CN1266249C - Water phase synthesis method for diluted magnetic fluorescent cobalt-doped cadmium telluride alloy quantum dot - Google Patents
Water phase synthesis method for diluted magnetic fluorescent cobalt-doped cadmium telluride alloy quantum dot Download PDFInfo
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- CN1266249C CN1266249C CN 200410093431 CN200410093431A CN1266249C CN 1266249 C CN1266249 C CN 1266249C CN 200410093431 CN200410093431 CN 200410093431 CN 200410093431 A CN200410093431 A CN 200410093431A CN 1266249 C CN1266249 C CN 1266249C
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Abstract
The present invention relates to a water-phase synthesis method for a diluted magnetic fluorescent cobalt-doped cadmium telluride alloy quantum dot. In the method, water is used as a solvent, and the method comprises the following steps: mixing cadmium salts (or cadmium oxides or cadmium hydroxides), cobalt salts (or cobalt oxides or cobalt hydroxides) with a water soluble sulfhydryl compound; injecting tellurium sodium hydride or tellurium potassium hydride generated by the reaction of sodium borohydride or potassium borohydride and tellurium powder to obtain a CdxCo1-xTe precursor solution; then, obtaining a CdxCo1-xTe diluted magnetic fluorescent quantum dot by utilizing temperature controlled microwave or water bath (oil bath) heating reaction. The present invention controls the magnetic strength of the quantum dot by controlling the added quantity of cobalt, and controls the light emitting range of the quantum dot by controlling the synthesis time of the CdxCo1-xTe quantum dot. The method has the characteristics of simple operation, mild condition and low cost. The synthetic product CdxCo1-xTe has the characteristics of good water solubility, high stability, high fluorescence quantum yield, adjustable magnetism and adjustable emission spectrum, and is easy to connect with a biological macromolecule, etc.
Description
Technical field
The present invention relates to Cd
xCo
1-xThe water phase synthesis method of Te diluted magnetic fluorescent quantum dot is to be raw material with cadmium salt (or its oxide compound, oxyhydroxide), cobalt salt (or its oxide compound, oxyhydroxide) and sodium hydrogen telluride or telluretted hydrogen, utilizes microwave heating or water-bath (oil bath) to prepare Cd at water
xCo
1-xTe diluted magnetic fluorescent quantum dot belongs to nano material, magneticsubstance, photoelectric material technology of preparing and bioanalysis detection technique field.
Background technology
Quantum dot (quantum dots) claims semiconductor nanocrystal again, is the elementary composition nano particle of a kind of IIB-VIA of having or IIIB-VA family, and CdTe, CdSe belong to wherein common two kinds.This material is compared with organic fluorescent dye, has unique photoluminescent property, and wide as excitation wavelength range, emission wavelength ranges is narrow, and the Stokes displacement is big, the quantum yield height, and fluorescence lifetime is long, characteristics such as be difficult for photodissociation or drift.Fluorescence quantum is linked to each other with biomacromolecule, constitute biological fluorescent labeling, at immunoassay, genetic analysis, the living body fluorescent imaging, clinical diagnosis, fields such as drug screening are with a wide range of applications.Magnetic nano crystal is generally by transition metal such as iron, cobalt, nickel, chromium, manganese etc. and alloy composition, widespread use biomedical sector at present, as separate as the immune magnetic microsphere application cell, organoid separates and dna sequence analysis in DNA purifying etc.The diluted magnetic fluorescent quantum dot is a kind of novel nanocrystal, and it has luminescent properties and has magnetic again.Fluorescence and magnetic nano crystal are used for biomarker, can realize easily separating and detect.This novel nano-material is with a wide range of applications in bioseparation and in detecting.In addition, magnetic nano crystal also is good magneto-optic memory technique.The organic synthesis of the synthetic mainly employing of diluted magnetic fluorescent quantum dot at present method (D.J.Norris, et.al., Nano letter, 1,2001,3-7), the required reagent of this method costs an arm and a leg, and toxicity is big, synthesis condition harshness (needing 300 celsius temperatures), explosive, particularly its product is water insoluble, has limited its application greatly.
Summary of the invention
The objective of the invention is to defective, propose a kind of at the synthetic Cd of water at present organic synthesis method
xCo
1-xTe quantum dot novel method, this method have that resultant velocity is fast, the product good water solubility, magnetic is strong, quantum yield is high, easily with advantages such as biomacromolecule is connected.
For achieving the above object, the present invention is solvent with water, cadmium salt (or oxyhydroxide of the oxide compound of cadmium, cadmium), cobalt salt (or oxyhydroxide of the oxide compound of cobalt, cobalt) are mixed with water-soluble sulfhydryl compound, inject the sodium hydrogen telluride or the hydrogen telluride potassium that adopt sodium borohydride or POTASSIUM BOROHYDRIDE and the reaction of tellurium powder to generate, obtain Cd
xCo
1-xThe Te precursor solution utilizes temperature control microwave or water-bath (oil bath) reacting by heating to obtain Cd again
xCo
1-xTe diluted magnetic fluorescent quantum dot, its average quantum yield is 1-30%, has paramagnetism (saturated magnetic intensity is 0.1emu/g-5emu/g).
The present invention can control the magnetic intensity of quantum dot by controlling the amount that adds cobalt, by control Cd
xCo
1-xThe generated time of Te quantum dot is controlled the light emitting region of quantum dot.
Method of the present invention specifically comprises the steps:
1, with mol ratio is 1: 4 to 4: 1 sodium borohydride (NaBH
4) or POTASSIUM BOROHYDRIDE (KBH
4) placing water with tellurium powder (Te), reaction generates sodium hydrogen telluride (NaHTe) or hydrogen telluride potassium (KHTe) under 0-50 degree centigrade temperature.
2, with water be solvent, with concentration be the oxide compound of the cobalt salt of oxyhydroxide, 0.0001～0.1 mol of the oxide compound of the cadmium salt of 0.0001～0.1 mol or cadmium or cadmium or cobalt or cobalt oxyhydroxide, mix with water-soluble sulfhydryl compound, the pH value of regulator solution is to 3-12, cadmium and cobalt mol ratio were controlled at 1: 10 to 10: 1, metal ion total concn (Cd
2+, Co
2+) with the mol ratio of water-soluble sulfhydryl compound be 1: 5 to 5: 1, the sodium hydrogen telluride (NaHTe) or the hydrogen telluride potassium (KHTe) that obtain of implantation step 1 then, metal ion total concn (Cd
2+, Co
2+) with the mol ratio of NaHTe or KHTe be 10: 1 to 1: 4, under 0-50 degree centigrade temperature, stirred 1-10 minute, obtain Cd
xCo
1-xThe Te precursor solution.
3, with Cd
xCo
1-xThe Te precursor solution injects airtight polytetrafluoroethyltank tank, but reacts in the microwave reactor of temperature controllable and pressure control, or directly injects flask and utilize water-bath (oil bath) reacting by heating, obtains Cd
xCo
1-xTe diluted magnetic fluorescent quantum dot sol solution.Microwave heating condition is: microwave oscillation frequency 300MHZ～3000MHZ, microwave power 50W～1000W, 1 minute～10 hours heat-up time, 50～250 degrees centigrade of Heating temperatures.Water-bath (oil bath) heating condition is: 80-100 degree centigrade, and 1 minute～24 hours heat-up time.
The oxide compound of cadmium salt of the present invention or cadmium or the oxyhydroxide of cadmium comprise: cadmium nitrate, Cadmium oxide, cadmium perchlorate, cadmium chlorate, cadmium acetate, Cadmium Sulphate, cadmium iodate, cadmium hydroxide, Cadmium chloride fine powder, cadmium iodide, cadmium bromide, cadmium carbonate, Deng: the oxide compound of cobalt salt or cobalt or the oxyhydroxide of cobalt comprise Xiao Suangu, cobalt oxide, cobaltous perchlorate, cobaltous chlorate, Cobaltous diacetate, rose vitriol, acid iodide cobalt, cobaltous hydroxide, cobalt chloride, cobaltous iodide, cobaltous bromide, cobaltous carbonate, etc.; Water miscible sulfhydryl compound comprises: Thiovanic acid, thiohydracrylic acid, sulfydryl butyric acid, thioglycolate salt, mercapto propionate, sulfydryl butyrates, halfcystine, Gelucystine, thioglycerin, mercaptoethanol, mercaprol, 2,3-dimercapto-1-propyl alcohol, two-thiohydracrylic acid etc.
Method of the present invention is simple to operate, mild condition, and cost is low.Synthetic product Cd
xCo
1-xTe has water-soluble and good stability, the fluorescence quantum yield height, and magnetic is adjustable, and emmission spectrum is adjustable (480nm-800nm), easily with characteristics such as biomacromolecule are connected.
Embodiment
Below by several specific embodiments technical scheme of the present invention is further described, but component that embodiment provides and technical parameter do not limit technical scheme of the present invention.
Embodiment 1
(1). the sodium hydrogen telluride preparation
With 0.8 gram NaBH
4Solid and 1.32 gram Te powder place little flask, add 20 ml waters., after 8 hours solution is taken out in reaction under 25 degrees centigrade, standby.
(2). microwave synthesizes Cd
xCo
1-xTe diluted magnetic fluorescent quantum dot
With water is solvent, with 20 mmoles/rise CdCl
2, 20 mmoles/rise Co (NO
3)
2With 20 mmoles/rising thiohydracrylic acid (MPA) equal-volume ratio mixes, and regulates pH value to 11.Inject sodium hydrogen telluride NaHTe solution to concentration then and be 1 mmole/liter, stirred 5 minutes down at 25 degrees centigrade, obtain Cd
xCo
1-xTe precursor mixed solution.This solution is placed airtight polytetrafluoroethyltank tank, in the microwave reactor of temperature-control pressure-control, heat, obtain Cd by following condition
xCo
1-xTe diluted magnetic fluorescent quantum dot.
Microwave heating condition is: microwave oscillation frequency: 2450MHZ, and microwave power: 400W, heat-up time: 4 hours, Heating temperature: 70 degrees centigrade.
Embodiment 2
(1). the preparation of hydrogen telluride potassium
With 0.9 gram KBH
4Solid and 1.32 gram Te powder place little flask, add 20 ml waters., after 8 hours solution is taken out in reaction under 25 degrees centigrade, standby.
(2). microwave synthesizes Cd
xCo
1-xTe diluted magnetic fluorescent quantum dot
With water is solvent, with 8 mmoles/rise CdCl
2, 20 mmoles/rise Co (NO
3)
2With 12 mmoles/rising MPA equal-volume ratio mixes, and regulates pH value to 6.Inject then KHTe to concentration be 0.4 mmole/liter, stirred 10 minutes, obtain Cd
xCo
1-xTe precursor mixed solution.This solution is placed airtight polytetrafluoroethyltank tank, but in the microwave reactor of temperature controllable and pressure control, heat, obtain Cd by following condition
xCo
1-xTe diluted magnetic fluorescent quantum dot.
Microwave heating condition is: microwave oscillation frequency: 2450MHZ, and microwave power: 600W, heat-up time: 2 hours, Heating temperature: 160 degrees centigrade.
Embodiment 3
(1). the sodium hydrogen telluride preparation is identical with example 1.
(2). Cd is synthesized in water-bath (oil bath)
xCo
1-xTe diluted magnetic fluorescent quantum dot
With water is solvent, with 20 mmoles/rise CdCl
2, 20 mmoles/rise Co (NO
3)
2With 20 mmoles/rising MPA equal-volume ratio mixes, and regulates pH value to 11.Inject NaHTe solution to concentration then and be 1 mmole/liter, stirred 5 minutes down at 25 degrees centigrade, obtain Cd
xCo
1-xTe precursor mixed solution.This solution is put the 50ml flask, carry out reflux, obtain Cd by following condition
xCo
1-xTe diluted magnetic fluorescent quantum dot.
Water-bath (oil bath) heating condition is: heat-up time: 5 hours, and Heating temperature: 100 degrees centigrade.
Embodiment 4
(1). the preparation of hydrogen telluride potassium is identical with example 2.
With 0.9 gram KBH
4Solid and 1.32 gram Te powder place little flask, add 20 ml waters., after 8 hours solution is taken out in reaction under 25 degrees centigrade, standby.
(2). Cd is synthesized in water-bath (oil bath)
xCo
1-xTe diluted magnetic fluorescent quantum dot
With water is solvent, with 8 mmoles/rise CdCl
2, 20 mmoles/rise Co (NO
3)
2With 12 mmoles/rising MPA equal-volume ratio mixes, and regulates pH value to 6.Inject then KHTe to concentration be 0.4 mmole/liter, stirred 10 minutes, obtain Cd
xCo
1-xTe precursor mixed solution.This solution is put the 50ml flask, carry out reflux, obtain Cd by following condition
xCo
1-xTe diluted magnetic fluorescent quantum dot.
Water-bath (oil bath) heating condition is: heat-up time: 8 hours, and Heating temperature: 80 degrees centigrade.
Claims (2)
1, a kind of water phase synthesis method of diluted magnetic fluorescent cobalt-doped cadmium telluride alloy quantum dot is characterized in that comprising the steps:
1) with mol ratio is 1: 4 to 4: 1 sodium borohydride NaBH
4Or POTASSIUM BOROHYDRIDE KBH
4Te places water with the tellurium powder, and reaction generates sodium hydrogen telluride NaHTe or hydrogen telluride potassium KHTe under 0-50 degree centigrade temperature;
2) with water be solvent, with concentration is cadmium salt or the oxide compound of cadmium or the oxyhydroxide of cadmium of 0.0001～0.1 mol, 0.0001 the oxyhydroxide of the cobalt salt of～0.1 mol or the oxide compound of cobalt or cobalt mixes with water-soluble sulfhydryl compound, the pH value of regulator solution is to 3-12, cadmium and cobalt mol ratio were controlled at 1: 10 to 10: 1, the mol ratio of cadmium and cobalt ion total concn and water-soluble sulfhydryl compound is 1: 5 to 5: 1, the sodium hydrogen telluride NaHTe or the hydrogen telluride potassium KHTe that obtain of implantation step 1 then, the mol ratio of cadmium and cobalt ion total concn and NaHTe or KHTe is 10: 1 to 1: 4, under 0-50 degree centigrade temperature, stirred 1-10 minute, obtain Cd
xCo
1-xThe Te precursor solution;
3) with Cd
xCo
1-xThe Te precursor solution injects airtight polytetrafluoroethyltank tank, but reacts in the microwave reactor of temperature controllable and pressure control, or directly injects flask and utilize water-bath or oil bath reacting by heating, obtains Cd
xCo
1-xTe diluted magnetic fluorescent quantum dot sol solution; Microwave heating condition is: microwave oscillation frequency 300MHZ～3000MHZ, microwave power 50W～1000W, 1 minute～10 hours heat-up time, 50～250 degrees centigrade of Heating temperatures; Water-bath or oil bath heating condition are: 80-100 degree centigrade, and 1 minute～24 hours heat-up time.
2, according to the water phase synthesis method of the diluted magnetic fluorescent cobalt-doped cadmium telluride alloy quantum dot of claim 1, it is characterized in that the oxide compound of described cadmium salt or cadmium or the oxyhydroxide of cadmium are cadmium nitrate, Cadmium oxide, cadmium perchlorate, cadmium chlorate, cadmium acetate, Cadmium Sulphate, cadmium iodate, cadmium hydroxide, Cadmium chloride fine powder, cadmium iodide, cadmium bromide or cadmium carbonate; The oxide compound of described cobalt salt or cobalt or the oxyhydroxide of cobalt are Xiao Suangu, cobalt oxide, cobaltous perchlorate, cobaltous chlorate, Cobaltous diacetate, rose vitriol, acid iodide cobalt, cobaltous hydroxide, cobalt chloride, cobaltous iodide, cobaltous bromide or cobaltous carbonate; Described water miscible sulfhydryl compound is Thiovanic acid, thiohydracrylic acid, sulfydryl butyric acid, thioglycolate salt, mercapto propionate, sulfydryl butyrates, halfcystine, Gelucystine, thioglycerin, mercaptoethanol, mercaprol, 2,3-dimercapto-1-propyl alcohol or two-thiohydracrylic acid.
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|---|---|---|---|
| CN 200410093431 CN1266249C (en) | 2004-12-23 | 2004-12-23 | Water phase synthesis method for diluted magnetic fluorescent cobalt-doped cadmium telluride alloy quantum dot |
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|---|---|---|---|
| CN 200410093431 CN1266249C (en) | 2004-12-23 | 2004-12-23 | Water phase synthesis method for diluted magnetic fluorescent cobalt-doped cadmium telluride alloy quantum dot |
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| CN1266249C true CN1266249C (en) | 2006-07-26 |
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Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1328351C (en) * | 2005-09-23 | 2007-07-25 | 上海大学 | Method for preparing II-VI family fluorescent mark semiconductor quantum point MX |
| JP2009527437A (en) * | 2006-01-20 | 2009-07-30 | エージェンシー フォー サイエンス， テクノロジー アンド リサーチ | Synthesis of alloy nanocrystals in aqueous or water-soluble solvents |
| CN102994093A (en) * | 2012-11-30 | 2013-03-27 | 广西师范学院 | Method for synthesizing Co-doped CdxCo1-xTe quantum dot by hydrothermal method |
| CN103074067A (en) * | 2012-12-19 | 2013-05-01 | 广西师范学院 | Preparation method of water-soluble Co-doped CdxCo1-xTe quantum dot |
| CN103760201A (en) * | 2013-12-10 | 2014-04-30 | 天津工业大学 | Preparation method of composite quantum dot-based electrochemical DNA sensor |
| CN105385436B (en) * | 2015-12-03 | 2017-06-23 | 东南大学 | A kind of nontoxic dilute coupled magnetic quantum dot material for having fluorescence and room-temperature ferromagnetic concurrently and preparation method thereof |
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