CN101423760B - High fluorescent efficiency cadmium telluride quantum point prepared by cathodic tellurium electric pole - Google Patents
High fluorescent efficiency cadmium telluride quantum point prepared by cathodic tellurium electric pole Download PDFInfo
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- CN101423760B CN101423760B CN2007101345343A CN200710134534A CN101423760B CN 101423760 B CN101423760 B CN 101423760B CN 2007101345343 A CN2007101345343 A CN 2007101345343A CN 200710134534 A CN200710134534 A CN 200710134534A CN 101423760 B CN101423760 B CN 101423760B
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Abstract
The invention relates to a method for preparing high fluorescence-efficiency cadmium telluride quantum dots through cathodic tellurium electrodes. The method is characterized in that: (1) stable tellurium rods are taken as tellurium electrodes; under the electric potential between 0.95 V below zero and 1.2 V below zero (relative to Ag|AgCl|KCl(sat.) electrodes), the cathodic tellurium electrodes are used as a tellurium source to prepare a cadmium telluride precursor solution, so as to replace a sodium hydrogen telluride or hydrogen telluride source easy to oxidize by air, or an aluminum telluride source easy to absorb water; therefore, the preparation of the quantum dots can be carried out in an open system without specific protective atmosphere; (2) the cadmium telluride quantum dots with different modified groups on the surfaces can be prepared by taking a mercapto-compound as a stabilizer; (3) preparation process is completed in an aqueous phase at a temperature between 70 and 100 DEG C, and the water-soluble quantum dots used for biological markers and detection can be prepared; and (4) the particle size and maximum emission wavelength of the cadmium telluride quantum dots canbe adjusted by controlling heating time. The cadmium telluride quantum dots synthesized in the invention have the particle size between 2.0 and 5.0 nanometers, the maximum emission wavelength between 500 and 650 nanometers, the emission-spectrum half-peak width between 40 and 55 nanometers, as well as the fluorescence quantum yield from 60 to 78 percent. The method has the characteristics of convenience, rapidness, environment protection, good reproducibility, low cost and the like, provides a feasible way for synthesizing high-quality cadmium telluride quantum dots, and can have wide application prospects in the nanometer devices, optoelectronics, biological sensing and other fields.
Description
One, technical field
The invention belongs to the preparation method of the semiconductor-quantum-point in the field of nanometer material technology.It uses electrochemical method, by negative electrode tellurium electrode preparation cadmium telluride presoma, with the compound that contains sulfydryl or can be stablizer with cadmium ion coordinate compound, water prepares the high fluorescence efficiency cadmium telluride quantum dot, and this quantum dot can all have broad application prospects in fields such as nano-device, photoelectronics and bio-sensings.
Two, background technology
Cadmium telluride quantum dot is because quantum size effect and dielectric confinement effect, emission wavelength can be by green glow to ruddiness, and its unique photoelectric characteristic makes cadmium telluride quantum dot receive publicity day by day in the application in solid luminescent [1], optical communication [2] and bio-imaging and detection [3] field.Compare advantage such as aqueous phase synthesis method has that cost is low, easy to operate, toxicity is little, stable height and bio-compatibility be good in the aqueous solution with the metal organic solvent method.At present, the tellurium source of the synthetic cadmium telluride quantum dot of water mainly is sodium hydrogen telluride and tellurium aluminium, and sodium hydrogen telluride need pass through tellurium powder and borane reducing agent sodium hydride prepared in reaction [4], and tellurium aluminium easily absorbs airborne water, be difficult for to store, during use with sulfuric acid reaction generation telluretted hydrogen.These two kinds of tellurium sources by airborne dioxygen oxidation, need on-site preparation because of easily, and need to use vacuum line technology (Schlenk line), so preparation process is comparatively complicated.
Because temperature was low when water was synthetic, nanocrystalline among the existing preparation method do not have clear and definite nucleation and growth boundary, causes the quantum dot fluorescence half-peak width broad that obtained, and size distribution is inhomogeneous, quantum yield lower (3%～10%) [5].Zhang Hao etc. [6] are in order to improve the fluorescence efficiency of the synthetic quantum dot of water, and under higher temperature and pressure, at the synthetic CdTe nano-quantum point of aqueous phase, the maximum fluorescence quantum yield also has only 30% with hydrothermal method.In order to overcome the shortcoming and the dealing with various requirements of existing quantum dot, people are constantly attempting changing synthesis condition, improve fluorescence quantum yield.Use tellurium electrode preparation cadmium telluride presoma among the present invention, the synthetic cadmium telluride quantum dot has higher high fluorescence efficiency, for the application of quantum dot is laid a good foundation.
[1]M.Gao，C.Lesser，S.Kirstein?et?al.，J.?Appl?Phys.2000，87，2297.
[2]G.Z.Zou，H.X.Ju，Anal.Chem.2004，76，6871.
[3]M.Bruchez，M.Moronne，P.Gin?et?al.，Science?1998，281，2013.
[4]D.L.Klayman，T.S.Griffin，J.?Am.Chem.Soc.1973，95，197.
[5]N.Gaponik，D.V.Talapin，A.L.Rogach?et?al.，J.?Phys.Chem.B?2002，106，7177.
[6]H.Zhang，L.Wang，H.Xiong，et?al.，Adv.Mater.2003，15，1712.
Three, summary of the invention
The objective of the invention is: propose a kind of method of synthetic high fluorescence efficiency cadmium telluride quantum dot, use electrochemical method, by negative electrode tellurium electrode preparation cadmium telluride presoma.Synthetic operation carries out in the system of opening wide; do not need to use specific protective atmosphere; have characteristics such as easy, quick, green, favorable reproducibility and cost be low; for synthetic high quality cadmium telluride quantum dot provides a practicable approach, will all have broad application prospects in fields such as nano-device, photoelectronics and clinical diagnosises.
The present invention is achieved through the following technical solutions, and its step is as follows:
(1) preparation of tellurium electrode is sealed in the tellurium rod in Glass tubing or the polyfluortetraethylene pipe with Resins, epoxy, and the other end links to each other with lead to fill graphite.
(2) cadmium source solution preparation: with Cadmium chloride fine powder, cadmium perchlorate, Cadmium Sulphate or cadmium nitrate is the cadmium source, is stablizer with sulfhydryl compound or water-soluble polymer, prepares the sulfydryl title complex of cadmium, and regulates pH value to 11 with sodium hydroxide.The mol ratio of Cadmium chloride fine powder and coloured glaze based compound is 1: 1.5～1: 4.
(3) preparation of cadmium telluride precursor solution: with the tellurium electrode is that working electrode, Ag/AgCl electrode are that reference electrode, Pt silk are counter electrode, cadmium source solution is electrolytic solution, behind the dissolved oxygen in the logical nitrogen removal electrolytic solution,-0.90～-carry out electrolysis under the negative electrode current potential of 1.2V, the tellurium ionic weight that generates can be by flowing through the electric energy control of working electrode, and the mol ratio of cadmium and tellurium was controlled at 1: 0.3～1: 0.6.
(4) formation of cadmium telluride quantum dot: the cadmium telluride precursor solution of preparation in (3) is heated (80 ℃ of quantum dot crystal formation the bests that add thermosetting) in 70～95 ℃ water-bath, control can be regulated the particle diameter of the cadmium telluride quantum dot that makes, maximum emission wavelength and fluorescence quantum yield heat-up time.
(5) purifying of cadmium telluride quantum dot: the cadmium telluride quantum dot solution that makes is placed dialysis tubing, and dialysis is 24 hours in secondary water, removes free ions and unnecessary stablizer, can get the cadmium telluride quantum dot solution that stablizer coats.
Cadmium telluride quantum dot has stability preferably, can preserve the several months under 4 ℃ of environment.
Characteristics of the present invention are to be electrode materials with stable tellurium, and preparation tellurium electrode provides the tellurium source with electrochemical method by negative electrode tellurium electrode.Reaction with the synthetic cadmium telluride quantum dot of this method can be carried out in the system of opening wide, and does not need to use vacuum line equipment, has simplified experimental implementation.By the nucleation time of control cadmium telluride quantum dot, can regulate the particle diameter and the emission wavelength of cadmium telluride quantum dot.The particle diameter of the cadmium telluride quantum dot that this method makes is that 2.0～5.0nm, maximum emission wavelength are 500～650nm, and the emission spectrum peak width at half height is that 40～55nm, fluorescence quantum yield are 60～78%.Reaction repeatability is high, and cost is low, and is little to the pollution of environment.
Four, description of drawings
Fig. 1. the synoptic diagram of the cadmium telluride quantum dot that preparation Thiovanic acid (TGA) coats.
Fig. 2. cadmium telluride quantum dot particle diameter that Thiovanic acid (TGA) and ethanoyl half light Gelucystine (ACYS) coat and fluorescence efficiency are with the variation of heat-up time in the water-bath.
Five, embodiment
The preparation of the cadmium telluride quantum dot that embodiment 1. Thiovanic acids (TGA) coat:
(1) with 20mL 5mM CdCl
2Mix with 17 μ L Thiovanic acids, with being diluted to 40mL behind the 0.1M NaOH adjusting pH to 11.2, the logical nitrogen of gained colorless cleared solution 30 minutes.
(2) be electrolytic solution with the solution that obtains in (1), the Ag/AgCl electrode is a reference electrode, the Pt silk is a counter electrode, the tellurium electrode is a working electrode, under the current potential of-0.95V, keep the regular hour, as controlling electrolysis time respectively is that the mol ratio of cadmium and tellurium was respectively 1: 0.41 and 1: 0.64 1: 0.20 in 15,30 and 46 minutes gained cadmium telluride precursor solutions.It is faint yellow that precursor solution is.
(3) the cadmium telluride precursor solution is placed different time of water-bath reflux of 80 ℃, the quantum dot size that obtains can prolong in time and increase, and cadmium telluride quantum dot particle diameter that Thiovanic acid coats and fluorescence efficiency are with the rule that changes heat-up time in the water-bath as shown in Figure 2.
(4) with after the solution cooling that obtains in (3), place dialysis tubing, dialysis is 24 hours in secondary water, removes free ions and unnecessary stablizer, obtains the cadmium telluride quantum dot solution that Thiovanic acid coats.
The preparation of the cadmium telluride quantum dot that embodiment 2. ethanoyl half light Gelucystine (ACYS) coats:
(1) with 20mL 5mM CdCl
2Mix with 17mg ACYS, with being diluted to 40mL behind the 0.1M NaOH adjusting pH to 11.2, the logical nitrogen of gained colorless cleared solution 30 minutes.
(2) be electrolytic solution with the solution that obtains in (1), the Ag/AgCl electrode is a reference electrode, and the Pt silk is a counter electrode, and the tellurium electrode is a working electrode, keeps the regular hour under the current potential of-0.95V, obtains faint yellow cadmium telluride precursor solution.
(3) the cadmium telluride precursor solution is placed different time of water-bath reflux of 80 ℃, obtain the cadmium telluride quantum dot that the ACYS of different size coats, its fluorescence efficiency with the rule that changes heat-up time as shown in Figure 2.
(4) with after the solution cooling that obtains in (3), place dialysis tubing, dialysis is 24 hours in secondary water, removes free ions and unnecessary stablizer, obtains the cadmium telluride quantum dot solution that ethanoyl half light Gelucystine coats.
Claims (4)
1. the method for a negative electrode tellurium electrode preparation high fluorescence efficiency cadmium telluride quantum dot, its step is as follows:
(1) preparation of tellurium electrode: with Resins, epoxy the tellurium rod is sealed in Glass tubing or the polyfluortetraethylene pipe, the other end links to each other with lead to fill graphite;
(2) cadmium source solution preparation: with Cadmium chloride fine powder, cadmium perchlorate, Cadmium Sulphate or cadmium nitrate is the cadmium source, with sulfhydryl compound or water-soluble polymer is stablizer, prepare the sulfydryl title complex of cadmium, and regulate pH value to 11 with sodium hydroxide, the mol ratio of Cadmium chloride fine powder and sulfhydryl compound is 1: 1.5～1: 4;
(3) preparation of cadmium telluride precursor solution: with the tellurium electrode is that working electrode, Ag/AgCl electrode are that reference electrode, Pt silk are counter electrode, cadmium source solution is electrolytic solution, behind the dissolved oxygen in the logical nitrogen removal electrolytic solution,-0.90～-carry out electrolysis under the negative electrode current potential of 1.2V, the tellurium ionic weight that generates can be by flowing through the electric energy control of working electrode, and the mol ratio of cadmium and tellurium was controlled at 1: 0.3～1: 0.6;
(4) formation of cadmium telluride quantum dot: the cadmium telluride precursor solution of preparation in (3) is heated in 70～95 ℃ water-bath, and control can be regulated the particle diameter of the cadmium telluride quantum dot that makes, maximum emission wavelength and fluorescence quantum yield heat-up time;
(5) purifying of cadmium telluride quantum dot: the cadmium telluride quantum dot solution that makes is placed dialysis tubing, and dialysis is 24 hours in secondary water, removes free ions and unnecessary stablizer, can get the cadmium telluride quantum dot solution that stablizer coats.
2. according to the preparation method of claim 1; it is characterized in that in the step (3) with negative electrode tellurium electrode being that the tellurium source prepares the cadmium telluride precursor solution; the sodium hydrogen telluride or the telluretted hydrogen tellurium source that have replaced easy oxidation by air; or the tellurium aluminium tellurium source that easily absorbs water; thereby the preparation of quantum dot can be carried out in the system of opening wide; do not need specific protective atmosphere, all reaction process can be finished in a reaction vessel.
3. according to the preparation method of claim 1, it is characterized in that the described stablizer of step (2), its selection can be regulated and control the surface group of cadmium telluride quantum dot, stablizer comprises mercaptoalcohol, halfcystine or cysteamine, reduced glutathion and polyvinyl alcohol, and what there were positively charged amino, electronegative carboxyl in the quantum dot surface that makes or had a biocompatibility goes back ortho states gsh or polyvinyl alcohol; Cadmium telluride quantum dot can be selected diverse ways according to the surface group of quantum dot with being connected of biomolecules.
4. according to the preparation method of claim 1, it is that 2.0～5.0nm, maximum emission wavelength are 500～650nm that the formation time that it is characterized in that controlling cadmium telluride quantum dot can obtain particle diameter, and the emission spectrum peak width at half height is that 40～55nm, fluorescence quantum yield are the cadmium telluride quantum dot solution that 60～78% stablizer coats.
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| CN1524783A (en) * | 2003-09-18 | 2004-09-01 | 吉林大学 | Method and apparatus for preparing water-soluble CdTe nanocrystalline |
| CN1710154A (en) * | 2005-04-22 | 2005-12-21 | 吉林大学 | Method for water-phase rapid synthesis of CdTe nano crystal at warm condition |
| CN101029896A (en) * | 2007-03-22 | 2007-09-05 | 南京大学 | Analysis of quantum-point electrogenerated chemiluminescent hydrophobic-based compound |
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| CN1524783A (en) * | 2003-09-18 | 2004-09-01 | 吉林大学 | Method and apparatus for preparing water-soluble CdTe nanocrystalline |
| CN1710154A (en) * | 2005-04-22 | 2005-12-21 | 吉林大学 | Method for water-phase rapid synthesis of CdTe nano crystal at warm condition |
| CN101029896A (en) * | 2007-03-22 | 2007-09-05 | 南京大学 | Analysis of quantum-point electrogenerated chemiluminescent hydrophobic-based compound |
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