CN104531141A - Microwave aqueous phase preparation method of cerium and erbium co-doped ZnS quantum dot - Google Patents

Microwave aqueous phase preparation method of cerium and erbium co-doped ZnS quantum dot Download PDF

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CN104531141A
CN104531141A CN201410771998.5A CN201410771998A CN104531141A CN 104531141 A CN104531141 A CN 104531141A CN 201410771998 A CN201410771998 A CN 201410771998A CN 104531141 A CN104531141 A CN 104531141A
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quantum dot
erbium
cerium
zns quantum
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CN104531141B (en
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胡智学
徐进
陈玉霞
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Nanjing College of Chemical Technology
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Nanjing College of Chemical Technology
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Abstract

The invention relates to a microwave aqueous phase preparation method of a cerium and erbium co-doped ZnS quantum dot. The method is characterized in that Zn (CH3COO)2.2H2O serving as a zinc source, Ce(NO3)3.6H2O serving as a cerium source and Er(NO3)3.5H2O serving as an erbium source are prepared to form a mixed solution containing three ions, and Na2S.9H2O serving as a sulfur source is subjected to microwave heating under protection of nitrogen by utilizing glutathione (GSH) as a stabilizing agent at a certain pH value so as to obtain the cerium and erbium co-doped ZnS quantum dot. The microwave preparation method uses non-toxic raw materials and is simple and environmentally-friendly in process, and the reaction time is less than 1 hour; the prepared quantum dot has a uniform grain size which is 2-5nm, has excellent water solubility, excellent electrochemical performance and good fluorescent stability, has controllable and adjustable fluorescence emission peak in a range of 430-503nm, and can be widely applied to the aspects of fluorescent probes, medicine screening, heavy metal ion detection and the like.

Description

The microwave aqueous phase preparation method of a kind of cerium, erbium-codoped ZnS quantum dot
Technical field
The present invention relates to a kind of preparing technical field of novel fluorescence quanta point material, particularly the microwave aqueous phase preparation method of a kind of cerium, erbium-codoped ZnS quantum dot.
Background technology
Quantum dot is a kind of novel semiconductor material, and due to quantum size effect, quantum dot has special physics and chemistry character.Doped quantum dot refers to introduce transition metal ion or rare earth ion impurity and the nano material formed in main body.The foreign ion of usual introducing is a small amount of or micro-, does not generally change the crystalline structure of main body nanoparticle.The foreign ion mixing host lattice can produce new electronic level or produce perturbation to the electronic level of main body, forms new electronics one hole recombination centers, thus makes doped with nanometer particle have brand-new optical, electrical or magnetic properties.ZnS quantum dots has excellent fluorescence property, and its body band gap is 3.66 ev, is excellent broad-band gap luminescent material, for metal ion mixing provides energy level scope.
The preparation method of ZnS quantum dots mainly adopts organic synthesis method, the shortcomings such as the method severe reaction conditions, expensive reagents, raw material are poisonous; Employing microwave-hydrothermal method is simple to operate, and temperature of reaction is low, and the reaction times is short.Coating materials adopts eco-friendly gsh modify the surface of quantum dot, avoid using poisonous Thiovanic acid.
Summary of the invention
The object of the present invention is to provide the microwave aqueous phase preparation method of a kind of cerium, erbium-codoped ZnS quantum dot.The particle diameter of this quantum dot is 2 nm ~ 5 nm, well water-soluble, has excellent chemical property and fluorescence property.
The technical solution used in the present invention is:
A kind of cerium of the present invention, erbium-codoped ZnS quantum dot, the molar ratio of cerium ion and zine ion is 0.01:1 ~ 0.03:1; The molar ratio of erbium ion and zine ion is 0.01:1 ~ 0.05:1.
A preparation method for cerium, erbium-codoped ZnS quantum dot, concrete steps are as follows:
(1) by the Ce (NO of certain mol proportion example 3) 36H 2o, Er (NO 3) 35H 2o and Zn (CH 3cOO) 22H 2o is dissolved in deionized water, wiring solution-forming, and magnetic agitation is even;
(2) by gsh (GSH), NaOH, Na 2s9H 2o is dissolved in deionized water respectively, is made into certain density GSH solution, NaOH solution, Na 2s9H 2o solution;
(3) under nitrogen protection, GSH solution is added dropwise in step (1) solution, stirs;
(4) by the pH value of NaOH solution regulating step (3) solution, stir; Slowly add Na 2s9H 2o solution, stirs;
(5) water-bath of step (4) solution microwave is heated to 70 ~ 90 DEG C, reacts 10 minutes ~ 50 minutes, namely arrive cerium, the erbium-codoped ZnS quantum dot aqueous solution;
(6) after the cooling of step (5) solution, add the dehydrated alcohol of equivalent, separate out white precipitate, centrifugation, with washes of absolute alcohol precipitation several, vacuum-drying obtains cadmium, ytterbium codoped ZnS quantum dot.
In step (1), the volumetric molar concentration of zine ion is 0.01 ~ 0.05 mol/L, and the volumetric molar concentration of cerium ion is 0.005 ~ 0.03mol/L, and the volumetric molar concentration of erbium ion is 0.005 ~ 0.02 mol/L.
In step (3), high pure nitrogen is passed in solution half an hour, then add GSH solution under nitrogen protection.
In step (3), the molar ratio of GSH and zine ion is 1:1 ~ 2:1.
In step (4), the molar ratio of sulfonium ion and zine ion is 1:1 ~ 1.2:1.
Major advantage of the present invention is: by the synthesis of microwave Aqueous phase cerium, erbium-codoped ZnS quantum dot, the advantages of nontoxic raw materials that this preparation method is used, the simple and environmental protection of technique, and temperature of reaction is low, and the reaction times is short; Gained quantum dot uniform particle sizes (2 nm ~ 5 nm), excellent water-solubility, chemical property is good, fluorescent stability is good, by changing ratio, the temperature of reaction of dopant ion, and the parameter such as reaction times, fluorescence emission peak is controllable adjustment between 430 nm ~ 503 nm.
Accompanying drawing explanation
Fig. 1 is cerium prepared in the embodiment of the present invention 1, the fluorescence emission spectrogram (PL) of erbium-codoped ZnS quantum dot.
Fig. 2 is cerium prepared in the embodiment of the present invention 1, the high-resolution electron microscopy figure (HRTEM) of erbium-codoped ZnS quantum dot.
Embodiment
In order to illustrate in greater detail feature of the present invention, below by concrete embodiment, the invention will be further elaborated, instead of limit the scope of the invention.
Embodiment 1:
By the Zn (CH that 60 mL volumetric molar concentrations are 0.02 mol/L 3cOO) 22H 2o solution is placed in a there-necked flask, adds the Ce (NO that 2 mL volumetric molar concentrations are 0.01 mol/L 3) 36H 2o solution 3 mL volumetric molar concentration is the Er (NO of 0.01 mol/L 3) 35H 2o solution, magnetic agitation is even; Pass into high pure nitrogen half an hour, be that gsh (GSH) solution of 0.1 mol/L is added drop-wise in above-mentioned solution by 12 mL volumetric molar concentrations, magnetic agitation is even;
Under nitrogen protection, regulate above-mentioned solution ph to be 11 by NaOH solution, continue magnetic agitation even; Slowly add the Na that 12mL concentration is 0.1 mol/L 2s9H 2o solution, continues to stir half an hour; Microwave Water heat phase, temperature of reaction 80 DEG C, the reaction times is 25 minutes, obtains cerium, the erbium-codoped ZnS quantum dot aqueous solution.After solution cooling, add the dehydrated alcohol of equivalent, solution separates out white precipitate, centrifugation, and with washes of absolute alcohol throw out 3 times, vacuum-drying obtains cerium, erbium-codoped ZnS quantum dot.
Embodiment 2:
By the Zn (CH that 50 mL volumetric molar concentrations are 0.01 mol/L 3cOO) 22H 2o solution is placed in a there-necked flask, adds the Ce (NO that 1 mL volumetric molar concentration is 0.01 mol/L 3) 36H 2o solution, 2 mL volumetric molar concentrations are the Er (NO of 0.01 mol/L 3) 35H 2o solution, magnetic agitation is even; Pass into high pure nitrogen half an hour, be that gsh (GSH) solution of 0.1 mol/L is added drop-wise in above-mentioned solution by 6 mL volumetric molar concentrations, magnetic agitation is even;
Under nitrogen protection, regulate above-mentioned solution ph to be 8 by NaOH solution, continue magnetic agitation even; Slowly add the Na that 5 mL concentration are 0.1 mol/L 2s9H 2o solution, continues to stir half an hour; Microwave Water heat phase, temperature of reaction 90 DEG C, the reaction times is 10 minutes, obtains cerium, the erbium-codoped ZnS quantum dot aqueous solution.After solution cooling, add the dehydrated alcohol of equivalent, solution separates out white precipitate, centrifugation, and with washes of absolute alcohol throw out 3 times, vacuum-drying obtains cerium, erbium-codoped ZnS quantum dot.
Embodiment 3:
By the Zn (CH that 30 mL volumetric molar concentrations are 0.03 mol/L 3cOO) 22H 2o solution is placed in a there-necked flask, adds the Ce (NO that 1 mL volumetric molar concentration is 0.02 mol/L 3) 36H 2o solution, 1 mL volumetric molar concentration is the Er (NO of 0.02 mol/L 3) 35H 2o solution, magnetic agitation is even; Pass into high pure nitrogen half an hour, be that gsh (GSH) solution of 0.1 mol/L is added drop-wise in above-mentioned solution by 15 mL volumetric molar concentrations, magnetic agitation is even;
Under nitrogen protection, regulate above-mentioned solution ph to be 13 by NaOH solution, continue magnetic agitation even; Slowly add the Na that 10mL concentration is 0.1 mol/L 2s9H 2o solution, continues to stir half an hour; Microwave Water heat phase, temperature of reaction 70 DEG C, the reaction times is 50 minutes, obtains cerium, the erbium-codoped ZnS quantum dot aqueous solution.After solution cooling, add the dehydrated alcohol of equivalent, solution separates out white precipitate, centrifugation, and with washes of absolute alcohol throw out 3 times, vacuum-drying obtains cerium, erbium-codoped ZnS quantum dot.
Embodiment 4:
By the Zn (CH that 30 mL volumetric molar concentrations are 0.05 mol/L 3cOO) 22H 2o solution is placed in a there-necked flask, adds the Ce (NO that 1 mL volumetric molar concentration is 0.03 mol/L 3) 36H 2o solution, 1 mL volumetric molar concentration is the Er (NO of 0.02 mol/L 3) 35H 2o solution, magnetic agitation is even; Pass into high pure nitrogen half an hour, be that gsh (GSH) solution of 0.1 mol/L is added drop-wise in above-mentioned solution by 18 ml volumetric molar concentrations, magnetic agitation is even;
Under nitrogen protection, regulate above-mentioned solution ph to be 10 by NaOH solution, continue magnetic agitation even; Slowly add the Na that 15 mL concentration are 0.1 mol/L 2s9H 2o solution, continues to stir half an hour; Microwave Water heat phase, temperature of reaction 90 DEG C, the reaction times is 20 minutes, obtains cerium, the erbium-codoped ZnS quantum dot aqueous solution.After solution cooling, add the dehydrated alcohol of equivalent, solution separates out white precipitate, centrifugation, and with washes of absolute alcohol throw out 3 times, vacuum-drying obtains cerium, erbium-codoped ZnS quantum dot.

Claims (2)

1. a microwave aqueous phase preparation method for cerium, erbium-codoped ZnS quantum dot, is characterized in that:
(1) by the Ce (NO of certain mol proportion example 3) 36H 2o, Er (NO 3) 35H 2o and Zn (CH 3cOO) 22H 2o is dissolved in deionized water, wiring solution-forming, and magnetic agitation is even;
(2) by gsh (GSH), NaOH, Na 2s9H 2o is dissolved in deionized water respectively, is made into certain density GSH solution, NaOH solution, Na 2s9H 2o solution;
(3) under nitrogen protection, GSH solution is added dropwise in step (1) solution, stirs;
(4) by the pH value of NaOH solution regulating step (3) solution, stir; Slowly add Na 2s9H 2o solution, stirs;
(5) by step (4) solution microwave heating in water bath, cerium, the erbium-codoped ZnS quantum dot aqueous solution is namely arrived;
(6) after the cooling of step (5) solution, add the dehydrated alcohol of equivalent, separate out white precipitate, centrifugation, with washes of absolute alcohol precipitation several, vacuum-drying obtains cadmium, ytterbium codoped ZnS quantum dot.
2. preparation method as claimed in claim 1, it is characterized in that: in step (1), the molar ratio of cerium ion and zine ion is 0.01:1 ~ 0.03:1; The molar ratio of erbium ion and zine ion is 0.01:1 ~ 0.05:1.
CN201410771998.5A 2014-12-16 2014-12-16 A kind of microwave aqueous phase preparation method of cerium, erbium-codoped ZnS quantum dot Expired - Fee Related CN104531141B (en)

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CN1324912A (en) * 2000-05-19 2001-12-05 中国科学院长春光学精密机械与物理研究所 Fluorescnet material to convert and combine blue light of LED into white light
JP2006077111A (en) * 2004-09-09 2006-03-23 Nippon Hoso Kyokai <Nhk> Phosphor material
CN1974719A (en) * 2006-12-12 2007-06-06 天津理工大学 Core-shell structure Zn(1-x)M2S4:Ax/ZnS quantum dot and its prepn process
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