CN102660258B - Method for preparing water-soluble CdS quantum dot - Google Patents
Method for preparing water-soluble CdS quantum dot Download PDFInfo
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- CN102660258B CN102660258B CN201210114801.1A CN201210114801A CN102660258B CN 102660258 B CN102660258 B CN 102660258B CN 201210114801 A CN201210114801 A CN 201210114801A CN 102660258 B CN102660258 B CN 102660258B
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Abstract
The invention discloses a method for preparing a water-soluble CdS quantum dot. The method includes the steps: (1) adding water solution containing CdC12*2.5H2O into water solution containing glutathione to obtain Cd-glutathione coordination polymer; (2) dispersing the Cd-glutathione coordination polymer into water to obtain water dispersion of the Cd-glutathione coordination polymer; and (3) adding NaOH water solution into the water dispersion of the Cd-glutathione coordination polymer to obtain the water-soluble CdS quantum dot after standing. Firstly, the method omits commonly used organic cadmium for synthesizing the CdS quantum dot; secondly, the easily obtained glutathione with biological compatibility is used as a sulfur source; and finally, external energy, organic reagents and the like are not introduced during preparation. Moreover, the size and the optical property of the prepared CdS quantum dot can be regulated and controlled by adjusting the pH (potential of hydrogen) value of a system, so that biological application of the CdS quantum dot can be facilitated.
Description
Technical field
The present invention relates to a kind of preparation method of water-soluble CdS quantum dot, belong to the synthesis technical field of inorganic nano material.
Background technology
Quantum dot is due to its good physicochemical property, as quantum size effect, luminescent properties and chemical process, and in the application in the fields such as biomarker, bio-sensing, photoelectronics and solar cell and receive much concern.Wherein, CdS quantum dot is studied extensively as the nanocrystal of a kind of II-VI family.At present, the synthetic method of CdS quantum dot is reported a lot, mainly includes the hot injection of machine metal precursor, hydro-thermal or solvent-thermal method, gas-liquid-solid auxiliary law, micelle assay etc.Although these methods are widely used in the synthetic of CdS nanocrystal, these methods mostly need expensive or poisonous raw material, and loaded down with trivial details step, and need to introduce external energy, as heat, microwave, ultrasonic and mechanical workout etc.In addition, the synthetic CdS quantum dot of these methods is hydrophobic mostly, is unfavorable for that it is in the application in the fields such as biomarker, bio-sensing and drug release.Therefore, developing a kind of simple, gentle, eco-friendly green synthesis method prepares water miscible CdS quantum dot and seems particularly important.
In recent years, ligand polymer (Coordination Polymers, CPs) has obtained fast development as a kind of novel porous hybrid material with controlled size and pattern being formed by self-assembly by metal ion or metal ion bunch and multiple tooth bridge ligand.Due to himself good performance, at numerous areas, attracted to study widely interest and show huge application prospect.In addition, Modulatory character due to its unique size and pattern, using ligand polymer as presoma or template, by it is heat-treated or chemical conversion, the nano material that has become preparation specific morphology, porous size and good interfacial property is a kind of novel method of metal oxide especially.Yet, up to now, by ligand polymer, carry out simple alkaline purification and prepare the method for water-soluble quantum dot and be not yet seen in report.
Summary of the invention
The preparation method who the object of this invention is to provide a kind of water-soluble CdS quantum dot.
The preparation method of a kind of water-soluble CdS quantum dot provided by the present invention, comprises the steps:
(1) by CdCl
22.5H
2the aqueous solution of O is added in the aqueous solution of gsh and obtains Cd-gsh ligand polymer;
(2) described Cd-gsh ligand polymer is scattered in to the aqueous dispersions that obtains Cd-gsh ligand polymer in water;
(3) in the aqueous dispersions of described Cd-gsh ligand polymer, add the NaOH aqueous solution, obtain described water-soluble CdS quantum dot after standing.
In above-mentioned preparation method, described CdCl
22.5H
2the volumetric molar concentration of the aqueous solution of O can be 10mM～20mM, and the volumetric molar concentration of the aqueous solution of described gsh can be 10mM～20mM.
In above-mentioned preparation method, described CdCl
22.5H
2the mol ratio of O and described gsh is 1: 1.
In above-mentioned preparation method, the pH value of the aqueous solution of described gsh can be 7.0～12.0, as 7.0,9.0 or 11.3.
In above-mentioned preparation method, the volumetric molar concentration of the described NaOH aqueous solution can be 10mM～50mM, and the aqueous dispersions of described Cd-gsh ligand polymer can be 1 with the volume parts ratio of the described NaOH aqueous solution: (1～5), and as 1: 1.
In above-mentioned preparation method, the described standing time can be 2～3 days, and standing temperature can be 20 ℃～35 ℃.
The invention provides a kind of preparation method who ligand polymer is carried out alkaline purification synthesizing water-solubility CdS quantum dot under simple, gentleness, eco-friendly condition, compare with traditional method, have advantages of following outstanding: first, cadmium source used is CdCl
2, avoided using CdS quantum dot synthetic in conventional organic cadmium; Secondly, sulphur source used gsh that be bio-compatibility, that be easy to get; Finally, in preparation process without introducing external energy and organic reagent etc.The method provides a kind of novel method of simple, gentle synthesizing water-solubility CdS quantum dot, and can the pH value by regulation system realizes size and the optical property of gained CdS quantum dot, will be conducive to its application aspect biological.
Accompanying drawing explanation
The SEM image of Fig. 1, the Cd-GSH ligand polymer that obtains for the present invention, wherein, Fig. 1 a), Fig. 1 b) and Fig. 1 c) be respectively the SEM image of the Cd-GSH ligand polymer that embodiment 1, embodiment 2 and embodiment 3 obtain.
The TEM image of the CdS quantum dot that Fig. 2, the present invention obtain, wherein, Fig. 2 a), Fig. 2 b) and Fig. 2 c) be respectively the TEM image of the CdS quantum dot that embodiment 1, embodiment 2 and embodiment 3 obtain.
Fig. 3 is the FT-IR collection of illustrative plates of GSH in the embodiment of the present invention 1, Cd-GSH ligand polymer and CdS quantum dot.
Fig. 4 is the EDX collection of illustrative plates of the CdS quantum dot of preparation in the embodiment of the present invention 1.
Fig. 5 is XRD, HR-TEM, SAED and the EDX collection of illustrative plates of CdS quantum dot of preparation in the embodiment of the present invention 1, wherein, Fig. 5 a), Fig. 5 b), Fig. 5 c) and Fig. 5 d) be respectively XRD, HR-TEM, SAED and the EDX collection of illustrative plates of CdS quantum dot.
Fig. 6 is the fluorescence spectrum figure of the CdS quantum dot of the embodiment of the present invention 1, embodiment 2 and embodiment 3 preparations.
The fluorescence spectrum figure that adds respectively the CdS quantum dot that the NaOH aqueous solution of inequality obtains in the aqueous dispersions of Fig. 7 for the Cd-gsh ligand polymer to obtaining in the embodiment of the present invention 3.
Embodiment
The experimental technique using in following embodiment if no special instructions, is ordinary method.
In following embodiment, material used, reagent etc., if no special instructions, all can obtain from commercial channels.
The preparation of embodiment 1, CdS quantum dot (pH 7.0)
(1) under room temperature, with NaOH, the pH value of gsh (GSH) aqueous solution is deployed into 7.0, its volumetric molar concentration is 10mM; By 1mL CdCl
22.5H
2the O aqueous solution (volumetric molar concentration is 10mM) is added in the aqueous solution of the above-mentioned gsh of 1mL, stir, after completion of the reaction, centrifugal, collecting precipitation, then with pure water washing, obtain Cd-GSH ligand polymer 3 times, finally this Cd-GSH ligand polymer is scattered in and in water, obtains Cd-GSH ligand polymer aqueous dispersions;
Above-mentioned gained Cd-GSH ligand polymer is carried out to FT-IR and EDX sign, respectively as shown in Figure 3 and Figure 4, confirmed its composition; By SEM, its pattern is characterized, its image as Fig. 1 a) as shown in its grain size be 400 ± 200nm;
(2) the 1mL NaOH aqueous solution (10mM) is added in the above-mentioned Cd-GSH aqueous dispersions of 1mL, within standing 3 days, obtains water-soluble CdS quantum dot at 35 ℃;
CdS quantum dot obtained above is carried out to XRD, HR-TEM, SAEX and EDX characterizes, respectively as Fig. 5 a), Fig. 5 b), Fig. 5 c) and Fig. 5 d) as shown in, confirmed its composition; Its TEM image as Fig. 2 a) as shown in, can find out that it is of a size of 4 ± 1nm.
The preparation of embodiment 2, CdS quantum dot (pH 9.0)
(1) under room temperature, with NaOH, the pH value of the aqueous solution of gsh is deployed into 9.0, its volumetric molar concentration is 10mM; By 1mL CdCl
22.5H
2the O aqueous solution (volumetric molar concentration is 10mM) is added in the aqueous solution of the above-mentioned gsh of 1mL, stir, after completion of the reaction, centrifugal, collecting precipitation, then with pure water washing, obtain Cd-GSH ligand polymer 2 times, finally this Cd-GSH ligand polymer is scattered in and in water, obtains Cd-GSH ligand polymer aqueous dispersions;
Above-mentioned gained Cd-GSH ligand polymer is carried out to FT-IR and EDX sign, and test result is similar to embodiment 1, has confirmed its composition; By SEM, its pattern is characterized, its image is as Fig. 1 b) as shown in; Can find out that synthesized Cd-GSH is of a size of 180 ± 30nm.
(2) the 1mL NaOH aqueous solution (10mM) is added in the above-mentioned Cd-GSH aqueous dispersions of 1mL, within standing 2 days, obtains water-soluble CdS quantum dot at 20 ℃;
CdS quantum dot obtained above is carried out to XRD, EDX, HR-TEM and SAEX and characterize, test result is similar to embodiment 1, has confirmed its composition; Its TEM image is as Fig. 2 b) as shown in, can find out that its grain size is 7 ± 2nm.
The preparation of embodiment 3, CdS quantum dot (pH 11.3)
(1) under room temperature, with NaOH, the pH value of the aqueous solution of gsh is deployed into 11.3, its volumetric molar concentration is 10mM; By 1mL CdCl
22.5H
2the O aqueous solution (volumetric molar concentration is 10mM) is added in the aqueous solution of the above-mentioned gsh of 1mL, stir, after completion of the reaction, centrifugal, collecting precipitation, then with pure water washing, obtain Cd-GSH ligand polymer 3 times, finally this Cd-GSH ligand polymer is scattered in and in water, obtains Cd-GSH ligand polymer aqueous dispersions;
Above-mentioned gained Cd-GSH ligand polymer is carried out to FT-IR and EDX sign, and test result is similar to embodiment 1, has confirmed its composition; By SEM, its pattern is characterized, its image is as Fig. 1 c) as shown in; Can find out that its grain size is 40 ± 10nm.
(2) the 1mL NaOH aqueous solution (10mM) is added in the above-mentioned Cd-GSH aqueous dispersions of 1mL, within standing 3 days, obtains water-soluble CdS quantum dot at 35 ℃;
CdS quantum dot obtained above is carried out to XRD, EDX, HR-TEM and SAEX and characterize, test result is similar to embodiment 1, has confirmed its composition; Its TEM image is as Fig. 2 c) as shown in, can find out that it is of a size of 10 ± 2nm.
Comparison diagram 1a), b) and c), can find out that resulting Cd-GSH ligand polymer size is micro/nano level, and its size presents with the increase of initial pH value the trend reducing.
B) and c), can find out that the size of prepared CdS quantum dot is nano level, and its size presents the trend of increase with the increase of the initial pH value of the gsh aqueous solution comparison diagram 2a).
Optical property to the prepared CdS quantum dot of embodiment 1,2 and 3 further characterizes, and finds that the photoluminescent property of gained CdS quantum dot and the initial pH value of the gsh aqueous solution also have certain relation; As shown in Figure 6, the maximum fluorescence intensity peak that is the synthetic CdS quantum dot obtaining under 7.0,9.0 and 11.3 condition at the Initial pH of the gsh aqueous solution lays respectively at 500nm, 540nm and 550nm (λ
ex=365nm), can draw, there is certain red shift with the increase of pH value in the maximum fluorescence emission peak of the lower synthetic CdS quantum dot of different pH values, and fluorescence intensity is different.
In alkaline purification process, when the amount of alkali strengthens, its fluorescence intensity is enhancing trend; As shown in Figure 7, the NaOH aqueous solution that adds equal-volume different concns in the aqueous dispersions of the Cd-gsh ligand polymer that is 11.3 to Initial pH, room temperature is two days later standing, and the fluorescence intensity of discovery gained CdS quantum dot is enhancing trend (λ with the increase of added alkali number
ex=365nm).
To sum up, the present invention carries out alkaline purification to ligand polymer and has synthesized water-soluble CdS quantum dot under simple, gentle, eco-friendly condition, finds that the particle diameter of synthesized quantum dot and optical property can be simply adjustable by changing the concentration realization of the NaOH aqueous solution used in the pH value of the gsh aqueous solution and last handling process; The preparation method of this CdS quantum dot provides potential possibility for it in biologic applications field.
Claims (1)
1. a preparation method for water-soluble CdS quantum dot, comprises the steps:
(1) by CdCl
22.5H
2the aqueous solution of O is added in the aqueous solution of gsh and obtains Cd-gsh ligand polymer;
(2) described Cd-gsh ligand polymer is scattered in to the aqueous dispersions that obtains Cd-gsh ligand polymer in water;
(3) in the aqueous dispersions of described Cd-gsh ligand polymer, add the NaOH aqueous solution, obtain described water-soluble CdS quantum dot after standing;
Described CdCl
22.5H
2the volumetric molar concentration of the aqueous solution of O is 10mM～20mM, and the volumetric molar concentration of the aqueous solution of described gsh is 10mM～20mM;
Described CdCl
22.5H
2the mol ratio of O and described gsh is 1:1;
The pH value of the aqueous solution of described gsh is 7.0～12.0;
The volumetric molar concentration of the described NaOH aqueous solution is 10mM～50mM; The aqueous dispersions of described Cd-gsh ligand polymer is 1:(1～5 with the volume parts of described NaOH aqueous solution ratio);
The described standing time is 2 days～3 days, and standing temperature is 20 ℃～35 ℃.
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| CN104045106B (en) * | 2014-05-22 | 2015-06-10 | 南京邮电大学 | Supercritical carbon dioxide method for preparing cadmium sulfide nanoparticles |
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