CN103400699B - A kind of quantum dot modifies ZnO nanorod array electrode and preparation method thereof - Google Patents
A kind of quantum dot modifies ZnO nanorod array electrode and preparation method thereof Download PDFInfo
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Abstract
A kind of quantum dot modifies ZnO nanorod array electrode and preparation method thereof, and it relates to a kind of array electrode and preparation method thereof.The present invention will solve ZnO nano material photocatalysis efficiency is low under visible light, the technical problem low to the utilance of sunlight.Preparation method of the present invention carries out according to the following steps: one, be substrate with electro-conductive glass, adopts hydro thermal method to obtain the ZnO nano-rod array of high-sequential; Two, at above-mentioned ZnO nano-rod array surface alternating deposit polyelectrolyte and quantum dot particle, obtain evenly coated quantum dot and modify ZnO nanorod array electrode.The thickness of method to the length of ZnO nano-rod array and coated quantum dot that the present invention prepares optoelectronic pole is controlled; The electrode that the present invention obtains under visible light illumination, shows good photoelectric catalytically active and visible light-responded characteristic.The present invention is used for photoelectric catalysis degrading environmental contaminants, photoelectrocatalysis synthesis and photodissociation aquatic products hydrogen field.
Description
Technical field
The present invention relates to a kind of array electrode and preparation method thereof.
Background technology
Zinc oxide (ZnO) is a kind of important direct wide bandgap semiconductor materials, have excellent piezoelectricity, thermoelectricity, photoelectric characteristic, ZnO nanorod causes people in the application in the fields such as Flied emission, gas sensor, solar cell, field-effect transistor and el light emitting device and studies interest widely.
Because ZnO nano material can only absorb and scatters ultraviolet, and ultraviolet only account for 5-6% in sunlight, thus causes the photocatalysis efficiency of the photovoltaic device based on ZnO nano material lower, low to the utilance of sunlight.
LBL self-assembly method (Layer-by-LayerSelf-assembly, LbL) method is also known as ion self assembly, and it refers to that nano particle or nano particle compound with just (bearing) electric charge dress up superstructure with being with the ion of negative (just) electric charge, supermolecule, biomolecule, nano particle or nano particle compound by electrostatic attraction alternate group.In an assembling process, the polyelectrolyte (PE) with plus or minus electric charge is the most often used alternately to assemble with nano material.
Summary of the invention
The object of the invention is to solve ZnO nano material that photocatalysis efficiency is lower under visible light, for the low technical problem of the utilance of sunlight, and a kind of quantum dot provided modifies ZnO nanorod array electrode and preparation method thereof.
A kind of quantum dot of the present invention is modified ZnO nanorod array electrode and is comprised substrate, ZnO nano-rod array and quantum dot coating layer, wherein, described substrate is conductive substrates, described ZnO nano-rod array is made up of the hexamethylenetetramine of concentration to be the zinc nitrate hexahydrate of 0.08 ~ 0.12M and concentration be 0.08 ~ 0.12M, described zinc nitrate hexahydrate and the volume ratio of hexamethylenetetramine are 1:1, described quantum dot coating layer replaces coated forming by cationic polyelectrolyte-phenanthroline cobalt layers and quantum dot nano-particle layer, described cationic polyelectrolyte-phenanthroline cobalt layers is coated on ZnO nano-rod array, quantum dot nano-particle layer is coated in cationic polyelectrolyte-phenanthroline cobalt layers, wherein, described quantum dot nano-particle layer is CdTe nano-particle layer, CdS nano-particle layer or CdSe nano-particle layer.
The preparation method that a kind of quantum dot of the present invention modifies ZnO nanorod array electrode carries out according to the following steps:
One, hydro thermal method making ZnO nanometer stick array: substrate is immersed in zinc nitrate hexahydrate-hexamethylenetetramine solution, after 70 ~ 95 DEG C of reaction 2.5h ~ 15h, take out substrate, ultrasonic cleaning is carried out successively with deionized water and absolute ethyl alcohol, then anneal 10 ~ 60min at 250 ~ 400 DEG C of temperature, obtains ZnO nano-rod array;
Two, the preparation of CdTe nanoparticles solution: a, take 0.5 ~ 1.4g six perchloric acid hydrate cadmium and be dissolved in 100 ~ 150mL redistilled water, after adding 0.2 ~ 0.8mL3-mercaptopropionic acid, regulate pH to 9 ~ 11 of solution by the NaOH solution that concentration is 0.5 ~ 2M, obtain solution A; B, in a nitrogen atmosphere, the sulfuric acid solution that 10 ~ 20mL concentration is 0.2 ~ 0.7M is added in 0.1 ~ 0.4g telluride aluminium powder, the gas that reaction produces is imported in solution A, simultaneously by solution A back flow reaction 12 ~ 48h at 80 ~ 150 DEG C, stir with magneton in course of reaction, obtain CdTe nanoparticles solution;
Three, the preparation of phenanthroline cobalt: the ratio of 1:3 in molar ratio, takes hydrated cobalt chloride and phenanthroline is put in mortar, at room temperature mixes, grinds more than 2.5h;
Four, to carry out quantum dot coated for LBL self-assembly method: gained ZnO nano-rod array in step one being immersed in pH is in the cationic polyelectrolyte-phenanthroline cobalt liquor of 6.2 ~ 8.5 after 5 ~ 20min, takes out and uses deionized water rinsing, drying up; Then be immersed in 5 ~ 20min in the CdTe nanoparticles solution of step 2 gained, take out and use deionized water rinsing, drying up;
Five, repeat step 4 10 ~ 25 times, namely obtain the ZnO nano-rod array that quantum dot is modified;
Wherein, the substrate described in step one is conductive substrates;
Zinc nitrate hexahydrate described in step one-hexamethylenetetramine solution is be the zinc nitrate hexahydrate of 0.08 ~ 0.12M and concentration by concentration is that the hexamethylenetetramine of 0.08 ~ 0.12M is by volume for the ratio of 1:1 mixes;
Cationic polyelectrolyte described in step 4-phenanthroline cobalt liquor is made up of the cationic polyelectrolyte of concentration to be the phenanthroline cobalt of 0.5 ~ 2mg/mL and concentration be 0.2 ~ 1mg/mL; Wherein, described cationic polyelectrolyte is polymine, polyallylamine hydrochloride or PDDA.
The preparation method that a kind of quantum dot of the present invention modifies ZnO nanorod array electrode carries out according to the following steps:
One, hydro thermal method making ZnO nanometer stick array: substrate is immersed in zinc nitrate hexahydrate-hexamethylenetetramine solution, after 70 ~ 95 DEG C of reaction 2.5h ~ 15h, take out substrate, ultrasonic cleaning is carried out successively with deionized water and absolute ethyl alcohol, then anneal 10 ~ 60min at 250 ~ 400 DEG C of temperature, obtains ZnO nano-rod array;
Two, CdS nanoparticles solution is prepared by the following method: a, take 0.5 ~ 1.4g six perchloric acid hydrate cadmium and be dissolved in 100 ~ 150mL redistilled water, after adding 0.2 ~ 0.8mL3-mercaptopropionic acid, regulate pH to 9 ~ 11 of solution by the NaOH solution that concentration is 0.5 ~ 2M, obtain solution A; B, in a nitrogen atmosphere, in solution A, add 0.09 ~ 0.25g thioacetamide, simultaneously by solution A back flow reaction 12 ~ 48h at 80 ~ 150 DEG C, stir with magneton in course of reaction, obtain CdS nanoparticles solution;
Three, the preparation of phenanthroline cobalt: the ratio of 1:3 in molar ratio, takes hydrated cobalt chloride and phenanthroline is put in mortar, at room temperature mixes, grinds more than 2.5h;
Four, to carry out quantum dot coated for LBL self-assembly method: gained ZnO nano-rod array in step one being immersed in pH is in the cationic polyelectrolyte-phenanthroline cobalt liquor of 6.2 ~ 8.5 after 5 ~ 20min, takes out and uses deionized water rinsing, drying up; Then be immersed in 5 ~ 20min in the CdS nanoparticles solution of step 2 gained, take out and use deionized water rinsing, drying up;
Five, repeat step 4 10 ~ 25 times, namely obtain the ZnO nano-rod array that quantum dot is modified;
Wherein, the substrate described in step one is conductive substrates;
Zinc nitrate hexahydrate described in step one-hexamethylenetetramine solution is be the zinc nitrate hexahydrate of 0.08 ~ 0.12M and concentration by concentration is that the hexamethylenetetramine of 0.08 ~ 0.12M is by volume for the ratio of 1:1 mixes;
Cationic polyelectrolyte described in step 4-phenanthroline cobalt liquor is made up of the cationic polyelectrolyte of concentration to be the phenanthroline cobalt of 0.5 ~ 2mg/mL and concentration be 0.2 ~ 1mg/mL; Wherein, described cationic polyelectrolyte is polymine, polyallylamine hydrochloride or PDDA.
The preparation method that a kind of quantum dot of the present invention modifies ZnO nanorod array electrode carries out according to the following steps:
One, hydro thermal method making ZnO nanometer stick array: substrate is immersed in zinc nitrate hexahydrate-hexamethylenetetramine solution, after 70 ~ 95 DEG C of reaction 2.5h ~ 15h, take out substrate, ultrasonic cleaning is carried out successively with deionized water and absolute ethyl alcohol, then anneal 10 ~ 60min at 250 ~ 400 DEG C of temperature, obtains ZnO nano-rod array;
Two, CdSe nanoparticles solution is prepared by the following method: take 0.04 ~ 0.09g six perchloric acid hydrate cadmium and be dissolved in 60 ~ 100mL deionized water, add the natrium citricum of 0.08 ~ 0.13g, then use 0.5 ~ 2M sodium hydroxide solution that pH value is adjusted to 9 ~ 11, logical nitrogen 10min; Taking 0.004 ~ 0.007g selenourea is dissolved in the deionized water of 4mL, adds above-mentioned mixed liquor after ultrasonic mixing, and mixed liquor is ultrasonic 50s in the microwave oven of 900W, obtains CdSe nanoparticles solution;
Three, the preparation of phenanthroline cobalt: the ratio of 1:3 in molar ratio, takes hydrated cobalt chloride and phenanthroline is put in mortar, at room temperature mixes, grinds more than 2.5h;
Four, to carry out quantum dot coated for LBL self-assembly method: gained ZnO nano-rod array in step one being immersed in pH is in the cationic polyelectrolyte-phenanthroline cobalt liquor of 6.2 ~ 8.5 after 5 ~ 20min, takes out and uses deionized water rinsing, drying up; Then be immersed in 5 ~ 20min in the CdSe nanoparticles solution of step 2 gained, take out and use deionized water rinsing, drying up;
Five, repeat step 4 10 ~ 25 times, namely obtain the ZnO nano-rod array that quantum dot is modified;
Wherein, the substrate described in step one is conductive substrates;
Zinc nitrate hexahydrate described in step one-hexamethylenetetramine solution is be the zinc nitrate hexahydrate of 0.08 ~ 0.12M and concentration by concentration is that the hexamethylenetetramine of 0.08 ~ 0.12M is by volume for the ratio of 1:1 mixes;
Cationic polyelectrolyte described in step 4-phenanthroline cobalt liquor is made up of the cationic polyelectrolyte of concentration to be the phenanthroline cobalt of 0.5 ~ 2mg/mL and concentration be 0.2 ~ 1mg/mL; Wherein, described cationic polyelectrolyte is polymine, polyallylamine hydrochloride or PDDA.
The present invention has following beneficial effect:
1, a kind of quantum dot of the present invention modifies the preparation method of ZnO nanorod array electrode, by regulating the number of plies coated layer by layer, and can the thickness of effective control CdTe shell.
2, the quantum dot prepared of the present invention is modified ZnO nano-rod array and is absorbed with significant enhancing at visible light wave range, and obvious photoelectric respone is had under the solar source of being simulated by xenon lamp irradiates, current-time curvel shows that it has higher photocurrent response speed and good reappearance.
3, to modify the expression activitiy of ZnO nanorod array electrode photoelectrocatalysis phenol under visible light high for the quantum dot prepared of the present invention, improves more than 35% compared with removing situation with the phenol of ZnO nanorod array electrode under similarity condition.Simultaneously, compared with simple photocatalysis phenol, the intermediate product that quantum dot prepared by the present invention modifies ZnO nanorod array electrode photoelectrocatalysis phenol is under visible light mainly the materials such as biodegradable glycerine, small molecular organic acid, and catalytic process is more efficient and thoroughly.The process injecting electronics from CdTe conduction band to ZnO conduction band can suppress the compound of electron hole pair.Therefore, on ZnO nano-rod array, coated CdTe will increase the light sensitivity of ZnO for visible ray, effectively can utilize in solar radiation the visible ray accounting for the overwhelming majority, thus improves the photocatalysis efficiency of ZnO.Electric field-assisted can suppress the compound of electron hole pair further, and the photoelectric catalysis degrading process therefore under electric field-assisted is more efficient and thorough.
4, a kind of quantum dot of the present invention preparation method that modifies ZnO nanorod array electrode growth time be 10 hours, under the coated number of plies is 20 double-deck conditions, the photoelectric properties of the ZnO/CdTe nano composite structure of acquisition are best.
Accompanying drawing explanation
Fig. 1 is the ultraviolet-visible absorption spectroscopy figure of ZnO nano-rod array in embodiment 1 and ZnO/CdTe nano composite structure; In figure, 1 is ZnO/CdTe nano composite structure, and 2 is ZnO nano-rod array, and 3 is MPA-CdTe quantum dot;
Fig. 2 is the SEM vertical view of the ZnO nano-rod array grown in ITO substrate in embodiment 1;
Fig. 3 is the SEM vertical view of the ZnO/CdTe nano composite structure in embodiment 1;
Fig. 4 be ZnO nano-rod array in embodiment 1 and ZnO/CdTe nano composite structure visible ray according under the phenol concentration of photoelectrocatalysis phenol and degradation time graph of a relation; In figure, 1 is ZnO nano-rod array, and 2 is ZnO/CdTe nano composite structure.
Embodiment
Technical solution of the present invention is not limited to following cited embodiment, also comprises the combination in any between each embodiment.
Embodiment one: a kind of quantum dot of present embodiment is modified ZnO nanorod array electrode and comprised substrate, ZnO nano-rod array and quantum dot coating layer, wherein, described substrate is conductive substrates, described ZnO nano-rod array is made up of the hexamethylenetetramine of concentration to be the zinc nitrate hexahydrate of 0.08 ~ 0.12M and concentration be 0.08 ~ 0.12M, described zinc nitrate hexahydrate and the volume ratio of hexamethylenetetramine are 1:1, described quantum dot coating layer replaces coated forming by cationic polyelectrolyte-phenanthroline cobalt layers and quantum dot nano-particle layer, described cationic polyelectrolyte-phenanthroline cobalt layers is coated on ZnO nano-rod array, quantum dot nano-particle layer is coated in cationic polyelectrolyte-phenanthroline cobalt layers, wherein, described quantum dot nano-particle layer is CdTe nano-particle layer, CdS nano-particle layer or CdSe nano-particle layer.
Quantum dot described in present embodiment modifies ZnO nanorod array electrode significantly to be increased in the absorption of visible light wave range.
Embodiment two: present embodiment and embodiment one unlike: described conductive substrates is ITO or FTO.Other is identical with embodiment one.
Embodiment three: present embodiment and embodiment one or two unlike: the preparation method of described cationic polyelectrolyte-phenanthroline cobalt layers is as follows: ZnO nano-rod array being immersed in pH is in the cationic polyelectrolyte-phenanthroline cobalt liquor of 6.2 ~ 8.5 after 5 ~ 20min, take out and use deionized water rinsing, dry up, namely complete;
Wherein, described cationic polyelectrolyte-phenanthroline cobalt liquor is made up of the cationic polyelectrolyte of concentration to be the phenanthroline cobalt of 0.5 ~ 2mg/mL and concentration be 0.2 ~ 1mg/mL; Wherein, the cationic polyelectrolyte in described cationic polyelectrolyte-phenanthroline cobalt layers is polymine, polyallylamine hydrochloride or PDDA.Other is identical with embodiment one or two.
Embodiment four: one of present embodiment and embodiment one to three unlike: the preparation method of described quantum dot nano-particle layer is as follows: to be immersed in by the ZnO nano-rod array of coated cationic polyelectrolyte-phenanthroline cobalt layers in quantum dot nano-particle solution after 5 ~ 20min, take out and use deionized water rinsing, dry up, namely complete;
Wherein, described quantum dot nano-particle solution is CdTe nanoparticles solution, CdS nanoparticles solution or CdSe nanoparticles solution;
Described CdTe nanoparticles solution is prepared by the following method: a, take 0.5 ~ 1.4g six perchloric acid hydrate cadmium and be dissolved in 100 ~ 150mL redistilled water, after adding 0.2 ~ 0.8mL3-mercaptopropionic acid, regulate pH to 9 ~ 11 of solution by the NaOH solution that concentration is 0.5 ~ 2M, obtain solution A; B, in a nitrogen atmosphere, the sulfuric acid solution that 10 ~ 20mL concentration is 0.2 ~ 0.7M is added in 0.1 ~ 0.4g telluride aluminium powder, the gas that reaction produces is imported in solution A, simultaneously by solution A back flow reaction 12 ~ 48h at 80 ~ 150 DEG C, stir with magneton in course of reaction, obtain CdTe nanoparticles solution;
Described CdS nanoparticles solution is prepared by the following method: a, take 0.5 ~ 1.4g six perchloric acid hydrate cadmium and be dissolved in 100 ~ 150mL redistilled water, after adding 0.2 ~ 0.8mL3-mercaptopropionic acid, regulate pH to 9 ~ 11 of solution by the NaOH solution that concentration is 0.5 ~ 2M, obtain solution A; B, in a nitrogen atmosphere, in solution A, add 0.09 ~ 0.25g thioacetamide, simultaneously by solution A back flow reaction 12 ~ 48h at 80 ~ 150 DEG C, stir with magneton in course of reaction, obtain CdS nanoparticles solution;
Described CdSe nanoparticles solution is prepared by the following method: take 0.04 ~ 0.09g six perchloric acid hydrate cadmium and be dissolved in 60 ~ 100mL deionized water, add the natrium citricum of 0.08 ~ 0.13g, then use 0.5 ~ 2M sodium hydroxide solution that pH value is adjusted to 9 ~ 11, logical nitrogen 10min; Taking 0.004 ~ 0.007g selenourea is dissolved in the deionized water of 4mL, adds above-mentioned mixed liquor after ultrasonic mixing, and mixed liquor is ultrasonic 50s in the microwave oven of 900W, obtains CdSe nanoparticles solution.Other is identical with one of embodiment one to three.
Embodiment five: the preparation method of a kind of quantum dot modification ZnO nanorod array electrode of present embodiment carries out according to the following steps:
One, hydro thermal method making ZnO nanometer stick array: substrate is immersed in zinc nitrate hexahydrate-hexamethylenetetramine solution, after 70 ~ 95 DEG C of reaction 2.5h ~ 15h, take out substrate, ultrasonic cleaning is carried out successively with deionized water and absolute ethyl alcohol, then anneal 10 ~ 60min at 250 ~ 400 DEG C of temperature, obtains ZnO nano-rod array;
Two, the preparation of CdTe nanoparticles solution: a, take 0.5 ~ 1.4g six perchloric acid hydrate cadmium and be dissolved in 100 ~ 150mL redistilled water, after adding 0.2 ~ 0.8mL3-mercaptopropionic acid, regulate pH to 9 ~ 11 of solution by the NaOH solution that concentration is 0.5 ~ 2M, obtain solution A; B, in a nitrogen atmosphere, the sulfuric acid solution that 10 ~ 20mL concentration is 0.2 ~ 0.7M is added in 0.1 ~ 0.4g telluride aluminium powder, the gas that reaction produces is imported in solution A, simultaneously by solution A back flow reaction 12 ~ 48h at 80 ~ 150 DEG C, stir with magneton in course of reaction, obtain CdTe nanoparticles solution;
Three, the preparation of phenanthroline cobalt: the ratio of 1:3 in molar ratio, takes hydrated cobalt chloride and phenanthroline is put in mortar, at room temperature mixes, grinds more than 2.5h;
Four, to carry out quantum dot coated for LBL self-assembly method: gained ZnO nano-rod array in step one being immersed in pH is in the cationic polyelectrolyte-phenanthroline cobalt liquor of 6.2 ~ 8.5 after 5 ~ 20min, takes out and uses deionized water rinsing, drying up; Then be immersed in 5 ~ 20min in the CdTe nanoparticles solution of step 2 gained, take out and use deionized water rinsing, drying up;
Five, repeat step 4 10 ~ 25 times, namely obtain the ZnO nano-rod array that quantum dot is modified;
Wherein, the substrate described in step one is conductive substrates;
Zinc nitrate hexahydrate described in step one-hexamethylenetetramine solution is be the zinc nitrate hexahydrate of 0.08 ~ 0.12M and concentration by concentration is that the hexamethylenetetramine of 0.08 ~ 0.12M is by volume for the ratio of 1:1 mixes;
Cationic polyelectrolyte described in step 4-phenanthroline cobalt liquor is made up of the cationic polyelectrolyte of concentration to be the phenanthroline cobalt of 0.5 ~ 2mg/mL and concentration be 0.2 ~ 1mg/mL; Wherein, described cationic polyelectrolyte is polymine, polyallylamine hydrochloride or PDDA.
At 250 ~ 400 DEG C of annealing 10 ~ 60min in step one described in present embodiment, be the conductivity in order to strengthen ZnO nanorod.
Reflux times different in step 2 described in present embodiment, can obtain the CdTe nano particle that the MPA of different-grain diameter is stable.
A kind of quantum dot described in present embodiment modifies the preparation method of ZnO nanorod array electrode, preparation technology is simple, can prepare on a large scale, the material prepared is evenly distributed in substrate, and the efficiency of photoelectrocatalysis phenol is higher by more than 35% than the catalytic efficiency of the ZnO optoelectronic pole not modifying quantum dot under visible light.
Embodiment six: present embodiment and embodiment five unlike: the conductive substrates described in step one is ITO or FTO.Other is identical with embodiment five.
Embodiment seven: present embodiment and embodiment five unlike: in the ZnO nano-rod array described in step one, the length of ZnO nanorod is 1 ~ 8 μm.Other is identical with embodiment five.
Embodiment eight: present embodiment and embodiment five unlike: taking six perchloric acid hydrate cadmium quality described in step 2 is 0.5 ~ 1.4g.Other is identical with embodiment five.
Embodiment nine: present embodiment and embodiment five unlike: adding 3-mercaptopropionic acid volume described in step 2 is 0.2 ~ 0.5mL.Other is identical with embodiment five.
Embodiment ten: present embodiment and embodiment five unlike: the quality adding telluride aluminium powder described in step 2 is 0.1 ~ 0.3g.Other is identical with embodiment five.
Embodiment 11: the preparation method of a kind of quantum dot modification ZnO nanorod array electrode of present embodiment carries out according to the following steps:
One, hydro thermal method making ZnO nanometer stick array: substrate is immersed in zinc nitrate hexahydrate-hexamethylenetetramine solution, after 70 ~ 95 DEG C of reaction 2.5h ~ 15h, take out substrate, ultrasonic cleaning is carried out successively with deionized water and absolute ethyl alcohol, then anneal 10 ~ 60min at 250 ~ 400 DEG C of temperature, obtains ZnO nano-rod array;
Two, CdS nanoparticles solution is prepared by the following method: a, take 0.5 ~ 1.4g six perchloric acid hydrate cadmium and be dissolved in 100 ~ 150mL redistilled water, after adding 0.2 ~ 0.8mL3-mercaptopropionic acid, regulate pH to 9 ~ 11 of solution by the NaOH solution that concentration is 0.5 ~ 2M, obtain solution A; B, in a nitrogen atmosphere, in solution A, add 0.09 ~ 0.25g thioacetamide, simultaneously by solution A back flow reaction 12 ~ 48h at 80 ~ 150 DEG C, stir with magneton in course of reaction, obtain CdS nanoparticles solution;
Three, the preparation of phenanthroline cobalt: the ratio of 1:3 in molar ratio, takes hydrated cobalt chloride and phenanthroline is put in mortar, at room temperature mixes, grinds more than 2.5h;
Four, to carry out quantum dot coated for LBL self-assembly method: gained ZnO nano-rod array in step one being immersed in pH is in the cationic polyelectrolyte-phenanthroline cobalt liquor of 6.2 ~ 8.5 after 5 ~ 20min, takes out and uses deionized water rinsing, drying up; Then be immersed in 5 ~ 20min in the CdS nanoparticles solution of step 2 gained, take out and use deionized water rinsing, drying up;
Five, repeat step 4 10 ~ 25 times, namely obtain the ZnO nano-rod array that quantum dot is modified;
Wherein, the substrate described in step one is conductive substrates;
Zinc nitrate hexahydrate described in step one-hexamethylenetetramine solution is be the zinc nitrate hexahydrate of 0.08 ~ 0.12M and concentration by concentration is that the hexamethylenetetramine of 0.08 ~ 0.12M is by volume for the ratio of 1:1 mixes;
Cationic polyelectrolyte described in step 4-phenanthroline cobalt liquor is made up of the cationic polyelectrolyte of concentration to be the phenanthroline cobalt of 0.5 ~ 2mg/mL and concentration be 0.2 ~ 1mg/mL; Wherein, described cationic polyelectrolyte is polymine, polyallylamine hydrochloride or PDDA.
At 250 ~ 400 DEG C of annealing 10 ~ 60min in step one described in present embodiment, be the conductivity in order to strengthen ZnO nanorod.
Reflux times different in step 2 described in present embodiment, can obtain the CdS nano particle that the MPA of different-grain diameter is stable.
A kind of quantum dot described in present embodiment modifies the preparation method of ZnO nanorod array electrode, preparation technology is simple, can prepare on a large scale, the material prepared is evenly distributed in substrate, and the efficiency of photoelectrocatalysis phenol is higher by more than 35% than the catalytic efficiency of the ZnO optoelectronic pole not modifying quantum dot under visible light.
Embodiment 12: present embodiment and embodiment 11 unlike: the conductive substrates described in step one is ITO or FTO.Other is identical with embodiment 11.
Embodiment 13: present embodiment and embodiment 11 unlike: in the ZnO nano-rod array described in step one, the length of ZnO nanorod is 1 ~ 8 μm.Other is identical with embodiment 11.
Embodiment 14: present embodiment and embodiment 11 unlike: taking six perchloric acid hydrate cadmium quality described in step 2 is 0.5 ~ 1.4g.Other is identical with embodiment 11.
Embodiment 15: present embodiment and embodiment 11 unlike: adding 3-mercaptopropionic acid volume described in step 2 is 0.2 ~ 0.5mL.Other is identical with embodiment 11.
Embodiment 16: present embodiment and embodiment 11 unlike: the quality adding thioacetamide described in step 2 is 0.09 ~ 0.25g.Other is identical with embodiment 11.
Embodiment 17: the preparation method of a kind of quantum dot modification ZnO nanorod array electrode of present embodiment carries out according to the following steps:
One, hydro thermal method making ZnO nanometer stick array: substrate is immersed in zinc nitrate hexahydrate-hexamethylenetetramine solution, after 70 ~ 95 DEG C of reaction 2.5h ~ 15h, take out substrate, ultrasonic cleaning is carried out successively with deionized water and absolute ethyl alcohol, then anneal 10 ~ 60min at 250 ~ 400 DEG C of temperature, obtains ZnO nano-rod array;
Two, CdSe nanoparticles solution is prepared by the following method: take 0.04 ~ 0.09g six perchloric acid hydrate cadmium and be dissolved in 60 ~ 100mL deionized water, add the natrium citricum of 0.08 ~ 0.13g, then use 0.5 ~ 2M sodium hydroxide solution that pH value is adjusted to 9 ~ 11, logical nitrogen 10min; Taking 0.004 ~ 0.007g selenourea is dissolved in the deionized water of 4mL, adds above-mentioned mixed liquor after ultrasonic mixing, and mixed liquor is ultrasonic 50s in the microwave oven of 900W, obtains CdSe nanoparticles solution;
Three, the preparation of phenanthroline cobalt: the ratio of 1:3 in molar ratio, takes hydrated cobalt chloride and phenanthroline is put in mortar, at room temperature mixes, grinds more than 2.5h;
Four, to carry out quantum dot coated for LBL self-assembly method: gained ZnO nano-rod array in step one being immersed in pH is in the cationic polyelectrolyte-phenanthroline cobalt liquor of 6.2 ~ 8.5 after 5 ~ 20min, takes out and uses deionized water rinsing, drying up; Then be immersed in 5 ~ 20min in the CdSe nanoparticles solution of step 2 gained, take out and use deionized water rinsing, drying up;
Five, repeat step 4 10 ~ 25 times, namely obtain the ZnO nano-rod array that quantum dot is modified;
Wherein, the substrate described in step one is conductive substrates;
Zinc nitrate hexahydrate described in step one-hexamethylenetetramine solution is be the zinc nitrate hexahydrate of 0.08 ~ 0.12M and concentration by concentration is that the hexamethylenetetramine of 0.08 ~ 0.12M is by volume for the ratio of 1:1 mixes;
Cationic polyelectrolyte described in step 4-phenanthroline cobalt liquor is made up of the cationic polyelectrolyte of concentration to be the phenanthroline cobalt of 0.5 ~ 2mg/mL and concentration be 0.2 ~ 1mg/mL; Wherein, described cationic polyelectrolyte is polymine, polyallylamine hydrochloride or PDDA.
At 250 ~ 400 DEG C of annealing 10 ~ 60min in step one described in present embodiment, be the conductivity in order to strengthen ZnO nanorod.
A kind of quantum dot described in present embodiment modifies the preparation method of ZnO nanorod array electrode, preparation technology is simple, can prepare on a large scale, the material prepared is evenly distributed in substrate, and the efficiency of photoelectrocatalysis phenol is higher by more than 35% than the catalytic efficiency of the ZnO optoelectronic pole not modifying quantum dot under visible light.
Embodiment 18: present embodiment and embodiment 17 unlike: the conductive substrates described in step one is ITO or FTO.Other is identical with embodiment 17.
Embodiment 19: present embodiment and embodiment 17 unlike: in the ZnO nano-rod array described in step one, the length of ZnO nanorod is 1 ~ 8 μm.Other is identical with embodiment 17.
Embodiment 20: present embodiment and embodiment 17 unlike: taking six perchloric acid hydrate cadmium quality described in step 2 is 0.04 ~ 0.09g.Other is identical with embodiment 17.
Embodiment 21: present embodiment and embodiment 17 unlike: adding natrium citricum quality described in step 2 is 0.08 ~ 0.13g.Other is identical with embodiment 17.
Embodiment 22: present embodiment and embodiment 17 unlike: the quality adding selenourea described in step 2 is 0.004 ~ 0.007g.Other is identical with embodiment 17.
Following examples and contrast experiment is adopted to verify beneficial effect of the present invention:
Embodiment one:
A kind of quantum dot of the present embodiment modifies the preparation method of ZnO nanorod array electrode, specifically prepares according to following steps:
One, hydro thermal method making ZnO nanometer stick array: using ITO as substrate, immerses in zinc nitrate hexahydrate-hexamethylenetetramine solution, after 90 DEG C of reaction 10h, obtains the ZnO nanorod that length is about 5 μm; Take out substrate, carry out ultrasonic cleaning with deionized water and absolute ethyl alcohol successively, then at 300 DEG C of annealing 30min, obtain ZnO nano-rod array;
Two, the preparation of CdTe nanoparticles solution: take 0.986g six perchloric acid hydrate cadmium and be dissolved in 125mL redistilled water, add 0.43ml3-mercaptopropionic acid, then regulates the pH to 11.2 of solution, obtains solution A by the NaOH solution that concentration is 2M; B, in a nitrogen atmosphere, in 0.2g telluride aluminium powder, add the sulfuric acid solution that 15mL concentration is 0.5M, the gas that reaction produces is imported in solution A, simultaneously by solution A back flow reaction 24h at 105 DEG C, stir with magneton in back flow reaction process, obtain CdTe nanoparticles solution;
Three, the preparation of phenanthroline cobalt: the ratio of 1:3 in molar ratio, takes hydrated cobalt chloride and phenanthroline is put in mortar, at room temperature mixes, grinds 2.5h.
Four, to carry out quantum dot coated for LBL self-assembly method: gained ZnO nano-rod array in step one being immersed in pH is in the aziridine-phenanthroline cobalt liquor of 7.2 after 10min, takes out and uses deionized water rinsing, drying up; Then be immersed in 10min in the CdTe nanoparticles solution of step 2 gained, take out and use deionized water rinsing, drying up;
Five, repeat step 4 20 times, namely obtain the ZnO nano-rod array that quantum dot is modified;
Wherein, the zinc nitrate hexahydrate described in step one-hexamethylenetetramine solution is be the zinc nitrate hexahydrate of 0.1M and concentration by concentration is that the hexamethylenetetramine of 0.1M is by volume for the ratio of 1:1 mixes;
Aziridine described in step 4-phenanthroline cobalt liquor by concentration be 1mg/mL Phen cluck and concentration be that the polymine of 0.5mg/mL forms.
In the present embodiment step one, the ZnO nano-rod array of preparation as shown in Figure 2, the ZnO nano-rod array prepared as shown in Figure 2 is equably perpendicular to substrate surface, there are hexagon looks more clearly, illustrate to be prepared by hydro thermal method to there is higher orientation, the ZnO nanorod of high crystalline quality.
Prepare in the present embodiment step 4 coated after ZnO/CdTe nano composite structure nanometer rods barred body as shown in Figure 3, as shown in Figure 3, gained nanometer rods barred body is comparatively level and smooth, and the top cross-section of rod is no longer hexagon, and the diameter of nanometer rods is obviously greater than the diameter of ZnO nanorod in Fig. 2.
In order to study the ultravioletvisible absorption performance of ZnO/CdTe composite construction, first the ZnO nano-rod array of preparation and the ultravioletvisible absorption characteristic of CdTe nano particle are studied.As shown in Figure 1, known cadmium telluride quantum dot has at 545nm place, visual field and absorbs very by force the ultraviolet-visible absorption spectroscopy of the cadmium telluride quantum dot of synthesis.Have studied the ultravioletvisible absorption characteristic of cadmium telluride nano particles coated front and back ZnO sample subsequently.The ultravioletvisible absorption intensity of the ZnO/CdTe composite construction of surface deposition 20 layers of cadmium telluride nano particles has an obvious enhancing, and have an obvious absworption peak at 551nm place, the ultraviolet and visible absorption peak position of the cadmium telluride nano particles measured is therewith close, prove that cadmium telluride quantum dot deposits to ZnO nano-rod array surface, ZnO/CdTe composite construction is in absorption obvious enhancing compared with ZnO nano-rod array of visible light wave range.
Using ZnO/CdTe electrode as work electrode, study the efficiency of its photoelectrocatalysis phenol, the initial concentration of phenol is 100mg/L, and applying bias is 1.0V.By comparing ZnO/CdTe and the ZnO electrode different catalytic efficiency for phenol, result as shown in Figure 4, show that the expression activitiy of ZnO/CdTe nano composite structure photoelectrocatalysis phenol is under visible light high, clearance rate for phenol reached 75% after 2.5 hours, improve 35% compared with removing situation with the phenol of ZnO nanorod array electrode under similarity condition.
By the ZnO nano-rod array of more different growth time and the photoelectric properties of the ZnO/CdTe nano composite structure of difference coated CdTe layer number, find that the photoelectric properties that growth time is 10 hours, the coated number of plies is 20 double-deck ZnO/CdTe nano composite structures are best, its density of photocurrent reaches 270 μ A/cm
2.
Claims (10)
1. quantum dot modifies a ZnO nanorod array electrode, it is characterized in that a kind of quantum dot is modified ZnO nanorod array electrode and comprised substrate, ZnO nano-rod array and quantum dot coating layer;
Wherein, described substrate is conductive substrates, described ZnO nano-rod array is made up of the hexamethylenetetramine of concentration to be the zinc nitrate hexahydrate of 0.08 ~ 0.12M and concentration be 0.08 ~ 0.12M, described zinc nitrate hexahydrate and the volume ratio of hexamethylenetetramine are 1:1, described quantum dot coating layer replaces coated forming by cationic polyelectrolyte-phenanthroline cobalt layers and quantum dot nano-particle layer, described cationic polyelectrolyte-phenanthroline cobalt layers is coated on ZnO nano-rod array, quantum dot nano-particle layer is coated in cationic polyelectrolyte-phenanthroline cobalt layers, wherein, described quantum dot nano-particle layer is CdTe nano-particle layer, CdS nano-particle layer or CdSe nano-particle layer.
2. a kind of quantum dot according to claim 1 modifies ZnO nanorod array electrode, it is characterized in that described conductive substrates is ITO or FTO.
3. a kind of quantum dot according to claim 1 and 2 modifies ZnO nanorod array electrode, it is characterized in that the preparation method of described cationic polyelectrolyte-phenanthroline cobalt layers is as follows: ZnO nano-rod array being immersed in pH is in the cationic polyelectrolyte-phenanthroline cobalt liquor of 6.2 ~ 8.5 after 5 ~ 20min, take out and use deionized water rinsing, dry up, namely complete;
Wherein, described cationic polyelectrolyte-phenanthroline cobalt liquor is made up of the cationic polyelectrolyte of concentration to be the phenanthroline cobalt of 0.5 ~ 2mg/mL and concentration be 0.2 ~ 1mg/mL; Wherein, the cationic polyelectrolyte in described cationic polyelectrolyte-phenanthroline cobalt layers is polymine, polyallylamine hydrochloride or PDDA.
4. a kind of quantum dot according to claim 1 modifies ZnO nanorod array electrode, it is characterized in that the preparation method of described quantum dot nano-particle layer is as follows: to be immersed in by the ZnO nano-rod array of coated cationic polyelectrolyte-phenanthroline cobalt layers in quantum dot nano-particle solution after 5 ~ 20min, take out and use deionized water rinsing, dry up, namely complete;
Wherein, described quantum dot nano-particle solution is CdTe nanoparticles solution, CdS nanoparticles solution or CdSe nanoparticles solution;
Described CdTe nanoparticles solution is prepared by the following method: a, take 0.5 ~ 1.4g six perchloric acid hydrate cadmium and be dissolved in 100 ~ 150mL redistilled water, after adding 0.2 ~ 0.8mL3-mercaptopropionic acid, regulate pH to 9 ~ 11 of solution by the NaOH solution that concentration is 0.5 ~ 2M, obtain solution A; B, in a nitrogen atmosphere, the sulfuric acid solution that 10 ~ 20mL concentration is 0.2 ~ 0.7M is added in 0.1 ~ 0.4g telluride aluminium powder, the gas that reaction produces is imported in solution A, simultaneously by solution A back flow reaction 12 ~ 48h at 80 ~ 150 DEG C, stir with magneton in course of reaction, obtain CdTe nanoparticles solution;
Described CdS nanoparticles solution is prepared by the following method: a, take 0.5 ~ 1.4g six perchloric acid hydrate cadmium and be dissolved in 100 ~ 150mL redistilled water, after adding 0.2 ~ 0.8mL3-mercaptopropionic acid, regulate pH to 9 ~ 11 of solution by the NaOH solution that concentration is 0.5 ~ 2M, obtain solution A; B, in a nitrogen atmosphere, in solution A, add 0.09 ~ 0.25g thioacetamide, simultaneously by solution A back flow reaction 12 ~ 48h at 80 ~ 150 DEG C, stir with magneton in course of reaction, obtain CdS nanoparticles solution;
Described CdSe nanoparticles solution is prepared by the following method: take 0.04 ~ 0.09g six perchloric acid hydrate cadmium and be dissolved in 60 ~ 100mL deionized water, add the natrium citricum of 0.08 ~ 0.13g, then use 0.5 ~ 2M sodium hydroxide solution that pH value is adjusted to 9 ~ 11, logical nitrogen 10min, forms mixed liquor; Taking 0.004 ~ 0.007g selenourea is dissolved in the deionized water of 4mL, adds above-mentioned mixed liquor after ultrasonic mixing, and mixed liquor is ultrasonic 50s in the microwave oven of 900W, obtains CdSe nanoparticles solution.
5. a preparation method for electrode, described electrode is that the quantum dot of claim 1 modifies ZnO nanorod array electrode, it is characterized in that a kind of quantum dot modifies the preparation method of ZnO nanorod array electrode, specifically carries out according to the following steps:
One, hydro thermal method making ZnO nanometer stick array: substrate is immersed in zinc nitrate hexahydrate-hexamethylenetetramine solution, after 70 ~ 95 DEG C of reaction 2.5h ~ 15h, take out substrate, ultrasonic cleaning is carried out successively with deionized water and absolute ethyl alcohol, then anneal 10 ~ 60min at 250 ~ 400 DEG C of temperature, obtains ZnO nano-rod array;
Two, the preparation of CdTe nanoparticles solution: a, take 0.5 ~ 1.4g six perchloric acid hydrate cadmium and be dissolved in 100 ~ 150mL redistilled water, after adding 0.2 ~ 0.8mL3-mercaptopropionic acid, regulate pH to 9 ~ 11 of solution by the NaOH solution that concentration is 0.5 ~ 2M, obtain solution A; B, in a nitrogen atmosphere, the sulfuric acid solution that 10 ~ 20mL concentration is 0.2 ~ 0.7M is added in 0.1 ~ 0.4g telluride aluminium powder, the gas that reaction produces is imported in solution A, simultaneously by solution A back flow reaction 12 ~ 48h at 80 ~ 150 DEG C, stir with magneton in course of reaction, obtain CdTe nanoparticles solution;
Three, the preparation of phenanthroline cobalt: the ratio of 1:3 in molar ratio, takes hydrated cobalt chloride and phenanthroline is put in mortar, at room temperature mixes, grinds more than 2.5h;
Four, to carry out quantum dot coated for LBL self-assembly method: gained ZnO nano-rod array in step one being immersed in pH is in the cationic polyelectrolyte-phenanthroline cobalt liquor of 6.2 ~ 8.5 after 5 ~ 20min, takes out and uses deionized water rinsing, drying up; Then be immersed in 5 ~ 20min in the CdTe nanoparticles solution of step 2 gained, take out and use deionized water rinsing, drying up;
Five, repeat step 4 10 ~ 25 times, namely obtain the ZnO nano-rod array that quantum dot is modified;
Wherein, the substrate described in step one is conductive substrates;
Zinc nitrate hexahydrate described in step one-hexamethylenetetramine solution is be the zinc nitrate hexahydrate of 0.08 ~ 0.12M and concentration by concentration is that the hexamethylenetetramine of 0.08 ~ 0.12M is by volume for the ratio of 1:1 mixes;
Cationic polyelectrolyte described in step 4-phenanthroline cobalt liquor is made up of the cationic polyelectrolyte of concentration to be the phenanthroline cobalt of 0.5 ~ 2mg/mL and concentration be 0.2 ~ 1mg/mL; Wherein, described cationic polyelectrolyte is polymine, polyallylamine hydrochloride or PDDA.
6. a kind of quantum dot according to claim 5 modifies the preparation method of ZnO nanorod array electrode, it is characterized in that the conductive substrates described in step one is ITO or FTO.
7. a preparation method for electrode, described electrode is that the quantum dot of claim 1 modifies ZnO nanorod array electrode, it is characterized in that a kind of quantum dot modifies the preparation method of ZnO nanorod array electrode, specifically carries out according to the following steps:
One, hydro thermal method making ZnO nanometer stick array: substrate is immersed in zinc nitrate hexahydrate-hexamethylenetetramine solution, after 70 ~ 95 DEG C of reaction 2.5h ~ 15h, take out substrate, ultrasonic cleaning is carried out successively with deionized water and absolute ethyl alcohol, then anneal 10 ~ 60min at 250 ~ 400 DEG C of temperature, obtains ZnO nano-rod array;
Two, CdS nanoparticles solution is prepared by the following method: a, take 0.5 ~ 1.4g six perchloric acid hydrate cadmium and be dissolved in 100 ~ 150mL redistilled water, after adding 0.2 ~ 0.8mL3-mercaptopropionic acid, regulate pH to 9 ~ 11 of solution by the NaOH solution that concentration is 0.5 ~ 2M, obtain solution A; B, in a nitrogen atmosphere, in solution A, add 0.09 ~ 0.25g thioacetamide, simultaneously by solution A back flow reaction 12 ~ 48h at 80 ~ 150 DEG C, stir with magneton in course of reaction, obtain CdS nanoparticles solution;
Three, the preparation of phenanthroline cobalt: the ratio of 1:3 in molar ratio, takes hydrated cobalt chloride and phenanthroline is put in mortar, at room temperature mixes, grinds more than 2.5h;
Four, to carry out quantum dot coated for LBL self-assembly method: gained ZnO nano-rod array in step one being immersed in pH is in the cationic polyelectrolyte-phenanthroline cobalt liquor of 6.2 ~ 8.5 after 5 ~ 20min, takes out and uses deionized water rinsing, drying up; Then be immersed in 5 ~ 20min in the CdS nanoparticles solution of step 2 gained, take out and use deionized water rinsing, drying up;
Five, repeat step 4 10 ~ 25 times, namely obtain the ZnO nano-rod array that quantum dot is modified;
Wherein, the substrate described in step one is conductive substrates;
Zinc nitrate hexahydrate described in step one-hexamethylenetetramine solution is be the zinc nitrate hexahydrate of 0.08 ~ 0.12M and concentration by concentration is that the hexamethylenetetramine of 0.08 ~ 0.12M is by volume for the ratio of 1:1 mixes;
Cationic polyelectrolyte described in step 4-phenanthroline cobalt liquor is made up of the cationic polyelectrolyte of concentration to be the phenanthroline cobalt of 0.5 ~ 2mg/mL and concentration be 0.2 ~ 1mg/mL; Wherein, described cationic polyelectrolyte is polymine, polyallylamine hydrochloride or PDDA.
8. a kind of quantum dot according to claim 7 modifies the preparation method of ZnO nanorod array electrode, it is characterized in that the conductive substrates described in step one is ITO or FTO.
9. a preparation method for electrode, described electrode is that the quantum dot of claim 1 modifies ZnO nanorod array electrode, it is characterized in that a kind of quantum dot modifies the preparation method of ZnO nanorod array electrode, specifically carries out according to the following steps:
One, hydro thermal method making ZnO nanometer stick array: substrate is immersed in zinc nitrate hexahydrate-hexamethylenetetramine solution, after 70 ~ 95 DEG C of reaction 2.5h ~ 15h, take out substrate, ultrasonic cleaning is carried out successively with deionized water and absolute ethyl alcohol, then anneal 10 ~ 60min at 250 ~ 400 DEG C of temperature, obtains ZnO nano-rod array;
Two, CdSe nanoparticles solution is prepared by the following method: take 0.04 ~ 0.09g six perchloric acid hydrate cadmium and be dissolved in 60 ~ 100mL deionized water, add the natrium citricum of 0.08 ~ 0.13g, then use 0.5 ~ 2M sodium hydroxide solution that pH value is adjusted to 9 ~ 11, logical nitrogen 10min, forms mixed liquor; Taking 0.004 ~ 0.007g selenourea is dissolved in the deionized water of 4mL, adds above-mentioned mixed liquor after ultrasonic mixing, and mixed liquor is ultrasonic 50s in the microwave oven of 900W, obtains CdSe nanoparticles solution;
Three, the preparation of phenanthroline cobalt: the ratio of 1:3 in molar ratio, takes hydrated cobalt chloride and phenanthroline is put in mortar, at room temperature mixes, grinds more than 2.5h;
Four, to carry out quantum dot coated for LBL self-assembly method: gained ZnO nano-rod array in step one being immersed in pH is in the cationic polyelectrolyte-phenanthroline cobalt liquor of 6.2 ~ 8.5 after 5 ~ 20min, takes out and uses deionized water rinsing, drying up; Then be immersed in 5 ~ 20min in the CdSe nanoparticles solution of step 2 gained, take out and use deionized water rinsing, drying up;
Five, repeat step 4 10 ~ 25 times, namely obtain the ZnO nano-rod array that quantum dot is modified;
Wherein, the substrate described in step one is conductive substrates;
Zinc nitrate hexahydrate described in step one-hexamethylenetetramine solution is be the zinc nitrate hexahydrate of 0.08 ~ 0.12M and concentration by concentration is that the hexamethylenetetramine of 0.08 ~ 0.12M is by volume for the ratio of 1:1 mixes;
Cationic polyelectrolyte described in step 4-phenanthroline cobalt liquor is made up of the cationic polyelectrolyte of concentration to be the phenanthroline cobalt of 0.5 ~ 2mg/mL and concentration be 0.2 ~ 1mg/mL; Wherein, described cationic polyelectrolyte is polymine, polyallylamine hydrochloride or PDDA.
10. a kind of quantum dot according to claim 9 modifies the preparation method of ZnO nanorod array electrode, it is characterized in that the conductive substrates described in step one is ITO or FTO.
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