CN111977617B - Method for preparing cadmium-based alloy nano material - Google Patents
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- CN111977617B CN111977617B CN201910430850.8A CN201910430850A CN111977617B CN 111977617 B CN111977617 B CN 111977617B CN 201910430850 A CN201910430850 A CN 201910430850A CN 111977617 B CN111977617 B CN 111977617B
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Abstract
The application discloses a method for preparing a cadmium-based alloy nano material. The method comprises the step of carrying out ion exchange reaction on a material I containing an alcohol-soluble cadmium-based nano material, a doped metal source and an organic polar solvent I to obtain the cadmium-based alloy nano material. The method can successfully synthesize various Cd with accurately controllable components and large-range tunable energy gapxM2/m‑xTe alloy semiconductor nanowire, CdxM2/m‑xSe alloy semiconductor nanosheet and CdxM2/m‑xSe alloy semiconductor nanodots.
Description
Technical Field
The application relates to a method for preparing a cadmium-based alloy nano material, belonging to the technical field of nano material synthesis.
Background
Inorganic semiconductor nanowires have attracted considerable attention due to the combination of the excellent photoelectric properties and one-dimensional photoelectric transmission characteristics of semiconductor materials. However, due to the very limited band gap available in the conventional semiconductor nanowires, the continuous adjustment of the energy gap cannot be realized, thereby limiting the application of the nanowire in multifunctional tunable nano optical/electronic devices and photoelectric conversion devices.
At present, alloying treatment of semiconductor materials with different band gaps has become an effective means for expanding the energy gap of nano materials. Therefore, the preparation of alloy semiconductor nanowires has become a hot spot of research. In recent years, alloy semiconductor nanowires with controllable components are successfully prepared by a liquid phase catalytic growth method (SLS). Unfortunately, this method generally requires a harsh reaction environment (e.g., high temperature conditions) and is easy to independently nucleate and grow into non-alloy semiconductor nanowires. In order to overcome the above problems, the ion exchange method has been widely used in the synthesis of alloy nanowires as a synthesis means with mild reaction conditions, rapidness and controllable components.
Recently, cesium-lead halogen perovskite alloy nanowires with controllable components and energy gaps and Hg are respectively prepared by using an ion exchange method1-xCdxAnd (3) Te alloy nanowires. Unfortunately, no reports are available for universally synthesizing a plurality of alloy semiconductor nanowires with precisely controllable components and widely tunable energy gaps by using an ion exchange method.
Disclosure of Invention
According to one aspect of the present application, a method of preparing a cadmium-based alloy nanomaterial is provided. Preparation Cd with universality provided by applicationxM2/m-xA method for preparing semiconductor nano material of alloy A can be successfully carried outSo as to synthesize various cadmium-base alloy semiconductor nano materials with accurately controllable components and large-range tunable energy gap.
A method for preparing a cadmium-based alloy nano material comprises the step of carrying out ion exchange reaction on a material I containing an alcohol-soluble cadmium-based nano material, a doped metal source and an organic polar solvent I to obtain the cadmium-based alloy nano material.
Optionally, the cadmium-based nanomaterial is selected from any one of CdTe nanomaterials and CdSe nanomaterials.
A method for preparing a cadmium-based alloy nano material comprises the step of carrying out ion exchange reaction on a material I containing an alcohol-soluble CdTe nano material, a doped metal source and an organic polar solvent I to obtain the cadmium-based alloy nano material.
A method for preparing a cadmium-based alloy nano material comprises the step of carrying out ion exchange reaction on a material I containing an alcohol-soluble CdSe nano material, a doped metal source and an organic polar solvent I to obtain the cadmium selenide-based alloy nano material.
Optionally, the cadmium-based alloy nano material is selected from at least one of compounds with a chemical formula shown in a formula I,
CdxM2/m-xa formula I
Wherein M represents a doping metal;
a is selected from Se or Te;
m represents the valence of the doping metal M;
m is selected from 1 or 2;
the value range of x is more than or equal to 0.1 and less than or equal to 1.9.
The cadmium-based alloy nano material is selected from any one of cadmium telluride-based alloy nano materials and cadmium selenide-based alloy nano materials.
The upper limit of the value range of x is 0.11, 0.12, 0.15, 0.20, 0.25, 0.36, 0.39, 0.45, 0.49, 0.53, 0.62, 0.67, 0.75, 0.77, 0.79, 0.83, 1.8 and 1.9; the lower limit of the value range of x is 0.1, 0.11, 0.12, 0.15, 0.20, 0.25, 0.36, 0.39, 0.45, 0.49, 0.53, 0.62, 0.67, 0.75, 0.77, 0.79, 0.83 and 1.8.
In some specific examples, the cadmium telluride-based alloy nanomaterial is selected from at least one compound having a chemical formula shown in formula I-1,
CdxM2/m-xte formula I-1
Wherein M represents a doping metal;
m represents the valence of the doping metal M;
m is selected from 1 or 2;
the value range of x is more than or equal to 0.1 and less than or equal to 1.9.
In other specific examples, the cadmium selenide-based alloy nanomaterial is at least one selected from compounds having a chemical formula shown in formula I-2,
CdxM2/m-xse formula I-2
Wherein M represents a doping metal;
m represents the valence of the doping metal M;
m is selected from 1 or 2;
the value range of x is more than or equal to 0.1 and less than or equal to 1.9.
Optionally, the M is selected from at least one of silver, lead, zinc, germanium, tin, antimony, bismuth, copper, manganese, europium, strontium, indium, thallium and mercury.
Specifically, the M is selected from at least one of Ag (+ 1-valent), Pb (+ 2-valent), Zn (+ 2-valent), Ge (+ 2-valent), Sn (+ 2-valent), Sb (+ 2-valent), Bi (+ 2-valent), Cu (+ 2-valent), Mn (+ 2-valent), Eu (+ 2-valent), Sr (+ 2-valent), In (+ 2-valent), Tl (+ 2-valent), and Hg (+ 2-valent).
Optionally, the cadmium-based alloy nanomaterial includes cadmium-based alloy nanowires, cadmium-based alloy nanosheets, cadmium-based alloy nanodots.
Optionally, the cadmium telluride-based alloy nanomaterial includes cadmium telluride-based alloy nanowires, cadmium telluride-based alloy nanosheets, and cadmium telluride-based alloy nanodots.
Optionally, the cadmium selenide-based alloy nanomaterial comprises a cadmium selenide-based alloy nanowire, a cadmium selenide-based alloy nanosheet, a cadmium selenide-based alloy nanodot.
Preferably, the cadmium-based alloy nanowires include cadmium telluride-based alloy nanowires.
Preferably, the cadmium-based alloy nanoplates include cadmium selenide-based alloy nanoplates.
Preferably, the cadmium-based alloy nanodots include cadmium selenide-based alloy nanodots.
Preparation Cd that this application providedxM2/m-xTe alloy semiconductor nanowire, CdxM2/m-xSe alloy semiconductor nanosheet or CdxM2/m-xThe method of Se alloy semiconductor nanodots can successfully synthesize various Cd with accurately controllable components and large-range tunable energy gapxM2/m-xSe or CdxM2/m-xTe alloy semiconductor nano material.
Optionally, the cadmium-based alloy nanowire has a diameter of 6-8 nm and a length of more than 1 μm.
Optionally, the cadmium-based alloy nanoplates have dimensions of: the thickness is 4-7nm and the length is 10-50 nm.
Optionally, the cadmium-based alloy nanodots have dimensions of: the diameter is 3-7 nm.
Optionally, the diameter of the cadmium telluride-based alloy nanowire is 6-8 nm, and the length of the cadmium telluride-based alloy nanowire is greater than 1 μm.
Optionally, the cadmium selenide-based alloy nanosheets have dimensions of: the thickness is 4-7nm and the length is 10-50 nm.
Optionally, the cadmium selenide-based alloy nanodots have the dimensions: the diameter is 3-7 nm.
Optionally, the material I also comprises an organic phosphine reagent;
the organic phosphine reagent is selected from any one of tri-n-octyl phosphine, tri-n-phenyl phosphine and tri-n-octyl phosphine oxide.
The organic phosphine reagent is used In Pb, Zn, Ge, Sr and In exchange, and the selection of the organic phosphine reagent can improve the realization of the alloy nano material.
A method for preparing a cadmium telluride-based alloy nano material comprises the step of carrying out ion exchange reaction on a material I containing an alcohol-soluble CdTe nano material, a doped metal source, an organic phosphine reagent and an organic polar solvent I to obtain the cadmium telluride-based alloy nano material.
A method for preparing a cadmium selenide-based alloy nano material comprises the step of carrying out ion exchange reaction on a material I containing an alcohol-soluble CdSe nano material, a doped metal source, an organic phosphine reagent and an organic polar solvent I to obtain the cadmium selenide-based alloy nano material.
Optionally, the method for preparing the cadmium-based alloy nanomaterial at least comprises the following steps:
a) obtaining alcohol-soluble cadmium-based nano material;
b) mixing a first solution containing an alcohol-soluble cadmium-based nano material and an organic polar solvent I with a second solution containing a doped metal source and the organic polar solvent I, and carrying out ion exchange reaction to obtain the cadmium-based alloy nano material.
Specifically, the method for preparing the cadmium selenide-based or cadmium telluride-based alloy nano material at least comprises the following steps:
a) obtaining alcohol-soluble CdSe or CdTe nano material;
b) mixing a first solution containing alcohol-soluble CdSe or CdTe nano material and an organic polar solvent I with a second solution containing a doped metal source and the organic polar solvent I, and carrying out ion exchange reaction to obtain the cadmium selenide-based or cadmium telluride-based alloy nano material.
Optionally, step b) comprises: mixing a first solution containing an alcohol-soluble cadmium-based nano material and an organic polar solvent I with a second solution containing a doped metal source and the organic polar solvent I, adding an organic phosphine reagent, and carrying out ion exchange reaction to obtain the cadmium-based alloy nano material.
Specifically, when the doping metal ion is Pb, Zn, Ge, Sr or In, and the binding energy of the doping metal ion and cadmium ion In CdSe or CdTe nano material is larger, an organophosphorus reagent (tri-n-octylphosphine, tri-n-phenylphosphine, tri-n-octylphosphine oxide) is used In the ion exchange process.
In some examples, step b) comprises: mixing a first solution containing an alcohol-soluble CdTe nano material and an organic polar solvent I with a second solution containing a doped metal source and the organic polar solvent I, adding an organic phosphine reagent, and carrying out ion exchange reaction to obtain the cadmium telluride-based alloy nano material.
In other examples, step b) includes: mixing a first solution containing an alcohol-soluble CdSe nano material and an organic polar solvent I with a second solution containing a doped metal source and the organic polar solvent I, adding an organic phosphine reagent, and carrying out an ion exchange reaction to obtain the cadmium selenide-based alloy nano material.
Specifically, the preparation method of the first solution comprises the following steps: dissolving the alcohol-soluble CdSe or CdTe nano material in an organic polar solvent I, and stirring the solution to be clear in an inert atmosphere to obtain an alcohol-soluble CdSe or CdTe nano material solution, namely a first solution. In the first solution, the solubility of the CdTe nanowire, the CdSe nanosheet and the CdSe nanodot can be greatly improved by selecting the organic polar solvent I.
The preparation method of the second solution comprises the following steps: dissolving a doped metal source In an organic polar solvent I, stirring the solution to be clear In an inert atmosphere to obtain a doped metal ion solution (when the binding energy of doped metal ions (Pb, Zn, Ge, Sr and In) and cadmium ions In CdSe or CdTe nano materials is larger, an organic phosphorus reagent can be used In the ion exchange process), namely a second solution, which contains different molar concentrations. The selection of the organic phosphine reagent can improve the realization of the alloy nanometer material.
Then mixing the first solution and the second solution, and carrying out ion exchange reaction to obtain CdxM2/m-xSe or CdxM2/m-xAnd (3) a Te alloy nano material.
In the application, the Cd can be obtained by carrying out ion exchange reaction under certain conditionsxM2/m-xSe or CdxM2/m-xAnd (3) a Te alloy nano material. By optimizing the species of doped metal ions, the concentration of the doped metal ions, the ion exchange time, the ion exchange temperature, the selective use of an organic phosphine reagent and the environment of an organic polar solvent I of the system, Cd with accurate and controllable components (0-190%) and large-range tunable energy gap (0.7-2.3 eV) can be preparedxM1-xSe or CdxM1-xAnd (3) a Te alloy nano material.
Optionally, the alcohol-soluble cadmium-based nanomaterial is obtained by a method at least comprising the following steps:
a-1) obtaining an oil-soluble cadmium-based nano material;
a-2) reacting a material II containing the oil-soluble cadmium-based nano material, mercaptoalcohol and an organic polar solvent II to obtain the alcohol-soluble cadmium-based nano material.
Specifically, the alcohol-soluble CdSe or CdTe nano material is obtained by a method at least comprising the following steps:
a-1) obtaining oil-soluble CdSe or CdTe nano material;
a-2) reacting a material II containing the oil-soluble CdSe or CdTe nano material, mercaptoalcohol and an organic polar solvent II to obtain the alcohol-soluble CdSe or CdTe nano material.
Specifically, the oil-soluble CdSe or CdTe nanomaterial may be any one of nanowires, nanosheets, and nanodots.
The alcohol-soluble CdSe or CdTe nano material can be any one of nano wire, nano sheet and nano point.
In the application, the alcohol-soluble CdTe nanowire, CdSe nanosheet or CdSe nanodot is prepared from the oil-soluble CdTe nanowire, CdSe nanosheet or CdSe nanodot, and the cadmium telluride-based alloy semiconductor nanowire, cadmium selenide-based alloy semiconductor nanosheet or cadmium selenide-based alloy semiconductor nanodot is prepared from the alcohol-soluble CdTe nanowire, CdSe nanosheet or CdSe nanodot. Other nanostructures are similar and will not be described further herein.
In the step a-1), the preparation method of the oil-soluble CdSe or CdTe nano material is any suitable method in the prior art. For example, oil-soluble CdTe nanowires can be prepared by the method in an issued Chinese invention patent (patent number: 201110050390. X). Oil-soluble CdSe nanosheets can be prepared by methods in the literature (adv. funct. mater.2018,28,1802012). The oil-soluble CdSe nanodots can be prepared by methods in the literature (J.Phys.chem.C 2007,111, 526-531).
Before the step a-2), the obtained oil-soluble CdSe or CdTe nano material is purified. Specifically, diluting the oil-soluble CdSe or CdTe nano material with toluene, adding excessive acetone and methanol according to the ratio of 3:1 to separate out the nano material, centrifuging to obtain oil-soluble nano material precipitate, and repeating the above cleaning process to obtain high-purity oil-soluble nano material. And finally, drying the nano material precipitate in vacuum at 50-70 ℃ and grinding to obtain oil-soluble nano material powder.
The step a-2) specifically comprises the following steps: oil-soluble CdSe or CdTe nano material, mercaptohexanol and organic polar solvent II are blended and added into a three-neck flask and continuously stirred to form turbid liquid, the reaction temperature is controlled to be 0-180 ℃, the reaction time is 10-50 min, the original turbid liquid of a reaction system is converted into clear and transparent solution, and at the moment, the oil-soluble CdSe or CdTe nano material is converted into alcohol-soluble nano material.
And then purifying the obtained alcohol-soluble CdSe or CdTe nano material. Specifically, excessive n-hexane is added into the reaction system (alcohol-soluble nano material) to separate out the alcohol-soluble nano wire, after centrifugation, the supernatant is poured off to obtain alcohol-soluble nano wire precipitate, and finally the nano wire material is dried in vacuum at 60 ℃ and ground to obtain alcohol-soluble nano wire powder.
Alternatively, the mercapto alcohol is selected from C1～C6At least one of the mercaptoalcohols of (1).
The mercaptoalcohols include mercaptohexanol, mercaptoethanol, mercaptobutanol, mercaptopropanol, mercaptopentanol.
Optionally, in the step a-2), the ratio of the mass of the oil-soluble cadmium-based nano material, the volume of mercaptohexanol and the volume of the organic polar solvent II is 80-120 mg: 2-6 ml: 2-15 ml.
Specifically, in the step a-2), the ratio of the mass of the oil-soluble CdSe or CdTe nano material, the volume of mercaptohexanol and the volume of the organic polar solvent II is 80-120 mg: 2-6 ml: 2-15 ml.
Alternatively, in step a-2), the reaction conditions are: the reaction temperature is 0-180 ℃; the reaction time is 10-50 min.
Optionally, the organic polar solvent I and the organic polar solvent II are independently selected from at least one of ethanol, ethylene glycol, N-dimethylformamide and dimethyl sulfoxide.
Optionally, the doped metal source comprises a soluble salt compound containing a doped metal.
For example, the doped metal source includes silver nitrate, silver chloride, lead nitrate, lead chloride, lead bromide, mercury nitrate, mercury chloride, mercury perchlorate, zinc chloride, zinc nitrate, zinc acetate, copper chloride, cuprous chloride, tin chloride, indium acetate, manganese chloride, manganese acetate, europium chloride, europium acetate, bismuth chloride, antimony chloride.
In the first solution, the volume ratio of the mass of the alcohol-soluble cadmium-based nano material to the volume of the organic polar solvent I is 50-800 mg/ml.
Specifically, in the first solution, the volume ratio of the mass of the alcohol-soluble CdSe or CdTe nano material to the volume of the organic polar solvent I is 50-800 mg/ml.
Optionally, in the second solution, the volume ratio of the mass of the doped metal source to the organic polar solvent I is 0.1-1.2 g/mL;
wherein the mass of the doped metal source is based on the mass of the doped metal source itself.
Optionally, the volume ratio of the organophosphinic reagent to the sum of the first solution and the second solution is 0.1 to 1.
Optionally, the conditions of the ion exchange are: the temperature is 20-150 ℃; the time is 0.1-1 h.
The upper limit of the ion exchange temperature is independently selected from the group consisting of 25 ℃, 30 ℃, 40 ℃, 50 ℃, 60 ℃, 70 ℃, 80 ℃, 90 ℃, 100 ℃, 120 ℃, 130 ℃, 150 ℃; the lower limit of the ion exchange temperature is independently selected from the group consisting of 20 deg.C, 25 deg.C, 30 deg.C, 40 deg.C, 50 deg.C, 60 deg.C, 70 deg.C, 80 deg.C, 90 deg.C, 100 deg.C, 120 deg.C, and 130 deg.C.
The upper limit of the ion exchange time is independently selected from 0.5h and 1 h; the lower limit of the ion exchange time is independently selected from 0.1h and 0.5 h.
Preferably, the ion exchange reaction is carried out at room temperature for 0.1-1 h. For example, the temperature is 20 to 30 ℃.
In the application, the introduction of the organic polar solvent enhances the solubility of the alcohol-soluble CdSe or CdTe nano material, so that the ion exchange reaction time can be greatly shortened.
The ion exchange time at room temperature is 0.1-1 h. Because of the introduction of the polar solvent, the solubility is enhanced, and thus the ion exchange reaction time can be shortened.
As a specific embodiment, the preparation method of the cadmium telluride-based alloy semiconductor nanowire comprises the following steps:
(1) the preparation method of the alcohol-soluble CdTe nanowire comprises the following steps:
1-1) according to the granted chinese invention patent (patent No.: cn201110050390.x), oil-soluble CdTe nanowires with diameter of about 7nm and length of more than 1 μm are prepared.
1-2) diluting the oil-soluble CdTe nanowire with toluene, adding excessive acetone and methanol according to the proportion of 3:1 to separate out the nanowire, centrifuging at 7000rpm for 3min, pouring out supernatant to obtain oil-soluble nanowire precipitate, repeating the cleaning process for 2-3 times to obtain high-purity oil-soluble nanowire material, and finally vacuum drying and grinding the nanowire precipitate at 60 ℃ to obtain oil-soluble nanowire powder.
1-3) mixing 100mg of oil-soluble CdTe nanowire powder, 2-6 mL of mercaptohexanol and 2-15 mL of organic polar solvent II, adding the mixture into a three-neck flask, continuously stirring the mixture to form suspension, controlling the reaction temperature to be 0-180 ℃ and the reaction time to be 10-50 min, so that the reaction system is converted into a clear and transparent solution from the original suspension, and at the moment, the oil-soluble CdTe nanowire is converted into the alcohol-soluble nanowire. Adding excessive n-hexane into the reaction system to separate out the alcohol-soluble nanowires, centrifuging at 7000rpm for 3min, pouring out the supernatant to obtain alcohol-soluble nanowire precipitates, and finally, drying the nanowire materials at 60 ℃ in vacuum and grinding to obtain alcohol-soluble nanowire powder.
(2)CdxM2/m-xThe preparation method of the Te alloy semiconductor nanowire comprises the following steps:
2-1) dissolving the alcohol-soluble CdTe nanowire powder in the organic polar solvent I, and stirring the mixture until the mixture is clear under the protection of inert gas to obtain an alcohol-soluble CdTe nanowire solution. The organic polar solvent environment is ethanol, ethylene glycol, N-dimethylformamide or dimethyl sulfoxide. The mass ratio of the alcohol-soluble CdTe nanowire to the organic polar solvent is 1: 2 to 5. The selection of the polar solvent I can greatly improve the solubility of the CdTe nanowire.
2-2) dissolving M metal ions in the organic polar solvent I, and stirring the mixture to be clear under the protection of inert gas to obtain M doped metal ion solutions with different molar concentrations. Wherein the M-doped metal ions comprise: ag. One of metal ions such as Pb, Zn, Ge, Sn, Sb, Bi, Cu, Mn, Eu, Sr, In, Tl and the like. The organic polar solvent environment is ethanol, ethylene glycol, N-dimethylformamide or dimethyl sulfoxide.
2-3) mixing the solutions obtained In the step 2-1) and the step 2-2) (when the binding energy of the doped metal ions (Pb, Zn, Ge, Sr and In) and the cadmium ions In the CdTe nanowire is larger, an organic phosphorus reagent is used In the ion exchange process), and carrying out ion exchange reaction under optimized reaction conditions to obtain CdxM1-xAnd (3) Te alloy nanowires. By optimizing the doped metal ion type, the doped metal ion concentration, the ion exchange time, the ion exchange temperature, the selective use of an organic phosphine reagent and the organic polar solvent environment of the system, the Cd with the accurate and controllable components (0-190%) and the large-range tunable energy gap (0.7-2.3 eV) can be preparedxM2/m-xAnd (3) Te alloy nanowires. The molar ratio of Cd ions to M metal ions in the CdTe nanowire is 1: 0-18, thereby ensuring that the prepared alloy nanowire has accurate components and an energy gap capable of being tuned in a large range. The ion exchange time at room temperature is 0.1-1 h. Because of the introduction of the organic polar solvent, the solubility is enhanced, so that the ion exchange reaction time can be greatly shortened.
In the application, the oil-soluble nano material is a nano material which has a long alkyl chain group on the surface and is stably dispersed in a high-boiling-point nonpolar organic solvent.
The alcohol-soluble nano material is a nano material which has polar groups (such as hydroxyl or amino) on the surface and can be stably dispersed in a polar organic solvent.
Mercaptoalcohols refer to organic compounds containing a mercapto group and a hydroxyl group.
C1～C6The subscripts in (a) each indicate the number of carbon atoms contained in the compound. For example, C1～C6The mercapto alcohol of (2) represents a mercapto alcohol having 1 to 6 carbon atoms.
The beneficial effects that this application can produce include:
1) the method for preparing the cadmium-based alloy nano material (cadmium selenide base or cadmium telluride base) provided by the application provides a universal method for preparing Cd on the basis of deeply analyzing the influence of an organic polar solvent on the realization of accurate and controllable component and large-range tuning of energy gap on the nano material in the ion exchange processxM2/m-xSe or CdxM2/m-xA method for preparing Te alloy semiconductor nano material. The method can successfully synthesize Cd with various components (namely the content of the doped metal M), which is accurately controllable (0-190%), and the energy gap can be tuned in a large range (0.7-2.3 eV)xM2/m-xSe or CdxM2/m-xTe alloy semiconductor nano material.
2) In the application, the introduction of the polar solvent enhances the solubility of the alcohol-soluble CdSe or CdTe nano material, so that the ion exchange reaction time can be greatly shortened.
3) Preparation Cd that this application providedxM2/m-xSe or CdxM2/m-xThe method for preparing the Te alloy semiconductor nano material has the advantages of simple operation, mild condition and suitability for a plurality of systems. The method is utilized to prepare Cd with accurately controllable components and large-range tunable energy gapxM2/m-xSe or CdxM2/m-xThe Te alloy semiconductor nano material has wide application value in the fields of photoelectric devices, nano devices and sensing.
4) In the prior art, the oil-soluble nano material is generally dispersed in a nonpolar solvent for ion exchange, and then the solubility of the oil-soluble nano material is very low and the ion exchange is insufficient. According to the method, the oil-soluble nano material is firstly processed into the alcohol-soluble nano material, and then the alcohol-soluble nano material is dissolved in an organic polar solvent, such as ethanol, ethylene glycol, N-dimethylformamide and dimethyl sulfoxide, so that the solubility of the alcohol-soluble nano material is greatly improved, the ion exchange effect is improved, the ion exchange reaction time is further shortened, and the prepared alloy nanowires, nanosheets and nanodots have accurate components and large-range tunable energy gaps.
Drawings
FIG. 1 shows Cd in one embodiment of the present applicationxAg2-xTransmission electron microscope images of the Te alloy semiconductor nanowires;
FIG. 2 shows Cd in one embodiment of the present applicationxAg2-xAn absorption spectrogram of the Te alloy semiconductor nanowire;
FIG. 3 shows Cd in an embodiment of the present applicationxZn1-xTransmission electron microscope images of the Te alloy semiconductor nanowires;
FIG. 4 shows Cd in an embodiment of the present applicationxZn1-xAn absorption spectrogram of the Te alloy semiconductor nanowire;
FIG. 5 shows Cd in an embodiment of the present applicationxPb1-xTransmission electron microscope images of the Te alloy semiconductor nanowires;
FIG. 6 shows Cd in one embodiment of the present applicationxPb1-xAn absorption spectrogram of the Te alloy semiconductor nanowire;
FIG. 7 shows Cd in one embodiment of the present applicationxHg1-xA transmission electron microscope image of the Te alloy semiconductor nanodots;
FIG. 8 shows Cd in one embodiment of the present applicationxHg1-xAbsorption spectrograms of the Te alloy semiconductor nanodots;
FIG. 9 shows Cd in an embodiment of the present applicationxCu1-xA transmission electron microscope image of the Te alloy semiconductor nanosheet;
FIG. 10 shows Cd in one embodiment of the present applicationxCu1-xAbsorption spectrum of Te alloy semiconductor nano-sheet.
Detailed Description
The present application will be described in detail with reference to examples, but the present application is not limited to these examples.
The raw materials in the examples of the present application were all purchased commercially, unless otherwise specified.
CdxM2/m-xThe preparation method of the Te alloy semiconductor nanowire comprises the following steps:
1) dissolving alcohol-soluble CdTe nanowire powder in a polar solvent I, and stirring the solution to be clear under the protection of inert gas to obtain an alcohol-soluble CdTe nanowire solution. The polar solvent environment is ethanol, ethylene glycol, N-dimethylformamide or dimethyl sulfoxide. The proportion of the alcohol-soluble CdTe nanowire to the polar solvent is 1: 2 to 5.
2) Dissolving M-doped metal ions in a polar solvent I, and stirring the mixture to be clear under the protection of inert gas to obtain M-doped metal ion solutions with different molar concentrations. Wherein the M-doped metal ions comprise: ag. One of metal ions such as Pb, Zn, Ge, Sn, Sb, Bi, Cu, Mn, Eu, Sr, In, Tl and the like. When metal ions (Pb, Zn, Ge, Sr and In) doped In the organic polar solvent and cadmium ions In the CdTe nanowire have larger combination energy, an organic phosphorus reagent (tri-n-octyl phosphine, tri-n-phenyl phosphine and tri-n-octyl phosphine oxide) is used In the ion exchange process. The polar solvent environment is ethanol, ethylene glycol, N-dimethylformamide or dimethyl sulfoxide.
3) Mixing the solutions obtained in the step 1) and the step 2), and carrying out ion exchange reaction under optimized reaction conditions to obtain CdxM2/m-xAnd (3) a Te alloy nanowire. Through the optimization of the metal ion species, the metal ion concentration, the ion exchange time, the ion exchange temperature, the selective use of an organic phosphine reagent and the organic polar solvent environment of the system, the Cd with the accurate and controllable components and the large-range tunable energy gap can be preparedxM2/m-xAnd (3) Te alloy nanowires. The molar ratio of Cd ions to M metal ions in the CdTe nanowire is 1: 0 to 18, and the ion exchange time is 0.1 to 1 hour. The ion exchange temperature is room temperature.
In the application, an ICP spectrometer is adopted for ICP element analysis, wherein the ICP spectrometer is a German Scheker inductively coupled plasma emission ICP spectrometer;
the TEM adopts a JEOL-JEM 2100F transmission electron microscope, and the working potential is 200 kV;
the absorption spectrum test adopts an Shimadzu UV-3600 ultraviolet visible near-infrared spectrophotometer;
example 1 preparation of alcohol-soluble CdTe nanowire
1) According to the granted chinese invention patent (patent number: 201110050390.X), oil-soluble CdTe nanowire with the diameter of about 7nm and the length of more than 1 μm is prepared.
2) Diluting the oil-soluble CdTe nanowire with toluene, adding a mixed solution of acetone and methanol (the volume ratio of the mass of the nanowire to the mixed solution of acetone and methanol is 20mg/mL) to separate out the nanowire, centrifuging at 7000rpm for 3min, pouring out the supernatant to obtain an oil-soluble nanowire precipitate, repeating the cleaning process for 3 times to obtain a high-purity oil-soluble nanowire material, and finally, drying the nanowire precipitate at 60 ℃ in vacuum and grinding to obtain oil-soluble nanowire powder.
3) 100mg of oil-soluble CdTe nanowire powder, 2mL of mercaptohexanol and 15mL of organic polar solvent II (ethanol) are blended and added into a three-neck flask and continuously stirred to form turbid liquid, the reaction temperature is controlled at 120 ℃ and the reaction time is controlled for 30min, so that the original turbid liquid of a reaction system is converted into a clear and transparent solution, and at the moment, the oil-soluble CdTe nanowire is converted into the alcohol-soluble nanowire. Adding excessive n-hexane into the reaction system to separate out the alcohol-soluble nanowires, centrifuging at 7000rpm for 3min, pouring out the supernatant to obtain alcohol-soluble nanowire precipitates, and finally, drying the nanowire materials at 60 ℃ in vacuum and grinding to obtain alcohol-soluble nanowire powder.
Example 2 preparation of alcohol-soluble CdTe nanowire
The difference from the embodiment 1 is that: 80mg of oil-soluble CdTe nanowire powder, 6mL of mercaptohexanol and 10mL of polar solvent are mixed and added into a three-neck flask and continuously stirred to form suspension, and the reaction temperature is controlled at 10 ℃ and the reaction time is controlled for 50 min.
Example 3 preparation of alcohol soluble CdTe nanowires
The difference from the embodiment 1 is that: 120mg of oil-soluble CdTe nanowire powder, 3mL of mercaptohexanol and 2mL of polar solvent are mixed and added into a three-neck flask and continuously stirred to form suspension, and the reaction temperature is controlled at 180 ℃ and the reaction time is controlled for 10 min.
Example 4 preparation of alcohol-soluble CdSe nanodots
1) According to the method of the granted Chinese invention patent (J.Phys.chem.C 2007,111,526-.
2) Diluting the oil-soluble CdSe nanodots with toluene, adding a mixed solution of acetone and methanol (the volume ratio of the mass of the nanodots to the mixed solution of acetone and methanol is 20mg/mL) to separate out the nanodots, centrifuging at 7000rpm for 3min, pouring out a supernatant to obtain an oil-soluble nanodot precipitate, repeating the cleaning process for 3 times to obtain a high-purity oil-soluble nanodot material, and finally vacuum-drying and grinding the nanodot precipitate at 60 ℃ to obtain oil-soluble nanodot powder.
3) 100mg of oil-soluble CdSe nano-dot powder, 2mL of mercaptohexanol and 15mL of organic polar solvent II (ethanol) are blended and added into a three-neck flask and continuously stirred to form suspension, the reaction temperature is controlled at 120 ℃ and the reaction time is controlled for 30min, so that the reaction system is changed into a clear and transparent solution from the original suspension, and at the moment, the oil-soluble CdSe nano-dot is changed into the alcohol-soluble nano-dot. Adding excessive n-hexane into the reaction system to separate out the alcohol-soluble nanodots, centrifuging at 7000rpm for 3min, pouring out the supernatant to obtain alcohol-soluble nanodot precipitates, and finally, drying the nanodot material at 60 ℃ in vacuum and grinding to obtain alcohol-soluble nanodot powder.
Example 5 preparation of alcohol-soluble CdSe nanosheets
1) According to the method of an authorized Chinese invention patent (adv.Funct.Mater.2018,28,1802012), an oil-soluble CdSe nano-sheet with the thickness of 4-7nm and the length of 10-50nm is prepared.
2) Diluting the oil-soluble CdSe nanosheets with toluene, adding a mixed solution of acetone and methanol (the volume ratio of the mass of the nanosheets to the mixed solution of acetone and methanol is 20mg/mL) to separate out the nanosheets, centrifuging at 7000rpm for 3min, pouring out a supernatant to obtain an oil-soluble nanosheet precipitate, repeating the cleaning process for 3 times to obtain a high-purity oil-soluble nanosheet material, and finally drying and grinding the nanosheet precipitate in vacuum at 60 ℃ to obtain oil-soluble nanosheet powder.
3) 100mg of oil-soluble CdSe nanosheet powder, 2mL of mercaptohexanol and 15mL of organic polar solvent II (ethanol) are blended and added into a three-neck flask and continuously stirred to form suspension, the reaction temperature is controlled at 120 ℃ and the reaction time is controlled for 30min, so that the reaction system is converted from the original suspension into a clear and transparent solution, and at the moment, the oil-soluble CdSe nanosheet is converted into the alcohol-soluble nanosheet. Adding excessive n-hexane into the reaction system to separate out the alcohol-soluble nanosheets, centrifuging at 7000rpm for 3min, pouring out the supernatant to obtain alcohol-soluble nanosheet precipitates, and finally, drying the nanosheet materials in vacuum at 60 ℃ and grinding to obtain alcohol-soluble nanosheet powder.
Examples 6 to 9 CdxAg2-xPreparation and characterization of Te nanowires
Example 6
1) 50mg of the alcohol-soluble CdTe nanowire powder of example 1 was dissolved in 1mL of ethanol under inert gas N2And stirring to be clear under the protection of gas to obtain the alcohol-soluble CdTe nanowire solution.
2) 0.6g of silver nitrate (Ag)+) Dissolved in 1mL of ethanol under inert gas N2Stirring to be clear under the protection of the solution to obtain the solution containing Ag+The solution of (1).
3) Mixing the solutions obtained in the step 1) and the step 2), and controlling Cd in the CdTe nanowire2+And Ag+In a molar ratio of 1: 18, the ion exchange time is 0.1h, the ion exchange temperature is room temperature (25 ℃), and the alloy nanowire is obtained and recorded as sample # 1.
ICP elemental analysis is carried out on the 1# alloy nanowire, and the analysis result is as follows: sample No. 1 has the chemical formula Cd0.11Ag1.89Te。
Example 7
The difference from example 6 is that:
200mg of the alcohol-soluble CdTe nanowire powder of example 1 was dissolved in 1mL of ethylene glycol; 0.6g of silver nitrate (Ag)+) Dissolving in 1mL of ethylene glycol;control of Cd in CdTe nanowires2+And Ag+In a molar ratio of 1: 4, the ion exchange time is 1h, the ion exchange temperature is 20 ℃, and the alloy nanowire is obtained and is marked as sample No. 2;
ICP elemental analysis is carried out on the 2# alloy nanowire, and the analysis result is as follows: sample No. 2 has the chemical formula Cd0.39Ag1.61Te。
Example 8
The difference from example 6 is that:
dissolving 800mg of the alcohol-soluble CdTe nanowire powder of example 1 in 1mL of dimethyl sulfoxide; 1.2g of silver nitrate (Ag)+) Dissolved in 1mL of dimethyl sulfoxide; control of Cd in CdTe nanowire2+And Ag+In a molar ratio of 1: 2, the ion exchange time is 0.5h, the ion exchange temperature is 30 ℃, and the alloy nanowire is obtained and is marked as sample # 3;
ICP elemental analysis is carried out on the 3# alloy nanowire, and the analysis result is as follows: sample No. 3 has the chemical formula Cd0.67Ag1.33Te。
Example 9
The difference from example 6 is that:
control of Cd in CdTe nanowire2+And Ag+In a molar ratio of 9: 1, finally obtaining the alloy nanowire with the chemical formula of Cd1.8Ag0.2Te。
Samples 1# -3 # TEM were characterized separately. The characterization result shows that the prepared CdxAg2-xThe diameter of the Te nano-wire is about 7nm, and the length is more than 1 μm. Taking sample 1# as a typical representative, fig. 1 is a TEM image of sample 1#, and it can be seen from fig. 1 that the diameter of the nanowire is about 7nm and the length is greater than 1 μm.
Respectively carrying out absorption spectrum tests on the alcohol-soluble CdTe nanowires in samples 1# to 3# and the embodiment 1, wherein FIG. 2 is a spectrum test chart, and as can be seen from FIG. 2, the alcohol-soluble Cd0.67Ag1.33Te、Cd0.39Ag1.61Te、Cd0.11Ag1.89And (3) a Te nanowire.
Examples 10 to 12 CdxZn1-xPreparation and characterization of Te nanowires
Example 10
1) Dissolving 50mg of the alcohol-soluble CdTe nanowire powder obtained in example 1 in 1mL of ethanol, and stirring the solution under the protection of inert gas until the solution is clear to obtain an alcohol-soluble CdTe nanowire solution;
2) 0.4g of zinc nitrate (Zn)2+) Dissolving in 1mL ethanol, stirring under the protection of inert gas until the solution is clear to obtain the solution containing Zn2+The solution of (1);
3) mixing the solutions obtained in the step 1) and the step 2), and controlling Cd in the CdTe nanowire2+And Zn2+In a molar ratio of 1: 5.6 (2 ml of alcohol-soluble CdTe nanowire solution, containing Zn)2+4mL of solution of (1), 1mL of tri-n-phenylphosphine, 1h of ion exchange time and 130 ℃ of ion exchange temperature to obtain alloy nanowires, which are recorded as a sample No. 4.
ICP elemental analysis is carried out on the 4# alloy nanowire, and the analysis result is as follows: sample No. 4 has the chemical formula Cd0.15Zn0.85Te。
Example 11
The difference from the example 10 is that: mixing the solutions obtained in the step 1) and the step 2), and controlling Cd in the CdTe nanowire2+And Zn2+In a molar ratio of 1: 1.2 (2 ml of alcohol-soluble CdTe nanowire solution containing Zn)2+4ml) of tri-n-phenylphosphine (5 ml);
finally obtaining alloy nanowires, and recording the alloy nanowires as a sample No. 5;
ICP elemental analysis is carried out on the 5# alloy nanowire, and the analysis result is as follows: sample No. 5 has the chemical formula Cd0.45Zn0.55Te。
Example 12
The difference from the example 10 is that: mixing the solutions obtained in the step 1) and the step 2), and controlling Cd in the CdTe nanowire2+And Zn2+Is 3.3: 1 (2 ml of alcohol-soluble CdTe nanowire solution containing Zn2+4ml) of tri-n-phenylphosphine (3 ml);
finally obtaining alloy nanowires, and recording the alloy nanowires as a sample 6 #;
ICP elemental analysis is carried out on the 6# alloy nanowire, and the analysis result is as follows: sample No. 6 has the chemical formula Cd0.77Zn0.23Te。
Samples 4# -6 # TEM were characterized separately. The characterization result shows that the prepared CdxZn1-xThe diameter of the Te nano-wire is about 7nm, and the length is more than 1 μm. Taking sample 4# as a representative, fig. 3 is a TEM image of sample 4#, and it can be seen from fig. 3 that the diameter of the nanowire is about 7nm and the length is greater than 1 μm.
Respectively carrying out absorption spectrum tests on the alcohol-soluble CdTe nanowires in samples No. 4-6 and the sample No. 1, wherein FIG. 4 is a spectrum test chart, and as can be seen from FIG. 4, the alcohol-soluble Cd0.15Zn0.85Te、Cd0.45Zn0.55Te、Cd0.77Zn0.23And (3) a Te nanowire.
Examples 13 to 17 CdxPb1-xPreparation and characterization of Te nanowires
Example 13
1) Dissolving 50mg of the alcohol-soluble CdTe nanowire powder obtained in the embodiment 1 in 1mL of ethanol, and stirring the solution to be clear under the protection of inert gas to obtain an alcohol-soluble CdTe nanowire solution;
2) 0.45g of lead chloride (Pb)2+) Dissolving in 1mL ethanol, stirring under the protection of inert gas until the solution is clear to obtain the solution containing Pb2+The solution of (1);
3) mixing the solutions obtained in the step 1) and the step 2), and controlling Cd in the CdTe nanowire2+And Pb2+In a molar ratio of 1: 7.3 (2 ml of alcohol-soluble CdTe nanowire solution containing Pb)2+4mL of solution of (1), the ion exchange time is 0.5h, and the ion exchange temperature is 130 ℃, so as to obtain the alloy nanowire which is marked as sample No. 7.
ICP elemental analysis is carried out on the 4# alloy nanowire, and the analysis result is as follows: sample No. 7 has the chemical formula Cd0.12Pb0.88Te。
Example 14
The difference from example 13 is that: mixing the solutions obtained in the step 1) and the step 2), and controlling Cd in the CdTe nanowire2+And Pb2+In a molar ratio of 1: 1.8 (2 ml of alcohol-soluble CdTe nanowire solution containing Pb)2+4mL) of the solution, 2mL of tri-n-phenylphosphine;
finally obtaining alloy nanowires, and recording the alloy nanowires as a sample No. 8;
ICP elemental analysis is carried out on the 8# alloy nanowire, and the analysis result is as follows: sample No. 8 has the chemical formula Cd0.36Pb0.64Te。
Example 15
The difference from example 13 is that: mixing the solutions obtained in the step 1) and the step 2), and controlling Cd in the CdTe nanowire2+And Pb2+In a molar ratio of 1: 1 (2 ml of alcohol-soluble CdTe nanowire solution containing Pb)2+4mL) of tri-n-phenylphosphine, 4 mL;
finally obtaining alloy nanowires, and recording the alloy nanowires as sample No. 9;
ICP elemental analysis is carried out on the 9# alloy nanowire, and the analysis result is as follows: sample No. 9 has the chemical formula Cd0.49Pb0.51Te。
Example 16
The difference from example 13 is that: mixing the solutions obtained in the step 1) and the step 2), and controlling Cd in the CdTe nanowire2+And Pb2+In a molar ratio of 1.6: 1 (2 ml of alcohol-soluble CdTe nanowire solution containing Pb)2+4mL) of the solution, 5mL of tri-n-phenylphosphine;
finally obtaining alloy nanowires, and recording the alloy nanowires as a sample No. 10;
ICP elemental analysis is carried out on the 10# alloy nanowire, and the analysis result is as follows: sample No. 10 has the chemical formula Cd0.62Pb0.38Te。
Example 17
The difference from example 13 is that: mixing the solutions obtained in the step 1) and the step 2), and controlling Cd in the CdTe nanowire2+And Pb2+Is 4.8: 1 (2 ml of alcohol-soluble CdTe nanowire solution containing Pb)2+4mL) of the solution, 3mL of tri-n-phenylphosphine;
finally obtaining the alloy nanowire which is marked as sample No. 11;
ICP elemental analysis is carried out on the 11# alloy nanowire, and the analysis result is as follows: sample No. 11 has the chemical formula Cd0.83Pb0.17Te。
Samples 7# -11 # TEM were characterized separately. Display of characterization resultsPreparation of the obtained CdxAg1-xThe diameter of the Te nano-wire is about 7nm, and the length is more than 1 μm. Taking sample 7# as a representative, fig. 5 is a TEM image of sample 7#, and it can be seen from fig. 5 that the diameter of the nanowire is about 7nm and the length is greater than 1 μm.
The absorption spectrum tests are respectively carried out on the alcohol-soluble CdTe nanowires in samples 7# to 11# and the embodiment 1, FIG. 6 is a spectrum test chart, and as can be seen from FIG. 6, the alcohol-soluble Cd0.83Pb0.17Te、Cd0.62Pb0.38Te、Cd0.49Pb0.51Te、Cd0.36Pb0.64Te、Cd0.12Pb0.88A Te nanowire.
Examples 18 to 21 CdxHg1-xPreparation and characterization of Se nanodots
Example 18
1) Dissolving 50mg of the alcohol-soluble CdSe nanodot powder obtained in example 4 in 1mL of ethanol, and stirring the solution to be clear under the protection of inert gas to obtain an alcohol-soluble CdSe nanodot solution;
2) 0.2g of mercury nitrate (Hg) was added2+) Dissolving in 1mL ethanol, stirring under inert gas protection to clarify to obtain the product containing Hg2+The solution of (1);
3) mixing the solutions obtained in the step 1) and the step 2), and controlling Cd in the CdSe nanodots2+And Hg2+In a molar ratio of 1: and 3, the ion exchange time is 1h, the ion exchange temperature is room temperature (25 ℃), and the alloy nanodots are obtained and are marked as sample No. 12.
ICP elemental analysis is carried out on the 12# alloy nanodots, and the analysis result is as follows: sample No. 12 has the chemical formula Cd0.25Hg0.75Se。
Example 19
The difference from example 18 is that: mixing the solutions obtained in the step 1) and the step 2), and controlling Cd in the CdSe nanodots2+And Hg2+In a molar ratio of 1.1: 1;
finally obtaining alloy nanodots which are marked as sample No. 13;
ICP element analysis is carried out on the 13# alloy nanodots, and the analysis result is as follows: sample No. 13 has the chemical formula Cd0.53Hg0.47Se。
Example 20
The difference from example 18 is that: mixing the solutions obtained in the step 1) and the step 2), and controlling Cd in the CdSe nanodots2+And Hg2+Is 3.3: 1;
finally obtaining alloy nanodots which are marked as sample No. 14;
ICP elemental analysis is carried out on the 14# alloy nanodots, and the analysis result is as follows: sample No. 14 has the chemical formula Cd0.79Hg0.21Se。
Example 21
Samples 12# -14 # TEMs were characterized separately. The characterization result shows that the prepared CdxHg1-xThe diameter of the Se nanodots is 3-7 nm. Taking sample 12# as a representative, fig. 7 is a TEM image of sample 12# and it can be seen from fig. 7 that the diameter of the nanodots is 3-7 nm.
The absorption spectrum tests were performed on the alcohol-soluble CdSe nanodots of samples No. 12 to No. 14 and example 4, respectively, FIG. 8 is a spectrum test chart, and it can be seen from FIG. 8 that the alcohol-soluble Cd0.79Hg0.21Se、Cd0.53Hg0.47Se、Cd0.25Hg0.75Se nanodots.
Examples 22 to 25 CdxCu1-xPreparation and characterization of Se nanoplates
Example 22
1) Dissolving 50mg of the alcohol-soluble CdSe nanosheet powder of embodiment 5 in 1mL of ethanol, and stirring to be clear under the protection of inert gas to obtain an alcohol-soluble CdSe nanosheet solution;
2) 0.15g of copper chloride (Cu)2+) Dissolving in 1mL ethanol, stirring under the protection of inert gas until the solution is clear to obtain the product containing Cu2+The solution of (1);
3) mixing the solutions obtained in the step 1) and the step 2), and controlling Cd in the CdSe nanosheets2+And Cu2+In a molar ratio of 1: 4, the ion exchange time is 1h, the ion exchange temperature is room temperature (25 ℃), and the alloy nanosheet is obtained and recorded as sample No. 15.
ICP elemental analysis is carried out on the 15# alloy nanosheet, and the analysis result is as follows: of sample No. 15Chemical formula is Cd0.20Cu0.80Se。
Example 23
The difference from example 22 is that: mixing the solutions obtained in the step 1) and the step 2), and controlling Cd in the CdSe nanosheets2+And Cu2+In a molar ratio of 1: 1.1;
finally obtaining an alloy nano sheet which is marked as a sample No. 16;
ICP elemental analysis is carried out on the 16# alloy nanosheets, and the analysis result is as follows: sample No. 16 has the chemical formula Cd0.49Cu0.51Se。
Example 24
The difference from example 22 is that: mixing the solutions obtained in the step 1) and the step 2), and controlling Cd in the CdSe nanosheets2+And Cu2+In a molar ratio of 3: 1;
finally obtaining an alloy nanosheet, and recording the alloy nanosheet as a sample No. 17;
ICP elemental analysis is carried out on the 17# alloy nanosheet, and the analysis result is as follows: sample No. 17 has the chemical formula Cd0.75Cu0.25Se。
Example 25
Samples 15# -17 # TEM were characterized separately. The characterization result shows that the prepared CdxCu1-xThe thickness of the Se nano-sheet is 4-7nm, and the length is 10-50 nm. Taking sample 15# as a representative, FIG. 9 is a TEM image of sample 15#, and from FIG. 9, it can be seen that the thickness of the nanosheet is 4-7nm, and the length is 10-50 nm.
Respectively carrying out absorption spectrum tests on the alcohol-soluble CdSe nanosheets of samples No. 15-17 # and the example 5, wherein FIG. 10 is a spectrum test chart, and as can be seen from FIG. 10, the alcohol-soluble Cd0.75Cu0.25Se、Cd0.49Cu0.51Se、Cd0.20Cu0.80Se nanosheet.
Although the present application has been described with reference to a few embodiments, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the application as defined by the appended claims.
Claims (18)
1. A method for preparing a cadmium-based alloy nano material is characterized in that a material I containing an alcohol-soluble cadmium-based nano material, a doped metal source and an organic polar solvent I is subjected to ion exchange reaction to obtain the cadmium-based alloy nano material;
the cadmium-based alloy nano material comprises a cadmium-based alloy nanowire, a cadmium-based alloy nanosheet and a cadmium-based alloy nanodot;
the cadmium-based alloy nanowire is 6-8 nm in diameter and more than 1 mu m in length;
the method for preparing the cadmium-based alloy nano material at least comprises the following steps:
a) obtaining alcohol-soluble cadmium-based nano material;
b) mixing a first solution containing an alcohol-soluble cadmium-based nano material and an organic polar solvent I with a second solution containing a doped metal source and the organic polar solvent I, and carrying out ion exchange reaction to obtain the cadmium-based alloy nano material;
the alcohol-soluble cadmium-based nano material is obtained by adopting a method at least comprising the following steps:
a-1) obtaining an oil-soluble cadmium-based nano material;
a-2) reacting a material II containing the oil-soluble cadmium-based nano material, mercaptoalcohol and an organic polar solvent II to obtain an alcohol-soluble cadmium-based nano material;
the organic polar solvent I and the organic polar solvent II are independently selected from at least one of ethanol, ethylene glycol, N-dimethylformamide and dimethyl sulfoxide.
2. The method according to claim 1, wherein the cadmium-based nanomaterial is selected from any of CdTe nanomaterials, CdSe nanomaterials.
3. The method of claim 1, wherein the cadmium-based alloy nanomaterial is at least one selected from the group consisting of compounds having the formula shown in formula I,
CdxM2/m-xa formula I
Wherein M represents a doping metal;
a is selected from Se or Te;
m represents the valence of the doping metal M;
m is selected from 1 or 2;
the value range of x is more than or equal to 0.1 and less than or equal to 1.9.
4. The method of claim 3, wherein M is selected from at least one of silver, lead, zinc, germanium, tin, copper, manganese, europium, strontium, thallium, and mercury.
5. The method of claim 1, wherein the cadmium-based alloy nanowires comprise cadmium telluride-based alloy nanowires.
6. The method of claim 1, wherein the cadmium-based alloy nanoplates comprise cadmium selenide-based alloy nanoplates.
7. The method of claim 1, wherein the cadmium-based alloy nanodots comprise cadmium selenide-based alloy nanodots.
8. The method of claim 1, wherein the cadmium-based alloy nanoplates have dimensions of: the thickness is 4-7nm and the length is 10-50 nm.
9. The method of claim 1, wherein the cadmium-based alloy nanodots have a size of: the diameter is 3-7 nm.
10. The method of claim 1, wherein said feed i further comprises an organophosphinic agent;
the organic phosphine reagent is selected from any one of tri-n-octyl phosphine, tri-n-phenyl phosphine and tri-n-octyl phosphine oxide.
11. The method of claim 1, wherein step b) comprises: mixing a first solution containing an alcohol-soluble cadmium-based nano material and an organic polar solvent I with a second solution containing a doped metal source and the organic polar solvent I, adding an organic phosphine reagent, and carrying out ion exchange reaction to obtain the cadmium-based alloy nano material.
12. The process according to claim 1, characterized in that said mercapto alcohol is selected from C1~C6At least one of mercaptoalcohols of (a).
13. The method as claimed in claim 1, wherein in the step a-2), the ratio of the mass of the oil-soluble cadmium-based nanomaterial, the volume of the mercaptoalcohol and the volume of the organic polar solvent II is 80-120 mg: 2-6 ml: 2-15 ml;
the mercaptoalcohol is mercaptohexanol.
14. The process according to claim 1, wherein in step a-2), the reaction conditions are: the reaction temperature is 0-180 ℃; the reaction time is 10-50 min.
15. The method as claimed in claim 1, wherein the volume ratio of the mass of the alcohol-soluble cadmium-based nanomaterial to the volume of the organic polar solvent I in the first solution is 50-800 mg/ml.
16. The method according to claim 1, wherein in the second solution, the volume ratio of the mass of the doping metal source to the organic polar solvent I is 0.1-1.2 g/mL;
wherein the mass of the doped metal source is based on the mass of the doped metal source itself.
17. The method of claim 1, wherein the source of dopant metal comprises a soluble salt compound comprising a dopant metal.
18. The method of claim 1, wherein the conditions of the ion exchange are: the temperature is 20-150 ℃; the time is 0.1-1 h.
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