CN1234601C - Aqueous phase synthesis for high quality cadmium selenide quantum dots in temperature controlled microwave reactor - Google Patents
Aqueous phase synthesis for high quality cadmium selenide quantum dots in temperature controlled microwave reactor Download PDFInfo
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- CN1234601C CN1234601C CN 200410018022 CN200410018022A CN1234601C CN 1234601 C CN1234601 C CN 1234601C CN 200410018022 CN200410018022 CN 200410018022 CN 200410018022 A CN200410018022 A CN 200410018022A CN 1234601 C CN1234601 C CN 1234601C
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Abstract
The present invention relates to a water phase synthesis method for cadmium selenide quantum dots of high quality in a temperature controlled microwave reactor. In the method, water is used as a solvent, and the method comprises the following steps: mixing cadmium salts or cadmium oxides with a water soluble sulfhydryl compound and injecting selenium sodium hydride or selenium potassium hydride generated by the reaction of sodium borohydride or potassium borohydride with selenium powder to obtain a cadmium selenide precursor solution; then putting the solution in an airtight polytetrafluoroethylene tank to react in a temperature controlled microwave reactor, and quickly synthesizing cadmium selenide fluorescent quantum dots. The method of the present invention has the characteristics of simple operation, mild condition and low cost. The synthetic product of cadmium selenide has the characteristics of good water solubility, high stability, high fluorescence quantum yield and adjustable emission spectrum, and is easy to connect with a biological macromolecule, etc.
Description
Technical field
The present invention relates to the temperature control microwave water phase synthesis method of a kind of cadmium selenide (CdSe) quantum dot, be with cadmium salt (or its oxide compound, oxyhydroxide) and sodium hydrogen selenide (or selenium potassium hydride KH), prepare the CdSe quantum dot at the microwave heating method of water by temperature controllable, belong to nano material preparation technology and bioanalysis detection technique field.
Background technology
The CdSe quantum dot is called the CdSe nanocrystal again, is a kind of luminescent material of excellent property.It is compared with organic fluorescent dye, has unique photoluminescent property, and wide as excitation wavelength range, emission wavelength ranges is narrow, and Stocks (this drags Ke Si) displacement is big, the quantum yield height, and fluorescence lifetime is long, characteristics such as be difficult for photodissociation or drift.In opto-electronic device preparation and life science, be with a wide range of applications.People link to each other the CdSe quantum dot with biomacromolecule at present, constitute biological fluorescent labeling, are used for immunoassay, genetic analysis, living body fluorescent imaging, clinical diagnosis, fields such as drug screening.The synthetic main at present employing organic synthesis method of CdSe (Murray C.B., et.al., J.Am.Chem.Soc., 1993,115,8706-8715.), the product C dSe quantum yield height that this method obtains, emmission spectrum narrow range.But the required reagent of this method costs an arm and a leg, and toxicity is big, synthesis condition harshness (needing 300 celsius temperatures), and explosive, particularly its product C dSe is water insoluble, has limited its application greatly.Studies show that recently the water method also can be used for the synthetic of CdSe quantum dot, the product good water solubility that this method obtains easily is connected with biomacromolecule.But the synthetic CdSe of water generally adopts heating in water bath method (RogachA.L at present, et.al., J.Phys.Chem.B, 1999,103,3065-3069.) required time of this method long, the gained quantum dot is a defect luminescence, so the quantum yield very low (below 1%) of its product can not be used for biomarker.
Summary of the invention
The objective of the invention is to defective at present water and organic synthesis method, a kind of novel method at the water synthetizing CdSe quantum dots is provided, has that synthesis step is simple, resultant velocity is fast, synthesis condition is gentle, a product good water solubility, emmission spectrum is adjustable, quantum yield is high advantage.
For achieving the above object, the present invention is a raw material with cadmium salt (or the oxide compound of cadmium, oxyhydroxide) and sodium hydrogen selenide (or selenium potassium hydride KH), in the aqueous solution, utilize the microwave heating of temperature controllable pressure control, synthetic rapidly CdSe fluorescence quantum, its quantum yield can reach more than 30%.
Method of the present invention specifically comprises the steps:
1, the preparation of sodium hydrogen selenide (or selenium potassium hydride KH):
With mol ratio 1: 4 to 4: 1 sodium borohydride (NaBH
4) or POTASSIUM BOROHYDRIDE (KBH
4) and selenium powder (Se) place water, reaction generates sodium hydrogen selenide (NaHSe) or selenium potassium hydride KH (KHSe) under 0-50 degree centigrade temperature.
2, synthesize the CdSe quantum dot by microwave heating at water:
With water is solvent, with concentration is that the cadmium salt of 0.00001～0.1 mol, the oxide compound or the oxyhydroxide of cadmium mix with water-soluble sulfhydryl compound, the pH value of regulator solution is to 7-12, the mol ratio of the oxide compound of cadmium salt, cadmium or oxyhydroxide and water-soluble sulfhydryl compound is 1: 5 to 5: 1, inject sodium hydrogen selenide (NaHSe) or selenium potassium hydride KH (KHSe) then, the mol ratio of the oxide compound of cadmium salt, cadmium or oxyhydroxide and NaHSe (or KHSe) is 10: 1 to 1: 4, under 0-100 degree centigrade temperature, stirred 1-10 minute, obtain the CdSe precursor solution.This solution is placed airtight polytetrafluoroethyltank tank, in the microwave reactor of temperature controllable, react, generate the CdSe fluorescence quantum.
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.
The oxide compound or the oxyhydroxide of cadmium salt of the present invention, 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, 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, dimercapto propionic acid etc.
Method of the present invention is simple to operate, mild condition, and cost is low.Synthetic product CdSe has water-soluble and good stability, the fluorescence quantum yield height, and emmission spectrum is adjustable, easily with characteristics such as biomacromolecule are connected.
Embodiment
Below by several specific embodiments technical scheme of the present invention is further described.
Embodiment 1
(1). the sodium hydrogen selenide preparation
0.8 gram sodium borohydride solids and 0.8 gram selenium powder are put in the little flask, added 10 ml waters., after 2 hours solution is taken out in reaction under 25 degrees centigrade, standby.
(2). synthesize the CdSe quantum dot by microwave heating at water
With water is solvent, with 20 mmoles/rise Cadmium chloride fine powder and 20 mmoles/rise the thiohydracrylic acid equal-volume than mixing, regulates pH value to 11.Inject sodium hydrogen selenide solution to concentration then and be 1 mmole/liter, stirred 5 minutes down at 25 degrees centigrade, obtain the CdSe precursor solution.This solution is placed airtight polytetrafluoroethyltank tank, in the microwave reactor of temperature controllable, heat, obtain the CdSe fluorescence quantum by following condition.
Microwave heating condition is:
Microwave oscillation frequency: 2450MHZ
Microwave power: 400W,
Heat-up time: 4 hours
Heating temperature: 100 degrees centigrade.
Embodiment 2
(1). the preparation of selenium potassium hydride KH
0.9 gram sodium borohydride solids and 0.9 gram selenium powder are put in the little flask, added 20 ml waters., after 2 hours solution is taken out in reaction under 25 degrees centigrade, standby.
(2). synthesize the CdSe quantum dot by microwave heating at water
With water is solvent, with 8 mmoles/rise Cadmium chloride fine powder and 12 mmoles/rise the thiohydracrylic acid equal-volume than mixing, regulates pH value to 7.Inject selenium potassium hydride KH to concentration then and be 0.4 mmole/liter, stirred 10 minutes, obtain the CdSe precursor solution.This solution is placed airtight polytetrafluoroethyltank tank, in the microwave reactor of temperature controllable, heat, obtain the CdSe fluorescence quantum by following condition.
Microwave heating condition is:
Microwave oscillation frequency: 2450MHZ
Microwave power: 600W
Heat-up time: 2 hours,
Heating temperature: 160 degrees centigrade.
Embodiment 3
(1). the sodium hydrogen selenide preparation is identical with example 1.
(2). synthesize the CdSe quantum dot by microwave heating at water
With water is solvent, with 1.2 mmoles/rise Cadmium chloride fine powder and 1 mmole/rise the thiohydracrylic acid equal-volume than mixing, regulates pH value to 9.Inject sodium hydrogen selenide to concentration then and be 0.2 mmole/liter, stirred 5 minutes down at 25 degrees centigrade, obtain the CdSe precursor solution.This solution is placed airtight polytetrafluoroethyltank tank, in the microwave reactor of temperature controllable, heat, obtain the CdSe fluorescence quantum by following condition.
Microwave heating condition is:
Microwave oscillation frequency: 2450MHZ
Microwave power: 600W,
Heat-up time: 0.5 hour
Heating temperature: 180 degrees centigrade.
Claims (2)
1, a kind of temperature control microwave water phase synthesis method of CdSe quantum dots is characterized in that comprising the steps:
1) preparation of sodium hydrogen selenide or selenium potassium hydride KH: with mol ratio is that 1: 4 to 4: 1 sodium borohydride or POTASSIUM BOROHYDRIDE and selenium powder place water, and reaction generates sodium hydrogen selenide or selenium potassium hydride KH under 0-50 degree centigrade temperature;
2) water of CdSe quantum dots is synthetic: with water is solvent, with concentration is the cadmium salt of 0.00001～0.1 mol, the oxide compound of cadmium or oxyhydroxide mix with water-soluble sulfhydryl compound, pH value to 7～12 of regulator solution, cadmium salt, the mol ratio of the oxide compound of cadmium or oxyhydroxide and water-soluble sulfhydryl compound is 1: 5 to 5: 1, inject sodium hydrogen selenide or selenium potassium hydride KH then, cadmium salt, the mol ratio of the oxide compound of cadmium or oxyhydroxide and sodium hydrogen selenide or selenium potassium hydride KH is 10: 1 to 1: 4, under 0～100 degree centigrade temperature, stirred 1～10 minute, obtain the cadmium selenide precursor solution, this solution is placed airtight polytetrafluoroethyltank tank, in the microwave reactor of temperature controllable, react, generate the cadmium selenide fluorescence quantum, 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.
2, the temperature control microwave water phase synthesis method of CdSe quantum dots as claimed in claim 1, it is characterized in that described cadmium salt, the oxide compound of cadmium or oxyhydroxide 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, described water miscible sulfhydryl compound is a Thiovanic acid, thiohydracrylic acid, the sulfydryl butyric acid, thioglycolate salt, mercapto propionate, the sulfydryl butyrates, halfcystine, Gelucystine, thioglycerin, mercaptoethanol, mercaprol, 2,3-dimercapto-1-propyl alcohol or dimercapto propionic acid.
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Families Citing this family (9)
| 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 |
| CN100567986C (en) * | 2005-12-22 | 2009-12-09 | 复旦大学 | The preparation method of a kind of water-soluble CdTe/CdS core/shell type quantum dot |
| CN100509617C (en) * | 2007-01-04 | 2009-07-08 | 山东师范大学 | Method of synthesizing cadmium selenide nano stick |
| CN101250403B (en) * | 2008-02-28 | 2010-06-23 | 上海交通大学 | Method for synthesizing water-soluble long-chain mercapto compound coated cadmium telluride quantum dot |
| CN102795605A (en) * | 2012-08-06 | 2012-11-28 | 西北工业大学 | Method for preparing nanometer material lead selenide by aqueous phase method |
| WO2016086511A1 (en) * | 2014-12-05 | 2016-06-09 | 上海交通大学 | Method for preparing self-passivating quantum dots |
| CN105618086B (en) * | 2015-12-17 | 2018-06-26 | 江苏大学 | A kind of preparation and its application of vesica shape CdSe Nano semiconductor photochemical catalysts |
| CN113443835B (en) * | 2021-06-25 | 2022-07-26 | 中山大学 | Preparation of ZnO/CdO/CdSe composite film and application thereof in photoelectrochemical cathode protection |
| CN115744967B (en) * | 2022-11-16 | 2023-05-09 | 唐山学院 | Preparation method of plate flower cluster epsilon-cadmium iodate and application of plate flower cluster epsilon-cadmium iodate in sewage treatment |
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