CN103400699A - Quantum dot-modified ZnO nanorod array electrode and preparation method thereof - Google Patents
Quantum dot-modified ZnO nanorod array electrode and preparation method thereof Download PDFInfo
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- CN103400699A CN103400699A CN2013103372482A CN201310337248A CN103400699A CN 103400699 A CN103400699 A CN 103400699A CN 2013103372482 A CN2013103372482 A CN 2013103372482A CN 201310337248 A CN201310337248 A CN 201310337248A CN 103400699 A CN103400699 A CN 103400699A
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Abstract
The invention relates to a quantum dot-modified ZnO nanorod array electrode and a preparation method thereof, and relates to an array electrode and a preparation method thereof. With the adoption of the quantum dot-modified ZnO nanorod array electrode and the preparation method thereof, the technical problems that the photocatalytic efficiency of ZnO nano materials is low under visible light, and the utilization rate of the sunlight is low are solved. The preparation method comprises the following steps: 1, taking conductive glass as a substrate, and preparing a highly ordered ZnO nanorod array by adopting a hydrothermal method; and 2, alternately depositing polyelectrolyte and quantum dot particles on the surface of the ZnO nanorod array, so as to obtain the uniform coated quantum dot-modified ZnO nanorod array electrode. With the adoption of the method for preparing photoelectrodes, the length of the ZnO nanorod array and the thickness of the coated quantum dot can be controlled; and the electrode prepared by the method provided by the invention exhibits good photoelectrocatalytic activity and visible-light response characteristics under irradiation of the visible light. The quantum dot-modified ZnO nanorod array electrode and the preparation method thereof are used in the fields of photoelectrocatalytic degradation of environmental pollutants, photoelectrocatalytic synthesis and water photolysis for hydrogen generation.
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 good piezoelectricity, thermoelectricity, photoelectric characteristic, the application in the fields such as ZnO nanorod emission on the scene, gas sensor, solar cell, field-effect transistor and el light emitting device has caused that people study interest widely.
Because ZnO nano material can only absorb and scatters ultraviolet, and ultraviolet ray has only accounted for 5-6% in sunlight, thus cause based on the photocatalysis efficiency of the photovoltaic device of ZnO nano material lower, low to the utilance of sunlight.
Self-assembling method (Layer-by-Layer Self-assembly layer by layer, LbL) method claims again the ion self assembly, and it refers to dress up superstructure with ion, supermolecule, biomolecule, nano particle or the nano particle compound of negative (just) electric charge of band by the electrostatic attraction alternate group with the nano particle of just (bearing) electric charge or nano particle compound.In assembling process, what the most often use is the polyelectrolyte (PE) and alternately assembling of nano material with plus or minus electric charge.
Summary of the invention
The objective of the invention is for solve ZnO nano material photocatalysis efficiency under visible light lower, for the low technical problem of the utilance of sunlight, and a kind of quantum dot that provides is modified ZnO nano-rod array electrode and preparation method thereof.
a kind of quantum dot of the present invention is modified the ZnO nano-rod 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 to be that the zinc nitrate hexahydrate of 0.08～0.12M and hexamethylenetetramine that concentration is 0.08～0.12M are made by concentration, the volume ratio of described zinc nitrate hexahydrate and hexamethylenetetramine is 1:1, described quantum dot coating layer is alternately coated and forms by cationic polyelectrolyte-phenanthroline cobalt layer and quantum dot nano-particle layer, described cationic polyelectrolyte-phenanthroline cobalt layer is coated on ZnO nano-rod array, the quantum dot nano-particle layer is coated on cationic polyelectrolyte-phenanthroline cobalt layer, wherein, described quantum dot nano-particle layer is the 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 is modified the ZnO nano-rod 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 ℃ of reaction 2.5h～15h, take out substrate, carry out ultrasonic cleaning with deionized water and absolute ethyl alcohol successively, then 10～the 60min that anneals at 250～400 ℃ of temperature, obtain ZnO nano-rod array;
Two, the preparation of CdTe nanoparticles solution: a, take 0.5～1.4g, six perchloric acid hydrate cadmiums and be dissolved in 100～150mL redistilled water, after adding 0.2～0.8mL3-mercaptopropionic acid, be the pH to 9～11 of the NaOH solution regulator solution of 0.5～2M with concentration, obtain solution A; B, under nitrogen atmosphere, be the sulfuric acid solution of 0.2～0.7M to adding 10～20mL concentration in 0.1～0.4g tellurium aluminium powder, the gas that reaction is produced imports in solution A, simultaneously with solution A at 80～150 ℃ of lower back flow reaction 12～48h, stir with magneton in course of reaction, obtain the CdTe nanoparticles solution;
Three, the preparation of phenanthroline cobalt: the ratio of 1:3 in molar ratio takes hydrated cobalt chloride and phenanthroline and is put in mortar, more than at room temperature mixing, grinding 2.5h;
Four, self-assembling method carries out quantum dot and coats layer by layer: it is in 6.2～8.5 cationic polyelectrolyte-phenanthroline cobalt liquor after 5～20min that gained ZnO nano-rod array in step 1 is immersed in pH, takes out and use deionized water rinsing, dries up; Then it is immersed in 5～20min in the CdTe nanoparticles solution of step 2 gained, takes out and use deionized water rinsing, dry up;
Five, repeating step is 4 10～25 times, namely obtains the ZnO nano-rod array that quantum dot is modified;
Wherein, the described substrate of step 1 is conductive substrates;
Zinc nitrate hexahydrate described in step 1-hexamethylenetetramine solution is to be that the zinc nitrate hexahydrate of 0.08～0.12M and hexamethylenetetramine that concentration is 0.08～0.12M mix for the ratio of 1:1 by volume by concentration;
Cationic polyelectrolyte described in step 4-phenanthroline cobalt liquor is that the phenanthroline cobalt of 0.5～2mg/mL and cationic polyelectrolyte that concentration is 0.2～1mg/mL form by concentration; Wherein, described cationic polyelectrolyte is polymine, polypropylene amine hydrochloride or PDDA.
The preparation method that a kind of quantum dot of the present invention is modified the ZnO nano-rod 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 ℃ of reaction 2.5h～15h, take out substrate, carry out ultrasonic cleaning with deionized water and absolute ethyl alcohol successively, then 10～the 60min that anneals at 250～400 ℃ of temperature, obtain ZnO nano-rod array;
Two, the CdS nanoparticles solution prepares by the following method: a, take 0.5～1.4g, six perchloric acid hydrate cadmiums and be dissolved in 100～150mL redistilled water, after adding 0.2～0.8mL3-mercaptopropionic acid, be the pH to 9～11 of the NaOH solution regulator solution of 0.5～2M with concentration, obtain solution A; B, under nitrogen atmosphere, add 0.09～0.25g thioacetamide in solution A, simultaneously with solution A at 80～150 ℃ of lower back flow reaction 12～48h, stir with magneton in course of reaction, obtain the CdS nanoparticles solution;
Three, the preparation of phenanthroline cobalt: the ratio of 1:3 in molar ratio takes hydrated cobalt chloride and phenanthroline and is put in mortar, more than at room temperature mixing, grinding 2.5h;
Four, self-assembling method carries out quantum dot and coats layer by layer: it is in 6.2～8.5 cationic polyelectrolyte-phenanthroline cobalt liquor after 5～20min that gained ZnO nano-rod array in step 1 is immersed in pH, takes out and use deionized water rinsing, dries up; Then it is immersed in 5～20min in the CdS nanoparticles solution of step 2 gained, takes out and use deionized water rinsing, dry up;
Five, repeating step is 4 10～25 times, namely obtains the ZnO nano-rod array that quantum dot is modified;
Wherein, the described substrate of step 1 is conductive substrates;
Zinc nitrate hexahydrate described in step 1-hexamethylenetetramine solution is to be that the zinc nitrate hexahydrate of 0.08～0.12M and hexamethylenetetramine that concentration is 0.08～0.12M mix for the ratio of 1:1 by volume by concentration;
Cationic polyelectrolyte described in step 4-phenanthroline cobalt liquor is that the phenanthroline cobalt of 0.5～2mg/mL and cationic polyelectrolyte that concentration is 0.2～1mg/mL form by concentration; Wherein, described cationic polyelectrolyte is polymine, polypropylene amine hydrochloride or PDDA.
The preparation method that a kind of quantum dot of the present invention is modified the ZnO nano-rod 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 ℃ of reaction 2.5h～15h, take out substrate, carry out ultrasonic cleaning with deionized water and absolute ethyl alcohol successively, then 10～the 60min that anneals at 250～400 ℃ of temperature, obtain ZnO nano-rod array;
Two, the CdSe nanoparticles solution prepares by the following method: take 0.04～0.09g, six perchloric acid hydrate cadmiums and be dissolved in 60～100mL deionized water, the natrium citricum that adds 0.08～0.13g, then use 0.5～2M sodium hydroxide solution that the pH value is transferred to 9～11, logical nitrogen 10min; Take in the deionized water that 0.004～0.007g selenourea is dissolved in 4mL, add above-mentioned mixed liquor after ultrasonic mixing, mixed liquor is ultrasonic 50s in the microwave oven of 900W, obtains the CdSe nanoparticles solution;
Three, the preparation of phenanthroline cobalt: the ratio of 1:3 in molar ratio takes hydrated cobalt chloride and phenanthroline and is put in mortar, more than at room temperature mixing, grinding 2.5h;
Four, self-assembling method carries out quantum dot and coats layer by layer: it is in 6.2～8.5 cationic polyelectrolyte-phenanthroline cobalt liquor after 5～20min that gained ZnO nano-rod array in step 1 is immersed in pH, takes out and use deionized water rinsing, dries up; Then it is immersed in 5～20min in the CdSe nanoparticles solution of step 2 gained, takes out and use deionized water rinsing, dry up;
Five, repeating step is 4 10～25 times, namely obtains the ZnO nano-rod array that quantum dot is modified;
Wherein, the described substrate of step 1 is conductive substrates;
Zinc nitrate hexahydrate described in step 1-hexamethylenetetramine solution is to be that the zinc nitrate hexahydrate of 0.08～0.12M and hexamethylenetetramine that concentration is 0.08～0.12M mix for the ratio of 1:1 by volume by concentration;
Cationic polyelectrolyte described in step 4-phenanthroline cobalt liquor is that the phenanthroline cobalt of 0.5～2mg/mL and cationic polyelectrolyte that concentration is 0.2～1mg/mL form by concentration; Wherein, described cationic polyelectrolyte is polymine, polypropylene amine hydrochloride or PDDA.
The present invention has following beneficial effect:
1, the preparation method of a kind of quantum dot modification ZnO nano-rod array electrode of the present invention,, by regulating the number of plies that coats layer by layer, can effectively control the thickness of CdTe shell.
2, the quantum dot of the present invention's preparation is modified ZnO nano-rod array in the significant enhancing of being absorbed with of visible light wave range, and under the solar source irradiation by the xenon lamp simulation, obvious photoelectric respone being arranged, current-time curvel shows that it has higher photocurrent response speed and good reappearance.
3, the specific activity of quantum dot modification ZnO nano-rod array electrode photoelectrocatalysis phenol under visible light of the present invention's preparation is higher, with the phenol removing situation of ZnO nano-rod array electrode under similarity condition, compares and has improved more than 35%.Simultaneously, compare with simple photocatalysis phenol, the intermediate product that the quantum dot of the present invention's preparation is modified ZnO nano-rod array electrode photoelectrocatalysis phenol under visible light is mainly the materials such as biodegradable glycerine, small molecular organic acid, and catalytic process is more efficient and thorough.Process from the CdTe conduction band to the ZnO conduction band that inject electronics from can suppress the compound of electron hole pair.Therefore, coating CdTe on ZnO nano-rod array will increase the light sensitivity of ZnO for visible light, can effectively utilize in solar radiation the visible light that accounts for the overwhelming majority, thereby improves the photocatalysis efficiency of ZnO.Electric field is auxiliary can further suppress the compound of electron hole pair, so the auxiliary lower photoelectric catalysis degrading process of electric field is more efficient and thorough.
4, to modify the preparation method of ZnO nano-rod array electrode be 10 hours at growth time to a kind of quantum dot of the present invention, coat the number of plies is under the condition of 20 bilayers, and the photoelectric properties of the ZnO/CdTe nano composite structure of acquisition are best.
Description of drawings
Fig. 1 is ZnO nano-rod array in embodiment 1 and the ultraviolet-visible absorption spectroscopy figure of ZnO/CdTe nano composite structure; In figure, 1 is the ZnO/CdTe nano composite structure, and 2 is ZnO nano-rod array, and 3 is the MPA-CdTe quantum dot;
Fig. 2 is the SEM vertical view of the ZnO nano-rod array of growing in the 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 light according under phenol concentration and the degradation time graph of a relation of photoelectrocatalysis phenol; In figure, 1 is ZnO nano-rod array, and 2 is the 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 the ZnO nano-rod 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 to be that the zinc nitrate hexahydrate of 0.08～0.12M and hexamethylenetetramine that concentration is 0.08～0.12M are made by concentration, the volume ratio of described zinc nitrate hexahydrate and hexamethylenetetramine is 1:1, described quantum dot coating layer is alternately coated and forms by cationic polyelectrolyte-phenanthroline cobalt layer and quantum dot nano-particle layer, described cationic polyelectrolyte-phenanthroline cobalt layer is coated on ZnO nano-rod array, the quantum dot nano-particle layer is coated on cationic polyelectrolyte-phenanthroline cobalt layer, wherein, described quantum dot nano-particle layer is the CdTe nano-particle layer, CdS nano-particle layer or CdSe nano-particle layer.
The described quantum dot of present embodiment is modified the ZnO nano-rod array electrode significantly to be increased in the absorption of visible light wave range.
Embodiment two: what present embodiment was different from embodiment one is: described conductive substrates is ITO or FTO.Other is identical with embodiment one.
Embodiment three: what present embodiment was different from embodiment one or two is: the preparation method of described cationic polyelectrolyte-phenanthroline cobalt layer is as follows: it is in 6.2～8.5 cationic polyelectrolyte-phenanthroline cobalt liquor after 5～20min that ZnO nano-rod array is immersed in pH, take out and use deionized water rinsing, dry up, namely complete;
Wherein, described cationic polyelectrolyte-phenanthroline cobalt liquor is that the phenanthroline cobalt of 0.5～2mg/mL and cationic polyelectrolyte that concentration is 0.2～1mg/mL form by concentration; Wherein, the cationic polyelectrolyte in described cationic polyelectrolyte-phenanthroline cobalt layer is polymine, polypropylene amine hydrochloride or PDDA.Other is identical with embodiment one or two.
Embodiment four: what present embodiment was different from one of embodiment one to three is: the preparation method of described quantum dot nano-particle layer is as follows: the ZnO nano-rod array that will coat cationic polyelectrolyte-phenanthroline cobalt layer is immersed 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 prepares by the following method: a, take 0.5～1.4g, six perchloric acid hydrate cadmiums and be dissolved in 100～150mL redistilled water, after adding 0.2～0.8mL3-mercaptopropionic acid, be the pH to 9～11 of the NaOH solution regulator solution of 0.5～2M with concentration, obtain solution A; B, under nitrogen atmosphere, be the sulfuric acid solution of 0.2～0.7M to adding 10～20mL concentration in 0.1～0.4g tellurium aluminium powder, the gas that reaction is produced imports in solution A, simultaneously with solution A at 80～150 ℃ of lower back flow reaction 12～48h, stir with magneton in course of reaction, obtain the CdTe nanoparticles solution;
Described CdS nanoparticles solution prepares by the following method: a, take 0.5～1.4g, six perchloric acid hydrate cadmiums and be dissolved in 100～150mL redistilled water, after adding 0.2～0.8mL3-mercaptopropionic acid, be the pH to 9～11 of the NaOH solution regulator solution of 0.5～2M with concentration, obtain solution A; B, under nitrogen atmosphere, add 0.09～0.25g thioacetamide in solution A, simultaneously with solution A at 80～150 ℃ of lower back flow reaction 12～48h, stir with magneton in course of reaction, obtain the CdS nanoparticles solution;
Described CdSe nanoparticles solution prepares by the following method: take 0.04～0.09g, six perchloric acid hydrate cadmiums and be dissolved in 60～100mL deionized water, the natrium citricum that adds 0.08～0.13g, then use 0.5～2M sodium hydroxide solution that the pH value is transferred to 9～11, logical nitrogen 10min; Take in the deionized water that 0.004～0.007g selenourea is dissolved in 4mL, add above-mentioned mixed liquor after ultrasonic mixing, mixed liquor is ultrasonic 50s in the microwave oven of 900W, obtains the CdSe nanoparticles solution.Other is identical with one of embodiment one to three.
Embodiment five: the preparation method that a kind of quantum dot of present embodiment is modified the ZnO nano-rod 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 ℃ of reaction 2.5h～15h, take out substrate, carry out ultrasonic cleaning with deionized water and absolute ethyl alcohol successively, then 10～the 60min that anneals at 250～400 ℃ of temperature, obtain ZnO nano-rod array;
Two, the preparation of CdTe nanoparticles solution: a, take 0.5～1.4g, six perchloric acid hydrate cadmiums and be dissolved in 100～150mL redistilled water, after adding 0.2～0.8mL3-mercaptopropionic acid, be the pH to 9～11 of the NaOH solution regulator solution of 0.5～2M with concentration, obtain solution A; B, under nitrogen atmosphere, be the sulfuric acid solution of 0.2～0.7M to adding 10～20mL concentration in 0.1～0.4g tellurium aluminium powder, the gas that reaction is produced imports in solution A, simultaneously with solution A at 80～150 ℃ of lower back flow reaction 12～48h, stir with magneton in course of reaction, obtain the CdTe nanoparticles solution;
Three, the preparation of phenanthroline cobalt: the ratio of 1:3 in molar ratio takes hydrated cobalt chloride and phenanthroline and is put in mortar, more than at room temperature mixing, grinding 2.5h;
Four, self-assembling method carries out quantum dot and coats layer by layer: it is in 6.2～8.5 cationic polyelectrolyte-phenanthroline cobalt liquor after 5～20min that gained ZnO nano-rod array in step 1 is immersed in pH, takes out and use deionized water rinsing, dries up; Then it is immersed in 5～20min in the CdTe nanoparticles solution of step 2 gained, takes out and use deionized water rinsing, dry up;
Five, repeating step is 4 10～25 times, namely obtains the ZnO nano-rod array that quantum dot is modified;
Wherein, the described substrate of step 1 is conductive substrates;
Zinc nitrate hexahydrate described in step 1-hexamethylenetetramine solution is to be that the zinc nitrate hexahydrate of 0.08～0.12M and hexamethylenetetramine that concentration is 0.08～0.12M mix for the ratio of 1:1 by volume by concentration;
Cationic polyelectrolyte described in step 4-phenanthroline cobalt liquor is that the phenanthroline cobalt of 0.5～2mg/mL and cationic polyelectrolyte that concentration is 0.2～1mg/mL form by concentration; Wherein, described cationic polyelectrolyte is polymine, polypropylene amine hydrochloride or PDDA.
, at 250～400 ℃ of annealing 10～60min, be in order to strengthen the conductivity of ZnO nanorod in the described step 1 of present embodiment.
Different reflux time in the described step 2 of present embodiment, can obtain the stable CdTe nano particle of MPA of different-grain diameter.
The preparation method that the described a kind of quantum dot of present embodiment is modified the ZnO nano-rod array electrode, preparation technology is simple, can prepare on a large scale, the material for preparing is evenly distributed in substrate, the efficiency of photoelectrocatalysis phenol is higher more than 35% than the catalytic efficiency of the ZnO optoelectronic pole of not modifying quantum dot under visible light.
Embodiment six: what present embodiment was different from embodiment five is: the conductive substrates described in step 1 is ITO or FTO.Other is identical with embodiment five.
Embodiment seven: what present embodiment was different from embodiment five is: in the ZnO nano-rod array described in step 1, the length of ZnO nanorod is 1～8 μ m.Other is identical with embodiment five.
Embodiment eight: what present embodiment was different from embodiment five is: taking six perchloric acid hydrate cadmium quality described in step 2 is 0.5～1.4g.Other is identical with embodiment five.
Embodiment nine: what present embodiment was different from embodiment five is: adding 3-mercaptopropionic acid volume described in step 2 is 0.2～0.5mL.Other is identical with embodiment five.
Embodiment ten: what present embodiment was different from embodiment five is: the quality that adds the tellurium aluminium powder described in step 2 is 0.1～0.3g.Other is identical with embodiment five.
Embodiment 11: the preparation method that a kind of quantum dot of present embodiment is modified the ZnO nano-rod 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 ℃ of reaction 2.5h～15h, take out substrate, carry out ultrasonic cleaning with deionized water and absolute ethyl alcohol successively, then 10～the 60min that anneals at 250～400 ℃ of temperature, obtain ZnO nano-rod array;
Two, the CdS nanoparticles solution prepares by the following method: a, take 0.5～1.4g, six perchloric acid hydrate cadmiums and be dissolved in 100～150mL redistilled water, after adding 0.2～0.8mL3-mercaptopropionic acid, be the pH to 9～11 of the NaOH solution regulator solution of 0.5～2M with concentration, obtain solution A; B, under nitrogen atmosphere, add 0.09～0.25g thioacetamide in solution A, simultaneously with solution A at 80～150 ℃ of lower back flow reaction 12～48h, stir with magneton in course of reaction, obtain the CdS nanoparticles solution;
Three, the preparation of phenanthroline cobalt: the ratio of 1:3 in molar ratio takes hydrated cobalt chloride and phenanthroline and is put in mortar, more than at room temperature mixing, grinding 2.5h;
Four, self-assembling method carries out quantum dot and coats layer by layer: it is in 6.2～8.5 cationic polyelectrolyte-phenanthroline cobalt liquor after 5～20min that gained ZnO nano-rod array in step 1 is immersed in pH, takes out and use deionized water rinsing, dries up; Then it is immersed in 5～20min in the CdS nanoparticles solution of step 2 gained, takes out and use deionized water rinsing, dry up;
Five, repeating step is 4 10～25 times, namely obtains the ZnO nano-rod array that quantum dot is modified;
Wherein, the described substrate of step 1 is conductive substrates;
Zinc nitrate hexahydrate described in step 1-hexamethylenetetramine solution is to be that the zinc nitrate hexahydrate of 0.08～0.12M and hexamethylenetetramine that concentration is 0.08～0.12M mix for the ratio of 1:1 by volume by concentration;
Cationic polyelectrolyte described in step 4-phenanthroline cobalt liquor is that the phenanthroline cobalt of 0.5～2mg/mL and cationic polyelectrolyte that concentration is 0.2～1mg/mL form by concentration; Wherein, described cationic polyelectrolyte is polymine, polypropylene amine hydrochloride or PDDA.
, at 250～400 ℃ of annealing 10～60min, be in order to strengthen the conductivity of ZnO nanorod in the described step 1 of present embodiment.
Different reflux time in the described step 2 of present embodiment, can obtain the stable CdS nano particle of MPA of different-grain diameter.
The preparation method that the described a kind of quantum dot of present embodiment is modified the ZnO nano-rod array electrode, preparation technology is simple, can prepare on a large scale, the material for preparing is evenly distributed in substrate, the efficiency of photoelectrocatalysis phenol is higher more than 35% than the catalytic efficiency of the ZnO optoelectronic pole of not modifying quantum dot under visible light.
Embodiment 12: what present embodiment was different from embodiment 11 is: the conductive substrates described in step 1 is ITO or FTO.Other is identical with embodiment 11.
Embodiment 13: what present embodiment was different from embodiment 11 is: in the ZnO nano-rod array described in step 1, the length of ZnO nanorod is 1～8 μ m.Other is identical with embodiment 11.
Embodiment 14: what present embodiment was different from embodiment 11 is: taking six perchloric acid hydrate cadmium quality described in step 2 is 0.5～1.4g.Other is identical with embodiment 11.
Embodiment 15: what present embodiment was different from embodiment 11 is: adding 3-mercaptopropionic acid volume described in step 2 is 0.2～0.5mL.Other is identical with embodiment 11.
Embodiment 16: what present embodiment was different from embodiment 11 is: the quality that adds thioacetamide described in step 2 is 0.09～0.25g.Other is identical with embodiment 11.
Embodiment 17: the preparation method that a kind of quantum dot of present embodiment is modified the ZnO nano-rod 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 ℃ of reaction 2.5h～15h, take out substrate, carry out ultrasonic cleaning with deionized water and absolute ethyl alcohol successively, then 10～the 60min that anneals at 250～400 ℃ of temperature, obtain ZnO nano-rod array;
Two, the CdSe nanoparticles solution prepares by the following method: take 0.04～0.09g, six perchloric acid hydrate cadmiums and be dissolved in 60～100mL deionized water, the natrium citricum that adds 0.08～0.13g, then use 0.5～2M sodium hydroxide solution that the pH value is transferred to 9～11, logical nitrogen 10min; Take in the deionized water that 0.004～0.007g selenourea is dissolved in 4mL, add above-mentioned mixed liquor after ultrasonic mixing, mixed liquor is ultrasonic 50s in the microwave oven of 900W, obtains the CdSe nanoparticles solution;
Three, the preparation of phenanthroline cobalt: the ratio of 1:3 in molar ratio takes hydrated cobalt chloride and phenanthroline and is put in mortar, more than at room temperature mixing, grinding 2.5h;
Four, self-assembling method carries out quantum dot and coats layer by layer: it is in 6.2～8.5 cationic polyelectrolyte-phenanthroline cobalt liquor after 5～20min that gained ZnO nano-rod array in step 1 is immersed in pH, takes out and use deionized water rinsing, dries up; Then it is immersed in 5～20min in the CdSe nanoparticles solution of step 2 gained, takes out and use deionized water rinsing, dry up;
Five, repeating step is 4 10～25 times, namely obtains the ZnO nano-rod array that quantum dot is modified;
Wherein, the described substrate of step 1 is conductive substrates;
Zinc nitrate hexahydrate described in step 1-hexamethylenetetramine solution is to be that the zinc nitrate hexahydrate of 0.08～0.12M and hexamethylenetetramine that concentration is 0.08～0.12M mix for the ratio of 1:1 by volume by concentration;
Cationic polyelectrolyte described in step 4-phenanthroline cobalt liquor is that the phenanthroline cobalt of 0.5～2mg/mL and cationic polyelectrolyte that concentration is 0.2～1mg/mL form by concentration; Wherein, described cationic polyelectrolyte is polymine, polypropylene amine hydrochloride or PDDA.
, at 250～400 ℃ of annealing 10～60min, be in order to strengthen the conductivity of ZnO nanorod in the described step 1 of present embodiment.
The preparation method that the described a kind of quantum dot of present embodiment is modified the ZnO nano-rod array electrode, preparation technology is simple, can prepare on a large scale, the material for preparing is evenly distributed in substrate, the efficiency of photoelectrocatalysis phenol is higher more than 35% than the catalytic efficiency of the ZnO optoelectronic pole of not modifying quantum dot under visible light.
Embodiment 18: what present embodiment was different from embodiment 17 is: the conductive substrates described in step 1 is ITO or FTO.Other is identical with embodiment 17.
Embodiment 19: what present embodiment was different from embodiment 17 is: in the ZnO nano-rod array described in step 1, the length of ZnO nanorod is 1～8 μ m.Other is identical with embodiment 17.
Embodiment 20: what present embodiment was different from embodiment 17 is: taking six perchloric acid hydrate cadmium quality described in step 2 is 0.04～0.09g.Other is identical with embodiment 17.
Embodiment 21: what present embodiment was different from embodiment 17 is: adding the natrium citricum quality described in step 2 is 0.08～0.13g.Other is identical with embodiment 17.
Embodiment 22: what present embodiment was different from embodiment 17 is: the quality that adds selenourea described in step 2 is 0.004～0.007g.Other is identical with embodiment 17.
Adopt following examples and contrast experiment to verify beneficial effect of the present invention:
Embodiment one:
The preparation method that a kind of quantum dot of the present embodiment is modified the ZnO nano-rod array electrode specifically prepares according to following steps:
One, hydro thermal method making ZnO nanometer stick array: ITO, as substrate, is immersed in zinc nitrate hexahydrate-hexamethylenetetramine solution, and after 90 ℃ of reaction 10h, obtaining length is the ZnO nanorod of 5 μ m left and right; Take out substrate, carry out ultrasonic cleaning with deionized water and absolute ethyl alcohol successively, then, at 300 ℃ of annealing 30min, obtain ZnO nano-rod array;
Two, the preparation of CdTe nanoparticles solution: taking 0.986g six perchloric acid hydrate cadmiums and be dissolved in the 125mL redistilled water, add the 0.43ml3-mercaptopropionic acid, is then the pH to 11.2 of the NaOH solution regulator solution of 2M with concentration, obtains solution A; B, under nitrogen atmosphere, be the sulfuric acid solution of 0.5M to adding 15mL concentration in 0.2g tellurium aluminium powder, the gas that reaction is produced imports in solution A, simultaneously with solution A at 105 ℃ of lower back flow reaction 24h, stir with magneton in the back flow reaction process, obtain the CdTe nanoparticles solution;
Three, the preparation of phenanthroline cobalt: the ratio of 1:3 in molar ratio, take hydrated cobalt chloride and phenanthroline and be put in mortar, at room temperature mix, grind 2.5h.
Four, self-assembling method carries out quantum dot and coats layer by layer: it is in 7.2 aziridine-phenanthroline cobalt liquor after 10min that gained ZnO nano-rod array in step 1 is immersed in pH, takes out and use deionized water rinsing, dries up; Then it is immersed in 10min in the CdTe nanoparticles solution of step 2 gained, takes out and use deionized water rinsing, dry up;
Five, repeating step is 4 20 times, namely obtains the ZnO nano-rod array that quantum dot is modified;
Wherein, the zinc nitrate hexahydrate described in step 1-hexamethylenetetramine solution is to be that the zinc nitrate hexahydrate of 0.1M and hexamethylenetetramine that concentration is 0.1M mix for the ratio of 1:1 by volume by concentration;
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.
The ZnO nano-rod array for preparing in the present embodiment step 1 as shown in Figure 2, the ZnO nano-rod array of preparing as shown in Figure 2 is equably perpendicular to substrate surface, have hexagon looks more clearly, illustrate by hydro thermal method and prepare and have higher orientation, the ZnO nanorod of high crystalline quality.
The nanometer rods barred body of the ZnO/CdTe nano composite structure after the coating for preparing in the present embodiment step 4 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 UV, visible light absorbent properties of ZnO/CdTe composite construction, at first the ZnO nano-rod array of preparation and the UV, visible light absorption characteristic of CdTe nano particle are studied.As shown in Figure 1, cadmium telluride quantum dot has absorption very by force to the ultraviolet-visible absorption spectroscopy of synthetic cadmium telluride quantum dot at 545nm place, visual field as can be known.Studied subsequently the UV, visible light absorption characteristic of ZnO sample before and after cadmium telluride nano particles coats.Surface deposition the UV, visible light absorption intensity of ZnO/CdTe composite construction of 20 layers of cadmium telluride nano particles obvious enhancing is arranged, and an obvious absworption peak is arranged at the 551nm place, the ultraviolet and visible absorption peak position of the cadmium telluride nano particles of measuring therewith is close, the proof cadmium telluride quantum dot deposits to the ZnO nano-rod array surface, and the ZnO/CdTe composite construction is compared obvious enhancing in the absorption of visible light wave range with ZnO nano-rod array.
Use the 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, the specific activity that shows ZnO/CdTe nano composite structure photoelectrocatalysis phenol under visible light is higher, clearance rate for phenol reached 75% after 2.5 hours, with the phenol removing situation of ZnO nano-rod array electrode under similarity condition, compare and improved 35%.
ZnO nano-rod array and the different photoelectric properties that coat the ZnO/CdTe nano composite structure of the CdTe number of plies by more different growth times, find that growth time is 10 hours, to coat the number of plies be that the photoelectric properties of ZnO/CdTe nano composite structure of 20 bilayers are best, its density of photocurrent reaches 270 μ A/cm
2
Claims (10)
1. a quantum dot is modified the ZnO nano-rod array electrode, it is characterized in that a kind of quantum dot modification ZnO nano-rod array electrode comprises substrate, ZnO nano-rod array and quantum dot coating layer;
wherein, described substrate is conductive substrates, described ZnO nano-rod array is to be that the zinc nitrate hexahydrate of 0.08～0.12M and hexamethylenetetramine that concentration is 0.08～0.12M are made by concentration, the volume ratio of described zinc nitrate hexahydrate and hexamethylenetetramine is 1:1, described quantum dot coating layer is alternately coated and forms by cationic polyelectrolyte-phenanthroline cobalt layer and quantum dot nano-particle layer, described cationic polyelectrolyte-phenanthroline cobalt layer is coated on ZnO nano-rod array, the quantum dot nano-particle layer is coated on cationic polyelectrolyte-phenanthroline cobalt layer, wherein, described quantum dot nano-particle layer is the CdTe nano-particle layer, CdS nano-particle layer or CdSe nano-particle layer.
2. a kind of quantum dot according to claim 1 is modified the ZnO nano-rod 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 is modified the ZnO nano-rod array electrode, the preparation method who it is characterized in that described cationic polyelectrolyte-phenanthroline cobalt layer is as follows: it is in 6.2～8.5 cationic polyelectrolyte-phenanthroline cobalt liquor after 5～20min that ZnO nano-rod array is immersed in pH, take out and use deionized water rinsing, dry up, namely complete;
Wherein, described cationic polyelectrolyte-phenanthroline cobalt liquor is that the phenanthroline cobalt of 0.5～2mg/mL and cationic polyelectrolyte that concentration is 0.2～1mg/mL form by concentration; Wherein, the cationic polyelectrolyte in described cationic polyelectrolyte-phenanthroline cobalt layer is polymine, polypropylene amine hydrochloride or PDDA.
4. a kind of quantum dot according to claim 1 is modified the ZnO nano-rod array electrode, the preparation method who it is characterized in that described quantum dot nano-particle layer is as follows: the ZnO nano-rod array that will coat cationic polyelectrolyte-phenanthroline cobalt layer is immersed 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 prepares by the following method: a, take 0.5～1.4g, six perchloric acid hydrate cadmiums and be dissolved in 100～150mL redistilled water, after adding 0.2～0.8mL3-mercaptopropionic acid, be the pH to 9～11 of the NaOH solution regulator solution of 0.5～2M with concentration, obtain solution A; B, under nitrogen atmosphere, be the sulfuric acid solution of 0.2～0.7M to adding 10～20mL concentration in 0.1～0.4g tellurium aluminium powder, the gas that reaction is produced imports in solution A, simultaneously with solution A at 80～150 ℃ of lower back flow reaction 12～48h, stir with magneton in course of reaction, obtain the CdTe nanoparticles solution;
Described CdS nanoparticles solution prepares by the following method: a, take 0.5～1.4g, six perchloric acid hydrate cadmiums and be dissolved in 100～150mL redistilled water, after adding 0.2～0.8mL3-mercaptopropionic acid, be the pH to 9～11 of the NaOH solution regulator solution of 0.5～2M with concentration, obtain solution A; B, under nitrogen atmosphere, add 0.09～0.25g thioacetamide in solution A, simultaneously with solution A at 80～150 ℃ of lower back flow reaction 12～48h, stir with magneton in course of reaction, obtain the CdS nanoparticles solution;
Described CdSe nanoparticles solution prepares by the following method: take 0.04～0.09g, six perchloric acid hydrate cadmiums and be dissolved in 60～100mL deionized water, the natrium citricum that adds 0.08～0.13g, then use 0.5～2M sodium hydroxide solution that the pH value is transferred to 9～11, logical nitrogen 10min; Take in the deionized water that 0.004～0.007g selenourea is dissolved in 4mL, add above-mentioned mixed liquor after ultrasonic mixing, mixed liquor is ultrasonic 50s in the microwave oven of 900W, obtains the CdSe nanoparticles solution.
5. prepare the method that a kind of quantum dot claimed in claim 1 is modified the ZnO nano-rod array electrode, it is characterized in that a kind of preparation method of quantum dot modification ZnO nano-rod array electrode, specifically carry 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 ℃ of reaction 2.5h～15h, take out substrate, carry out ultrasonic cleaning with deionized water and absolute ethyl alcohol successively, then 10～the 60min that anneals at 250～400 ℃ of temperature, obtain ZnO nano-rod array;
Two, the preparation of CdTe nanoparticles solution: a, take 0.5～1.4g, six perchloric acid hydrate cadmiums and be dissolved in 100～150mL redistilled water, after adding 0.2～0.8mL3-mercaptopropionic acid, be the pH to 9～11 of the NaOH solution regulator solution of 0.5～2M with concentration, obtain solution A; B, under nitrogen atmosphere, be the sulfuric acid solution of 0.2～0.7M to adding 10～20mL concentration in 0.1～0.4g tellurium aluminium powder, the gas that reaction is produced imports in solution A, simultaneously with solution A at 80～150 ℃ of lower back flow reaction 12～48h, stir with magneton in course of reaction, obtain the CdTe nanoparticles solution;
Three, the preparation of phenanthroline cobalt: the ratio of 1:3 in molar ratio takes hydrated cobalt chloride and phenanthroline and is put in mortar, more than at room temperature mixing, grinding 2.5h;
Four, self-assembling method carries out quantum dot and coats layer by layer: it is in 6.2～8.5 cationic polyelectrolyte-phenanthroline cobalt liquor after 5～20min that gained ZnO nano-rod array in step 1 is immersed in pH, takes out and use deionized water rinsing, dries up; Then it is immersed in 5～20min in the CdTe nanoparticles solution of step 2 gained, takes out and use deionized water rinsing, dry up;
Five, repeating step is 4 10～25 times, namely obtains the ZnO nano-rod array that quantum dot is modified;
Wherein, the described substrate of step 1 is conductive substrates;
Zinc nitrate hexahydrate described in step 1-hexamethylenetetramine solution is to be that the zinc nitrate hexahydrate of 0.08～0.12M and hexamethylenetetramine that concentration is 0.08～0.12M mix for the ratio of 1:1 by volume by concentration;
Cationic polyelectrolyte described in step 4-phenanthroline cobalt liquor is that the phenanthroline cobalt of 0.5～2mg/mL and cationic polyelectrolyte that concentration is 0.2～1mg/mL form by concentration; Wherein, described cationic polyelectrolyte is polymine, polypropylene amine hydrochloride or PDDA.
6. the preparation method of a kind of quantum dot modification ZnO nano-rod array electrode according to claim 5, is characterized in that the conductive substrates described in step 1 is ITO or FTO.
7. prepare the method that a kind of quantum dot claimed in claim 1 is modified the ZnO nano-rod array electrode, it is characterized in that a kind of preparation method of quantum dot modification ZnO nano-rod array electrode, specifically carry 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 ℃ of reaction 2.5h～15h, take out substrate, carry out ultrasonic cleaning with deionized water and absolute ethyl alcohol successively, then 10～the 60min that anneals at 250～400 ℃ of temperature, obtain ZnO nano-rod array;
Two, the CdS nanoparticles solution prepares by the following method: a, take 0.5～1.4g, six perchloric acid hydrate cadmiums and be dissolved in 100～150mL redistilled water, after adding 0.2～0.8mL3-mercaptopropionic acid, be the pH to 9～11 of the NaOH solution regulator solution of 0.5～2M with concentration, obtain solution A; B, under nitrogen atmosphere, add 0.09～0.25g thioacetamide in solution A, simultaneously with solution A at 80～150 ℃ of lower back flow reaction 12～48h, stir with magneton in course of reaction, obtain the CdS nanoparticles solution;
Three, the preparation of phenanthroline cobalt: the ratio of 1:3 in molar ratio takes hydrated cobalt chloride and phenanthroline and is put in mortar, more than at room temperature mixing, grinding 2.5h;
Four, self-assembling method carries out quantum dot and coats layer by layer: it is in 6.2～8.5 cationic polyelectrolyte-phenanthroline cobalt liquor after 5～20min that gained ZnO nano-rod array in step 1 is immersed in pH, takes out and use deionized water rinsing, dries up; Then it is immersed in 5～20min in the CdS nanoparticles solution of step 2 gained, takes out and use deionized water rinsing, dry up;
Five, repeating step is 4 10～25 times, namely obtains the ZnO nano-rod array that quantum dot is modified;
Wherein, the described substrate of step 1 is conductive substrates;
Zinc nitrate hexahydrate described in step 1-hexamethylenetetramine solution is to be that the zinc nitrate hexahydrate of 0.08～0.12M and hexamethylenetetramine that concentration is 0.08～0.12M mix for the ratio of 1:1 by volume by concentration;
Cationic polyelectrolyte described in step 4-phenanthroline cobalt liquor is that the phenanthroline cobalt of 0.5～2mg/mL and cationic polyelectrolyte that concentration is 0.2～1mg/mL form by concentration; Wherein, described cationic polyelectrolyte is polymine, polypropylene amine hydrochloride or PDDA.
8. the preparation method of a kind of quantum dot modification ZnO nano-rod array electrode according to claim 7, is characterized in that the conductive substrates described in step 1 is ITO or FTO.
9. prepare the method that a kind of quantum dot claimed in claim 1 is modified the ZnO nano-rod array electrode, it is characterized in that a kind of preparation method of quantum dot modification ZnO nano-rod array electrode, specifically carry 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 ℃ of reaction 2.5h～15h, take out substrate, carry out ultrasonic cleaning with deionized water and absolute ethyl alcohol successively, then 10～the 60min that anneals at 250～400 ℃ of temperature, obtain ZnO nano-rod array;
Two, the CdSe nanoparticles solution prepares by the following method: take 0.04～0.09g, six perchloric acid hydrate cadmiums and be dissolved in 60～100mL deionized water, the natrium citricum that adds 0.08～0.13g, then use 0.5～2M sodium hydroxide solution that the pH value is transferred to 9～11, logical nitrogen 10min; Take in the deionized water that 0.004～0.007g selenourea is dissolved in 4mL, add above-mentioned mixed liquor after ultrasonic mixing, mixed liquor is ultrasonic 50s in the microwave oven of 900W, obtains the CdSe nanoparticles solution;
Three, the preparation of phenanthroline cobalt: the ratio of 1:3 in molar ratio takes hydrated cobalt chloride and phenanthroline and is put in mortar, more than at room temperature mixing, grinding 2.5h;
Four, self-assembling method carries out quantum dot and coats layer by layer: it is in 6.2～8.5 cationic polyelectrolyte-phenanthroline cobalt liquor after 5～20min that gained ZnO nano-rod array in step 1 is immersed in pH, takes out and use deionized water rinsing, dries up; Then it is immersed in 5～20min in the CdSe nanoparticles solution of step 2 gained, takes out and use deionized water rinsing, dry up;
Five, repeating step is 4 10～25 times, namely obtains the ZnO nano-rod array that quantum dot is modified;
Wherein, the described substrate of step 1 is conductive substrates;
Zinc nitrate hexahydrate described in step 1-hexamethylenetetramine solution is to be that the zinc nitrate hexahydrate of 0.08～0.12M and hexamethylenetetramine that concentration is 0.08～0.12M mix for the ratio of 1:1 by volume by concentration;
Cationic polyelectrolyte described in step 4-phenanthroline cobalt liquor is that the phenanthroline cobalt of 0.5～2mg/mL and cationic polyelectrolyte that concentration is 0.2～1mg/mL form by concentration; Wherein, described cationic polyelectrolyte is polymine, polypropylene amine hydrochloride or PDDA.
10. the preparation method of a kind of quantum dot modification ZnO nano-rod array electrode according to claim 9, is characterized in that the conductive substrates described in step 1 is ITO or FTO.
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