CN104722779A - Silver nanocluster preparation method with hydrogen serving as reducing agent - Google Patents
Silver nanocluster preparation method with hydrogen serving as reducing agent Download PDFInfo
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- CN104722779A CN104722779A CN201310715263.6A CN201310715263A CN104722779A CN 104722779 A CN104722779 A CN 104722779A CN 201310715263 A CN201310715263 A CN 201310715263A CN 104722779 A CN104722779 A CN 104722779A
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- polyacrylic acid
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Abstract
The invention provides a silver nanocluster preparation method with hydrogen serving as a reducing agent. The silver nanocluster preparation method is characterized in that polyelectrolyte and silver salt react at a room temperature in a hydrogen atmosphere by taking the polyelectrolyte as a template and the hydrogen as the reducing agent so as to obtain a near-infrared emission silver nanocluster. The silver nanocluster preparation method has the advantages of low cost, simplicity, mild reacting conditions, no participation of highly-toxic substance and more economy and environmental protection, and the prepared silver nanocluster is excellent in fluorescence characteristic and stability.
Description
Technical field
The present invention relates to the synthesis field of noble metal nanometer material, specifically a kind of is that reducing agent preparation has the method for light to the Silver Clusters of fluorescent emission phenomenon with hydrogen.
Background technology
Silver Clusters (silver nanoclusters, AgNCs) is by several the tool fluorescence, the water miscible molecule level aggregation that form to tens silver atoms.Its distinctive quantum size effect makes its optical property have the characteristic changed with particle size, and this characteristic makes its fluorescence emission spectrum tunable within the scope of visible ray to near-infrared region.In addition, AgNCs has good biocompatibility, photostability is strong, depolymerize ability strong, stoke shift is comparatively large and on all relevant time scale the feature such as flicker free, substantially improve its performance as biomarker, significantly improve the sensitivity of existing analytical method.Therefore, AgNCs is just becoming the new lover of field of bioanalysis.Current AgNCs is progressively applied to biology sensor, cell marking and the field such as imaging and bioprobe.
At present, the preparation method of AgNCs is mainly divided into template, monolayer Protection Code and part etching method.
Template is one of the most frequently used at present method, and it is with certain material for matrix or model are to synthesize AgNCs, as polyaniline (PANI), PVOH amine (PEI), polyglycereol-b-polyacrylic acid etc.But because the shortcomings such as preparation method's complexity of template, length consuming time bring difficulty to the synthesis of AgNCs, in addition, template also hinders the application of AgNCs in biological field to the toxic and side effect of organism.Recently, protein and nucleic acid are used to the preparation template of AgNCs, and show good biocompatibility, but the extensive use of its high cost restriction AgNCs.Meanwhile, the reducing agent used in template mostly is NaBH human body to toxic and side effect
4, how removing its residue is also a large difficult point.
And monolayer Protection Code and part etching method are as the emerging preparation method of AgNCs preparation field; the research of its synthesis and application is still in the starting stage; detailed preparation mechanism still imperfectly understands, and still can not be widely used in biological detection and medical diagnosis.
In summary, the preparation method of current AgNCs is under template complex exists, and uses NaBH
4or more complicated photoreduction agent is prepared from, it mainly deposits problem both ways: 1) template problem: adopt polyaniline (PANI), PVOH amine (PEI), polyglycereol-b-polyacrylic acid etc. to have operating process complexity, the shortcoming such as consuming time as synthesis template; Protein and nucleic acid is adopted to have the deficiencies such as with high costs as soft template.2) use of reducing agent: most of reducing agents that preparation AgNCs adopts at present are NaBH
4, the shortcomings such as this reducing agent existence and stability is poor, operating process is complicated.These drawbacks hinder the application of AgNCs.
Therefore, we need a kind of new AgNCs preparation method, have that cost is low, preparation is simple and the features such as environmental protection.
Summary of the invention
For solving the deficiencies in the prior art, the present invention proposes a kind of method using hydrogen to be soft template synthesis AgNCs as reducing agent, polyacrylic acid (PAA).The method has the advantages such as simple to operate, cost is low, synthesis condition is gentle.Meanwhile, the AgNCs of the method synthesis is adopted to have the features such as larger stoke shift, fluorescence emission spectrum is tunable.
For achieving the above object, the technical scheme taked is: a kind of take hydrogen as the method that Silver Clusters prepared by reducing agent, be template with polyelectrolyte, take hydrogen as reducing agent, make described polyelectrolyte and silver salt room temperature reaction under described hydrogen atmosphere, obtain Silver Clusters.
In an embodiment of the present invention, described polyelectrolyte is selected from polyacrylic acid.
In an embodiment of the present invention, described silver salt is selected from silver nitrate.
In an embodiment of the present invention, in described preparation method, the molar ratio range of the silver ion in described silver salt and described polyacrylic acid monomers is (2 ~ 1): (1 ~ 10), and the silver ion molar concentration scope in reaction system is 0.1mmol/l ~ 4.0 mmol/l; Preferably, in described silver salt, the mol ratio of silver ion and described polyacrylic acid monomers is 1:6.
In the present invention one preferred embodiment, thering is provided a kind of take hydrogen as the method that Silver Clusters prepared by reducing agent, described method is is template with polyacrylic acid, take hydrogen as reducing agent, make described polyacrylic acid and silver nitrate under Hydrogen Vapor Pressure is 0.1 ~ 3.5bar 25 DEG C react 5 ~ 40 minutes, preferred reaction 15 minutes, thus obtain the Silver Clusters with near infrared emission; Wherein, the molar ratio range of the silver ion in described silver nitrate and described polyacrylic acid monomers is in (2 ~ 1): (1 ~ 10), and the silver ion molar concentration scope in reaction system is 0.1mmol/l ~ 4.0 mmol/l.
In the present invention one preferred embodiment, the mol ratio of the silver ion in described silver nitrate and described polyacrylic acid monomers is 1:6.
In the present invention one preferred embodiment, described polyacrylic acid and silver nitrate under Hydrogen Vapor Pressure is 1.5 bar 25 DEG C react 15 minutes.
In the present invention one preferred embodiment, thering is provided a kind of take hydrogen as the method that Silver Clusters prepared by reducing agent, described method is is template with polyacrylic acid, take hydrogen as reducing agent, make described polyacrylic acid and silver nitrate under Hydrogen Vapor Pressure is 1.5 bar 25 DEG C react 15 minutes, thus obtain there is the Silver Clusters of near infrared emission; Wherein, the mol ratio of the silver ion in described silver nitrate and described polyacrylic acid monomers is 1:6, and the silver ion molar concentration scope in reaction system is 1.5 mmol/l.
It should be noted that: in the method for the invention, hydrogen, as reducing agent, can make Ag
+be reduced to silver-colored simple substance, the preparation of change on Silver Clusters of its pressure has remarkable impact, and in experiment, Hydrogen Vapor Pressure is by 0.1bar to 3.5bar consecutive variations, and the Silver Clusters fluorescence property of preparation first strengthens, after weaken, determine that 1.5bar is optimal conditions thus.
Silver Clusters preparation method of the present invention, by simple low pressure hydrogen reduction PAA, AgNO
3mixed solution thus prepared the Silver Clusters with near infrared emission.
Preparation method's cost of the present invention is low, method is simple, reaction condition is gentle, and participates in without extremely toxic substance, more economic environmental protection; And obtained Silver Clusters has excellent fluorescent characteristic and stability.Preparation method of the present invention overcomes the shortcomings such as the reducing agent existed in existing Silver Clusters preparation method is poisonous, template is complicated, cost is higher.Meanwhile, compared with existing Silver Clusters preparation method, the Silver Clusters applying preparation method of the present invention acquisition has the features such as larger stoke shift, monodispersity is good, stability is high, fluorescence intensity is large.The present invention can be widely used in multiple technical field such as environment measuring, food security.
Accompanying drawing explanation
Fig. 1 is the fluorescence spectrum of the AgNCs obtained by embodiments of the invention 1 ~ 3;
Fig. 2 is the electron microscopic picture of the AgNCs obtained by embodiments of the invention 2.
Detailed description of the invention
Be described in detail the present invention below in conjunction with embodiment, embodiment is intended to explain and non-limiting technical scheme of the present invention.
embodiment 1
In the present embodiment, be template with polyacrylic acid, take hydrogen as reducing agent, make described polyacrylic acid and silver nitrate under described hydrogen atmosphere 25 DEG C react 5 ~ 40 minutes, thus obtain the Silver Clusters with near infrared emission; Wherein, the silver ion in described silver nitrate and the mol ratio of described polyacrylic acid monomers are 1:6.Concrete steps describe as follows.
Accurately pipetting 5ml deionized water in 10ml beaker with pipette, adding the PAA solution of freshly prepared 0.5 mol/l of 6 μ l and the AgNO of 1 μ l 0.5 mol/l when stirring with liquid-transfering gun
3solution, obtains mixed solution, as calculated: Ag in described mixed solution
+concentration is 0.1mmol/l, Ag
+be 1:6 with the mol ratio of PAA monomer.Described mixed solution is stirred 10 minutes under lucifuge condition, then transfers them in 50ml autoclave, and be filled with the high-purity H of 1.5bar wherein
2, stir 5 ~ 40 minutes at 25 DEG C.Finally the AgNCs solution of preparation is stored in the refrigerator of 4 DEG C under the condition of lucifuge.
Get AgNCs solution that 1ml prepares in four-way cuvette, obtain the fluorescence spectrum of AgNCs, preferred reaction 15 minutes, as shown in Figure 1.By finding that the emission peak of the AgNCs that the present embodiment obtains appears at near-infrared region to the measurement of its fluorescence spectrum, increase along with the reaction time has occurred that AgNCs emission peak grows out of nothing, from weak to strong, again from strong to weak to the process disappeared, simultaneously also there is red shift along with the increase of mixing time in its emission wavelength.
embodiment 2
In the present embodiment, be template with polyacrylic acid, take hydrogen as reducing agent, make described polyacrylic acid and silver nitrate under described hydrogen atmosphere 25 DEG C react 5 ~ 40 minutes, thus obtain the Silver Clusters with near infrared emission; Wherein, the silver ion in described silver nitrate and the mol ratio of described polyacrylic acid monomers are 1:6.Concrete steps describe as follows.
Accurately pipetting 5ml deionized water in 10ml beaker with pipette, adding the PAA solution of freshly prepared 0.5 mol/l of 90 μ l with liquid-transfering gun when stirring, the AgNO of 15 μ l 0.5mol/l
3solution, obtains mixed solution, as calculated: Ag in described mixed solution
+concentration is 1.5mmol/l, Ag
+be 1:6 with the mol ratio of PAA monomer.Described mixed solution is stirred 10 minutes under lucifuge condition, then transfers them in 50ml autoclave, and be filled with the high-purity H of 1.5bar wherein
2, stir 5 ~ 40 minutes at 25 DEG C.Finally the AgNCs solution of preparation is stored in the refrigerator of 4 DEG C under the condition of lucifuge.
Get AgNCs solution that 1ml prepares in four-way cuvette, obtain the fluorescence spectrum of AgNCs, preferred reaction 15 minutes, as shown in Figure 1.Applicant also observes the AgNCs obtained, and obtains electron microscopic picture as shown in Figure 2.By finding that the emission peak of AgNCs appears at near-infrared region to the measurement of its fluorescence spectrum, increase along with the reaction time has occurred that AgNCs emission peak grows out of nothing, from weak to strong, again from strong to weak to the process disappeared, simultaneously also there is red shift along with the increase of mixing time in its emission wavelength.
embodiment 3
In the present embodiment, be template with polyacrylic acid, take hydrogen as reducing agent, make described polyacrylic acid and silver nitrate under described hydrogen atmosphere 25 DEG C react 5 ~ 40 minutes, thus obtain the Silver Clusters with near infrared emission; Wherein, the silver ion in described silver nitrate and the mol ratio of described polyacrylic acid monomers are 1:6.Concrete steps describe as follows.
Accurately pipetting 5ml deionized water in 10ml beaker with pipette, adding the PAA solution of freshly prepared 0.5 mmol/l of 240 μ l with liquid-transfering gun when stirring, the AgNO of 40 μ l 0.5 mmol/l
3solution, obtains mixed solution, as calculated: Ag in described mixed solution
+concentration is 3.8mmol/l, Ag
+be 1:6 with the mol ratio of PAA monomer.Described mixed solution is stirred 10 minutes under lucifuge condition, then transfers them in 50ml autoclave, and be filled with the high-purity H of 1.5bar wherein
2, stir 5 ~ 40 minutes at 25 DEG C.Finally the AgNCs solution of preparation is stored in the refrigerator of 4 DEG C under the condition of lucifuge.
Get AgNCs solution that 1ml prepares in four-way cuvette, obtain the fluorescence spectrum of AgNCs, preferred reaction 15 minutes, as shown in Figure 1.By finding that the emission peak of AgNCs appears at near-infrared region to the measurement of its fluorescence spectrum, increase along with the reaction time has occurred that AgNCs emission peak grows out of nothing, from weak to strong, again from strong to weak to the process disappeared, simultaneously also there is red shift along with the increase of mixing time in its emission wavelength.
Silver Clusters preparation method of the present invention, by simple low pressure hydrogen reduction PAA, AgNO
3mixed solution thus prepared the Silver Clusters with near infrared emission.
Preparation method's cost of the present invention is low, method is simple, reaction condition is gentle, and participates in without extremely toxic substance, more economic environmental protection; And obtained Silver Clusters has excellent fluorescent characteristic and stability.Preparation method of the present invention overcomes the shortcomings such as the reducing agent existed in existing Silver Clusters preparation method is poisonous, template is complicated, cost is higher.Meanwhile, compared with existing Silver Clusters preparation method, the Silver Clusters applying preparation method of the present invention acquisition has the features such as larger stoke shift, monodispersity is good, stability is high, fluorescence intensity is large.
The above is only the preferred embodiment of the present invention; it should be pointed out that for those skilled in the art, without departing from the inventive concept of the premise; can also make some changes, improvements and modifications, these changes, improvements and modifications also should be considered as protection scope of the present invention.
Claims (10)
1. one kind is the method that Silver Clusters prepared by reducing agent with hydrogen, it is characterized in that, described method is is template with polyelectrolyte, take hydrogen as reducing agent, make described polyelectrolyte and silver salt room temperature reaction under described hydrogen atmosphere, obtain the Silver Clusters with near infrared emission.
2. the method for claim 1, is characterized in that, described polyelectrolyte is selected from polyacrylic acid.
3. the method for claim 1, is characterized in that, described silver salt is selected from silver nitrate.
4. the method for claim 1, it is characterized in that, in described preparation method, in described silver salt, the molar ratio range of silver ion and described polyacrylic acid monomers is (2 ~ 1): (1 ~ 10), further, the silver ion molar concentration scope in reaction system is 0.1mmol/l ~ 4.0 mmol/l.
5. method as claimed in claim 4, it is characterized in that, in described silver salt, the mol ratio of silver ion and described polyacrylic acid monomers is 1:6.
6. the method for claim 1, is characterized in that, described polyelectrolyte and silver salt room temperature reaction under Hydrogen Vapor Pressure is 0.1 ~ 3.5bar.
7. method as claimed in claim 6, it is characterized in that, described Hydrogen Vapor Pressure is 1.5bar.
8. one kind is the method that Silver Clusters prepared by reducing agent with hydrogen, it is characterized in that, described method is is template with polyacrylic acid, take hydrogen as reducing agent, make described polyacrylic acid and silver nitrate under Hydrogen Vapor Pressure is 0.1 ~ 3.5bar 25 DEG C react 5 ~ 40 minutes, obtain and there is the Silver Clusters of near infrared emission; Wherein,
The molar ratio range of the silver ion in described silver nitrate and described polyacrylic acid monomers is in (2 ~ 1): (1 ~ 10), and the silver ion molar concentration scope in reaction system is 0.1mmol/l ~ 4.0 mmol/l.
9. method as claimed in claim 8, it is characterized in that, the mol ratio of the silver ion in described silver nitrate and described polyacrylic acid monomers is 1:6.
10. method as claimed in claim 9, is characterized in that, described polyacrylic acid and silver nitrate under Hydrogen Vapor Pressure is 1.5 bar 25 DEG C react 15 minutes.
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