferably 3.38～7.55mol/L, is more preferably 5.36mol/L; Constant voltage with respect to open circuit potential is preferably 1-1.25V, and the time that feeds voltage is preferably 1.5-2h; In the said step (1), bath temperature is 60-70 ℃.
9. a kind of cadmium sulfide nano particulate method that in the titanium oxide structure of nanoporous, deposits according to claim 6 is characterized in that the connate water bath temperature in the said step (2) is preferably 60-75 ℃, is more preferably 70 ℃; The preferred 10-20 of depositing time minute, be more preferably 12 minutes; In the said step (2), CdCl in the CdS deposit fluid
2Concentration be preferably 0.004～0.006mol/L, 0.005mol/L more preferably, Na
3The concentration of NTA is preferably 0.007～0.01mol/L, and more preferably the concentration of 0.0075mol/L and thiocarbamide is preferably 0.005～0.0065mol/L, more preferably 0.00625mol/L.
10. a kind of cadmium sulfide nano particulate method that in the titanium oxide structure of nanoporous, deposits according to claim 6 is characterized in that the annealing temperature in the said step (3) is preferably 190-200 ℃, and the time is preferably 1-2 hour.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2019091096A1 (en) * | 2017-11-13 | 2019-05-16 | 吉科猛 | Nanoporous metal/metal oxide hybrid structure material, preparation, and energy storage application |
| CN109930087A (en) * | 2019-05-08 | 2019-06-25 | 常州世竟液态金属有限公司 | A kind of preparation method of zirconium-base amorphous alloy surface nano-structure layer |
| CN113410507A (en) * | 2021-06-07 | 2021-09-17 | 北京化工大学 | Novel light gain lithium-sulfur battery and preparation method thereof |
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| CN102201459A (en) * | 2011-03-30 | 2011-09-28 | 山东大学 | Photoelectrode material of nanometer porous metal load semiconductor and preparation method thereof |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2019091096A1 (en) * | 2017-11-13 | 2019-05-16 | 吉科猛 | Nanoporous metal/metal oxide hybrid structure material, preparation, and energy storage application |
| CN109930087A (en) * | 2019-05-08 | 2019-06-25 | 常州世竟液态金属有限公司 | A kind of preparation method of zirconium-base amorphous alloy surface nano-structure layer |
| CN109930087B (en) * | 2019-05-08 | 2021-04-02 | 常州世竟液态金属有限公司 | Preparation method of zirconium-based amorphous alloy surface nano-structure layer |
| CN113410507A (en) * | 2021-06-07 | 2021-09-17 | 北京化工大学 | Novel light gain lithium-sulfur battery and preparation method thereof |
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Application publication date: 20120725 |