CN103774198B - Help electrodip process on titania nanotube, prepare rare earth Eu doping CaF by light 2the method of film - Google Patents
Help electrodip process on titania nanotube, prepare rare earth Eu doping CaF by light 2the method of film Download PDFInfo
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- CN103774198B CN103774198B CN201410017632.9A CN201410017632A CN103774198B CN 103774198 B CN103774198 B CN 103774198B CN 201410017632 A CN201410017632 A CN 201410017632A CN 103774198 B CN103774198 B CN 103774198B
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Abstract
The invention discloses one helps electrodip process on titania nanotube, prepare rare earth Eu doping CaF by light
2the method of film.The present invention helps the method for galvanic deposit in sodium ethylene diamine tetracetate and Ca with a kind of light
2+, Eu
3+carry out constant potential galvanic deposit in the neutral mixed electrolytic solution of complexing respectively, the rare earth Eu obtaining having spherical morphology on titania nanotube adulterates CaF
2membrane electrode, then membrane electrode is calcined in air atmosphere, after to adulterate CaF to depositing the rare earth Eu obtained under different anodically deposit electricity again
2membrane electrode has carried out the photoelectric properties test under simulated solar irradiation, has investigated anodically deposit electricity to rare earth Eu doping CaF
2the impact of film electrode photoelectric performance.The low raw-material cost that the present invention uses, equipment is simple, and easy handling, has advantages of environment protection simultaneously.
Description
Technical field
The present invention relates to one helps electrodip process on titania nanotube, prepare rare earth Eu doping CaF by light
2the method of film, belongs to inorganic photovoltaic material preparation process technical field.
Background technology
TiO
2be a kind of n-type semiconductor, because chemical property is nontoxic, stable, indissoluble, cheap etc., have broad application prospects in the storage of opto-electronic conversion, sun power and utilization, photochromic and photocatalytic degradation air and water pollutant etc.In recent years, because Ti02 nanotube has larger specific surface area, stronger adsorptive power and electronic conduction ability, start to be paid close attention to widely.
Compounds exhibit containing rare earth goes out chemical property and the physical properties of many uniquenesses, is thus widely used in optical, electrical, magnetic field, is described as the treasure-house of material.Up to now, rare earth doped material has had the preparation method of a lot of relative maturity, as hydrothermal synthesis method, co-electrodeposition method, sol-gel method, pulsed laser deposition, sputtering etc., but be have not been reported by the method that light assist in electrodeposition prepares rear-earth-doped Calcium Fluoride (Fluorspan) on Nano tube array of titanium dioxide.
There is employed herein the experimental technique of light assist in electrodeposition, by applying suitable experiment condition, making to grow rare-earth europium doping calcium fluoride particles on Nano tube array of titanium dioxide, experimental installation is simple, easy and simple to handle, can carry out under low-temperature atmosphere-pressure.
Summary of the invention
The object of the invention is to the shortcoming and defect for prior art, what provide a kind of simple and effective helps electrodip process on titania nanotube, prepare rare earth Eu doping CaF by light
2the method of film.
Help electrodip process on titania nanotube, prepare rare earth Eu doping CaF by light
2the step of the method for film is as follows:
1) titanium sheet is soaked by the NaOH solution of 1 ~ 3mol/L, then deionized water and acetone ultrasonic cleaning titanium sheet 3 ~ 5 times is used, titanium sheet is cleaned until there is obvious metalluster on surface again with nitric acid and hydrofluoric acid mixed acid solution, then titanium sheet is placed in dehydrated alcohol and cleans 2 ~ 3 times, again titanium sheet is put in electrolytic solution and its Surface Oxygen is changed into titania nanotube, after 450 DEG C ~ 500 DEG C calcining 3h, obtain the titanium nano-tube array of the blueness of crystallization in titanium plate surface oxidation;
2) by the anhydrous CaCl of 0.005mol
2with 12.2mlEu (NO
3)
3solution is dissolved in the distilled water of 20mL, stirs 5 ~ 10min, adds the disodium ethylene diamine tetraacetate of 0.005mol, stirs 10 ~ 20min, makes it and Ca
2+, Eu
3+abundant complexing, then adds the NaF of 0.02mol, after being stirred to solution clarification, continuing stirring 10 ~ 20min, adds deionized water, obtain the clarification electrolytic solution that volume is 100mL; The titanium sheet of the titanium nano-tube array of the blueness of crystallization is obtained for working electrode with oxidation, platinum plate electrode is to electrode, saturated calomel electrode is reference electrode, using 500WXe lamp as light source, being placed in electrolytic solution and carrying out constant potential galvanic deposit, is 0.5 ~ 0.8V relative to the anode potential of saturated calomel electrode, deposition electricity is 0.01C ~ 8C, dry with after deionized water rinsing, in air atmosphere after 450 DEG C ~ 500 DEG C calcining 3h, the CaF that the rare earth Eu that titanium sheet obtains white adulterates
2film;
3) by step 2) obtain in titanium sheet white rare earth Eu adulterate CaF
2film carries out X-ray powder diffraction sign, XRD spectra is done by from the data Origin8 software of gained on X-ray powder diffractometer, in figure, spectral line a represents the X-ray collection of illustrative plates of titania nanotube, spectral line b represents that deposition electricity is the X-ray collection of illustrative plates after the rare-earth europium doping Calcium Fluoride (Fluorspan) thin film high temperature calcining of 0.2C, spectral line c represents that deposition electricity is the X-ray collection of illustrative plates after the rare-earth europium doping Calcium Fluoride (Fluorspan) thin film high temperature calcining of 5C, when occurring the diffraction peak of titanium dioxide in spectral line a, find that titanium dioxide has rutile and anatase octahedrite two kinds of thing phases, spectral line b, all there is the diffraction peak of titanium dioxide and the diffraction peak of Calcium Fluoride (Fluorspan) in spectral line c, all find that titanium dioxide has rutile and anatase octahedrite two kinds of thing phases, or when finding in SEM figure that spherical particle growth is on nano-tube array, in EDS energy spectrogram, there is the characteristic spectral line of O, F, Ti, Ca and Eu element simultaneously, then show to adopt light assist in electrodeposition method successfully must prepare the Calcium Fluoride (Fluorspan) of rare earth Eu doping on Nano tube array of titanium dioxide, otherwise repeating step 2) to step 3).
Described dense NaOH solution is the NaOH solution of 2 ~ 10mol/L.In described nitric acid and hydrofluoric acid mixed acid solution, the volume ratio of nitric acid and hydrofluoric acid is 2 ~ 3:1.Consisting of of described electrolytic solution: the Neutral ammonium fluoride that the polyoxyethylene glycol that volume fraction is 92% ~ 97%, massfraction are 0.3% ~ 0.5%, all the other are water.
The present invention has that equipment is simple, sedimentation rate is fast, can carry out at normal temperatures and pressures, cost is low, eco-friendly advantage, is expected to carry out suitability for industrialized production.
Accompanying drawing explanation
Fig. 1 is gained CaF in titania nanotube and embodiment 1,2
2: Eu-TiO
2the X ray diffracting spectrum of membrane electrode, wherein: that F represents is CaF
2: the diffraction peak of Eu, A representative be the diffraction peak of anatase octahedrite, R representative be the diffraction peak of rutile, all the other are the diffraction peak of titanium sheet;
Fig. 2 is gained CaF in embodiment 2
2: Eu-TiO
2sEM figure before membrane electrode high-temperature calcination
Fig. 3 is gained CaF in embodiment 2
2: Eu-TiO
2the figure of film EDS.
Embodiment
Embodiment 1
1) titanium sheet is soaked by the NaOH solution of 2mol/L, then deionized water and acetone ultrasonic cleaning titanium sheet 3 times is used, be that the nitric acid of 3:1 and hydrofluoric acid mixed acid solution cleaning titanium sheet are until there is obvious metalluster on surface by volume ratio again, then titanium sheet is placed in dehydrated alcohol and cleans 2 times, again titanium sheet is put in electrolytic solution and its Surface Oxygen is changed into titania nanotube, after 450 DEG C of calcining 3h, obtain the titanium nano-tube array of the blueness of crystallization in titanium plate surface oxidation; Consisting of of described electrolytic solution: the Neutral ammonium fluoride that the polyoxyethylene glycol that volume fraction is 98%, massfraction are 0.5%, all the other are water;
2) by the anhydrous CaCl of 0.005mol
2with 12.2mlEu (NO
3)
3solution is dissolved in the distilled water of 20mL, stirs 10min, adds the disodium ethylene diamine tetraacetate of 0.005mol, stirs 10min, makes it and Ca
2+, Eu
3+abundant complexing, then adds the NaF of 0.02mol, after being stirred to solution clarification, continuing to stir 10min, adds deionized water, obtain the clarification electrolytic solution that volume is 100mL; The titanium sheet of the titanium nano-tube array of the blueness of crystallization is obtained for working electrode with oxidation, platinum plate electrode is to electrode, saturated calomel electrode is reference electrode, using 500WXe lamp as light source, being placed in electrolytic solution and carrying out constant potential galvanic deposit, is 0.5 ~ 0.8V relative to the anode potential of saturated calomel electrode, deposition electricity is 0.2C, dry with after deionized water rinsing, in air atmosphere after 450 DEG C of calcining 3h, the CaF that the rare earth Eu that titanium sheet obtains white adulterates
2film;
3) by step 2) obtain in titanium sheet white rare earth Eu adulterate CaF
2film carries out X-ray powder diffraction sign, XRD spectra is done by from the data Origin8 software of gained on X-ray powder diffractometer, in figure, spectral line a represents the X-ray collection of illustrative plates of titania nanotube, spectral line b represents that deposition electricity is the X-ray collection of illustrative plates after the rare-earth europium doping Calcium Fluoride (Fluorspan) thin film high temperature calcining of 0.2C, when occurring the diffraction peak of titanium dioxide in spectral line a, find that titanium dioxide has rutile and anatase octahedrite two kinds of thing phases, there is the diffraction peak of titanium dioxide and the diffraction peak of Calcium Fluoride (Fluorspan) in spectral line b, find that titanium dioxide has rutile and anatase octahedrite two kinds of thing phases (see Fig. 1), or when finding in SEM figure that spherical particle growth is on nano-tube array, in EDS energy spectrogram, there is the characteristic spectral line of O, F, Ti, Ca and Eu element simultaneously, then show to adopt light assist in electrodeposition method successfully must prepare the Calcium Fluoride (Fluorspan) of rare earth Eu doping on Nano tube array of titanium dioxide.
Embodiment 2
1) titanium sheet is soaked by the NaOH solution of 2mol/L, then deionized water and acetone ultrasonic cleaning titanium sheet 3 times is used, be that the nitric acid of 3:1 and hydrofluoric acid mixed acid solution cleaning titanium sheet are until there is obvious metalluster on surface by volume ratio again, then titanium sheet is placed in dehydrated alcohol and cleans 2 times, again titanium sheet is put in electrolytic solution and its Surface Oxygen is changed into titania nanotube, after 450 DEG C of calcining 3h, obtain the titanium nano-tube array of the blueness of crystallization in titanium plate surface oxidation; Consisting of of described electrolytic solution: the Neutral ammonium fluoride that the polyoxyethylene glycol that volume fraction is 98%, massfraction are 0.5%, all the other are water;
2) by the anhydrous CaCl of 0.005mol
2with 12.2mlEu (NO
3)
3solution is dissolved in the distilled water of 20mL, stirs 10min, adds the disodium ethylene diamine tetraacetate of 0.005mol, stirs 10min, makes it and Ca
2+, Eu
3+abundant complexing, then adds the NaF of 0.02mol, after being stirred to solution clarification, continuing to stir 10min, adds deionized water, obtain the clarification electrolytic solution that volume is 100mL; The titanium sheet of the titanium nano-tube array of the blueness of crystallization is obtained for working electrode with oxidation, platinum plate electrode is to electrode, saturated calomel electrode is reference electrode, using 500WXe lamp as light source, being placed in electrolytic solution and carrying out constant potential galvanic deposit, is 0.5 ~ 0.8V relative to the anode potential of saturated calomel electrode, deposition electricity is 5C, dry with after deionized water rinsing, in air atmosphere after 450 DEG C of calcining 3h, the CaF that the rare earth Eu that titanium sheet obtains white adulterates
2film;
3) by step 2) obtain in titanium sheet white rare earth Eu adulterate CaF
2film carries out X-ray powder diffraction sign, XRD spectra is done by from the data Origin8 software of gained on X-ray powder diffractometer, in figure, spectral line a represents the X-ray collection of illustrative plates of titania nanotube, spectral line c represents that deposition electricity is the X-ray collection of illustrative plates after the rare-earth europium doping Calcium Fluoride (Fluorspan) thin film high temperature calcining of 5C, when occurring the diffraction peak of titanium dioxide in spectral line a, find that titanium dioxide has rutile and anatase octahedrite two kinds of thing phases, there is the diffraction peak of titanium dioxide and the diffraction peak of Calcium Fluoride (Fluorspan) in spectral line c, find that titanium dioxide has rutile and anatase octahedrite two kinds of thing phases (see Fig. 1), or when finding in SEM figure (see Fig. 2) that spherical particle growth is on nano-tube array, in EDS energy spectrogram (see Fig. 3), there is the characteristic spectral line of O, F, Ti, Ca and Eu element simultaneously, then show to adopt light assist in electrodeposition method successfully must prepare the Calcium Fluoride (Fluorspan) of rare earth Eu doping on Nano tube array of titanium dioxide.
Embodiment 3
1) titanium sheet is soaked by the NaOH solution of 1mol/L, then deionized water and acetone ultrasonic cleaning titanium sheet 3 times is used, be that the nitric acid of 2:1 and hydrofluoric acid mixed acid solution cleaning titanium sheet are until there is obvious metalluster on surface by volume ratio again, then titanium sheet is placed in dehydrated alcohol and cleans 2 times, again titanium sheet is put in electrolytic solution and its Surface Oxygen is changed into titania nanotube, after 450 DEG C of calcining 3h, obtain the titanium nano-tube array of the blueness of crystallization in titanium plate surface oxidation; Consisting of of described electrolytic solution: the Neutral ammonium fluoride that the polyoxyethylene glycol that volume fraction is 92%, massfraction are 0.3%, all the other are water;
2) by the anhydrous CaCl of 0.005mol
2with 12.2mlEu (NO
3)
3solution is dissolved in the distilled water of 20mL, stirs 5min, adds the disodium ethylene diamine tetraacetate of 0.005mol, stirs 10min, makes it and Ca
2+, Eu
3+abundant complexing, then adds the NaF of 0.02mol, after being stirred to solution clarification, continuing to stir 10min, adds deionized water, obtain the clarification electrolytic solution that volume is 100mL; The titanium sheet of the titanium nano-tube array of the blueness of crystallization is obtained for working electrode with oxidation, platinum plate electrode is to electrode, saturated calomel electrode is reference electrode, using 500WXe lamp as light source, being placed in electrolytic solution and carrying out constant potential galvanic deposit, is 0.5V relative to the anode potential of saturated calomel electrode, deposition electricity is 0.01C, dry with after deionized water rinsing, in air atmosphere after 450 DEG C of calcining 3h, the CaF that the rare earth Eu that titanium sheet obtains white adulterates
2film;
3) by step 2) obtain in titanium sheet white rare earth Eu adulterate CaF
2film carries out X-ray powder diffraction sign, XRD spectra is done by from the data Origin8 software of gained on X-ray powder diffractometer, in figure, spectral line a represents the X-ray collection of illustrative plates of titania nanotube, spectral line b represents that deposition electricity is the X-ray collection of illustrative plates after the rare-earth europium doping Calcium Fluoride (Fluorspan) thin film high temperature calcining of 0.01C, when occurring the diffraction peak of titanium dioxide in spectral line a, find that titanium dioxide has rutile and anatase octahedrite two kinds of thing phases, there is the diffraction peak of titanium dioxide and the diffraction peak of Calcium Fluoride (Fluorspan) in spectral line b, finds that titanium dioxide has rutile and anatase octahedrite two kinds of thing phases; Or when finding in SEM figure that spherical particle growth is on nano-tube array, in EDS energy spectrogram, there is the characteristic spectral line of O, F, Ti, Ca and Eu element simultaneously, then show to adopt light assist in electrodeposition method successfully must prepare the Calcium Fluoride (Fluorspan) of rare earth Eu doping on Nano tube array of titanium dioxide.
Embodiment 4
1) titanium sheet is soaked by the NaOH solution of 3mol/L, then deionized water and acetone ultrasonic cleaning titanium sheet 5 times is used, again with volume ratio be 3:1 nitric acid and hydrofluoric acid mixed acid solution cleaning titanium sheet until there is obvious metalluster on surface, then titanium sheet is placed in dehydrated alcohol and cleans 3 times, again titanium sheet is put in electrolytic solution and its Surface Oxygen is changed into titania nanotube, after 500 DEG C of calcining 3h, obtain the titanium nano-tube array of the blueness of crystallization in titanium plate surface oxidation; Consisting of of described electrolytic solution: the Neutral ammonium fluoride that the polyoxyethylene glycol that volume fraction is 97%, massfraction are 0.5%, all the other are water;
2) by the anhydrous CaCl of 0.005mol
2with 12.2mlEu (NO
3)
3solution is dissolved in the distilled water of 20mL, stirs 10min, adds the disodium ethylene diamine tetraacetate of 0.005mol, stirs 20min, makes it and Ca
2+, Eu
3+abundant complexing, then adds the NaF of 0.02mol, after being stirred to solution clarification, continuing to stir 20min, adds deionized water, obtain the clarification electrolytic solution that volume is 100mL; The titanium sheet of the titanium nano-tube array of the blueness of crystallization is obtained for working electrode with oxidation, platinum plate electrode is to electrode, saturated calomel electrode is reference electrode, using 500WXe lamp as light source, being placed in electrolytic solution and carrying out constant potential galvanic deposit, is 0.8V relative to the anode potential of saturated calomel electrode, deposition electricity is 8C, dry with after deionized water rinsing, in air atmosphere after 500 DEG C of calcining 3h, the CaF that the rare earth Eu that titanium sheet obtains white adulterates
2film;
3) by step 2) obtain in titanium sheet white rare earth Eu adulterate CaF
2film carries out X-ray powder diffraction sign, XRD spectra is done by from the data Origin8 software of gained on X-ray powder diffractometer, in figure, spectral line a represents the X-ray collection of illustrative plates of titania nanotube, spectral line b represents that deposition electricity is the X-ray collection of illustrative plates after the rare-earth europium doping Calcium Fluoride (Fluorspan) thin film high temperature calcining of 8C, when occurring the diffraction peak of titanium dioxide in spectral line a, find that titanium dioxide has rutile and anatase octahedrite two kinds of thing phases, there is the diffraction peak of titanium dioxide and the diffraction peak of Calcium Fluoride (Fluorspan) in spectral line b, all finds that titanium dioxide has rutile and anatase octahedrite two kinds of thing phases; Or when finding in SEM figure that spherical particle growth is on nano-tube array, in EDS energy spectrogram, there is the characteristic spectral line of O, F, Ti, Ca and Eu element simultaneously, then show to adopt light assist in electrodeposition method successfully must prepare the Calcium Fluoride (Fluorspan) of rare earth Eu doping on Nano tube array of titanium dioxide.
Claims (3)
1. one kind is helped electrodip process on titania nanotube, prepare rare earth Eu doping CaF by light
2the method of film, is characterized in that its step is as follows:
1) titanium sheet is soaked by dense NaOH solution, then deionized water and acetone ultrasonic cleaning titanium sheet 3 ~ 5 times is used, titanium sheet is cleaned until there is obvious metalluster on surface again with nitric acid and hydrofluoric acid mixed acid solution, then titanium sheet is placed in dehydrated alcohol and cleans 2 ~ 3 times, again titanium sheet is put in electrolytic solution and its Surface Oxygen is changed into titania nanotube, after 450 DEG C ~ 500 DEG C calcining 3h, obtain the titanium nano-tube array of the blueness of crystallization in titanium plate surface oxidation;
2) by the anhydrous CaCl of 0.005mol
2with 12.2mlEu (NO
3)
3solution is dissolved in the distilled water of 20mL, stirs 5 ~ 10min, adds the disodium ethylene diamine tetraacetate of 0.005mol, stirs 10 ~ 20min, makes it and Ca
2+, Eu
3+abundant complexing, then adds the NaF of 0.02mol, after being stirred to solution clarification, continuing stirring 10 ~ 20min, adds deionized water, obtain the clarification electrolytic solution that volume is 100mL; The titanium sheet of the titanium nano-tube array of the blueness of crystallization is obtained for working electrode with oxidation, platinum plate electrode is to electrode, saturated calomel electrode is reference electrode, using 500WXe lamp as light source, being placed in electrolytic solution and carrying out constant potential galvanic deposit, is 0.5 ~ 0.8V relative to the anode potential of saturated calomel electrode, deposition electricity is 0.01C ~ 8C, dry with after deionized water rinsing, in air atmosphere after 450 DEG C ~ 500 DEG C calcining 3h, the CaF that the rare earth Eu that titanium sheet obtains white adulterates
2film;
3) by step 2) obtain in titanium sheet white rare earth Eu adulterate CaF
2film carries out X-ray powder diffraction sign, XRD spectra is done by from the data Origin8 software of gained on X-ray powder diffractometer, in figure, spectral line a represents the X-ray collection of illustrative plates of titania nanotube, spectral line b represents that deposition electricity is the X-ray collection of illustrative plates after the rare-earth europium doping Calcium Fluoride (Fluorspan) thin film high temperature calcining of 0.2C, spectral line c represents that deposition electricity is the X-ray collection of illustrative plates after the rare-earth europium doping Calcium Fluoride (Fluorspan) thin film high temperature calcining of 5C, when occurring the diffraction peak of titanium dioxide in spectral line a, find that titanium dioxide has rutile and anatase octahedrite two kinds of thing phases, spectral line b, all there is the diffraction peak of titanium dioxide and the diffraction peak of Calcium Fluoride (Fluorspan) in spectral line c, all find that titanium dioxide has rutile and anatase octahedrite two kinds of thing phases, or when finding in SEM figure that spherical particle growth is on nano-tube array, in EDS energy spectrogram, there is the characteristic spectral line of O, F, Ti, Ca and Eu element simultaneously, then show to adopt light assist in electrodeposition method on Nano tube array of titanium dioxide, successfully prepared the Calcium Fluoride (Fluorspan) of rare earth Eu doping, otherwise repeating step 2) to step 3),
Described dense NaOH solution is the NaOH solution of 1 ~ 3mol/L.
2. one according to claim 1 helps electrodip process on titania nanotube, prepare rare earth Eu doping CaF by light
2the method of film, is characterized in that the volume ratio of nitric acid and hydrofluoric acid in described nitric acid and hydrofluoric acid mixed acid solution is 2 ~ 3:1.
3. one according to claim 1 helps electrodip process on titania nanotube, prepare rare earth Eu doping CaF by light
2the method of film, is characterized in that consisting of of described electrolytic solution: the Neutral ammonium fluoride that the polyoxyethylene glycol that volume fraction is 92% ~ 97%, massfraction are 0.3% ~ 0.5%, all the other are water.
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