CN102504802A - Metallic organic luminescent molecule and hydrotalcite compounded electrochemiluminiscent ultrathin film and method of preparing same - Google Patents
Metallic organic luminescent molecule and hydrotalcite compounded electrochemiluminiscent ultrathin film and method of preparing same Download PDFInfo
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- CN102504802A CN102504802A CN2011102964099A CN201110296409A CN102504802A CN 102504802 A CN102504802 A CN 102504802A CN 2011102964099 A CN2011102964099 A CN 2011102964099A CN 201110296409 A CN201110296409 A CN 201110296409A CN 102504802 A CN102504802 A CN 102504802A
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Abstract
The invention discloses a tris(2, 2'-bipyridyl) ruthenium(II) chloride and hydrotalcite compounded electrochemiluminiscent ultrathin film and a method of preparing the same, which belong to the technical field of preparation of compound luminescent materials. The film and the method have the advantages that by the aid of rigid structure of hydrotalcite laminates and confinement effect of a two-dimensional space, photo-activated complexes are immobilized and orderly arranged at molecular scale, redshift and fluorescence quenching caused by molecule aggregation are reduced, and electrochemiluminiscence analysis experimental apparatus are simplified and solvent consumption is reduced; and the film preparation process is easy in operation, and luminescence intensity of the film and thickness of the film can both be precisely controlled by changing assembly frequency.
Description
Affiliated field
The invention belongs to the composite luminescent material preparing technical field, particularly a kind of terpyridyl ruthenium chloride (II) and hydrotalcite compound electrochemiluminescence ultrathin membrane and preparation method thereof.
Background technology
The bimetal complex hydroxide is called hydrotalcite (Layered Double Hydroxides again; Be abbreviated as LDHs); Be a kind of novel multifunctional stratified material, its chemicalstability is good, has strong heat resistanceheat resistant performance; And LDHs laminate species of metal ion and adjustable ratio become, and interlayer anion has interchangeability.The crystalline structure of this uniqueness and physicochemical characteristic make it show very wide application in many fields such as IX, absorption, catalysis, macromolecule modified, optical material, magnetics material, electricity materials.Hydrotalcite material is through carrying out the individual layer nanometer sheet of the peelable one-tenth high dispersing of churned mechanically mode in organic solvent; Count electrostatic force then; Hydrogen bond; Reactive forces such as close and distant water can pass through the polymer anion of laminate of peeling off and difference in functionality characteristic the method for self-assembly layer by layer, and assembling becomes the thin-film material of ordered arrangement.
Electrogenerated chemiluminescence(ECL) (ECL) is highly sensitive, favorable reproducibility, can survey continuously, easy and simple to handle, be easy to control.Especially at biochemical analysis.Aspect such as pharmaceutical analysis and immunoassay shows unique characteristics.Electrochemiluminescence is to produce luminous phenomenon through the electrochemistry provocative reaction, is the product that CL method and electrochemical method mutually combine.Therefore; The ECL analytical method is except highly sensitive, the advantage such as linearity range is wide and instrument is simple that has that the CL analytical method has; The many advantages that also have electrochemical method: (1) adopts electrochemical method can be easy to change the redox ability of material, and the recycle and being convenient to of can select more stable reagent, being convenient to the material of electrochemical reversible realizes the chemiluminometry need extremely unsettled reagent participated in; (2) excite through electrochemistry owing to luminous, be convenient to regulate luminous time and space; (3) can current signal be provided simultaneously, be convenient to luminescence mechanism research etc.
In the research of electrochemiluminescence,, utilize immobilization of reagents that the method for chemically modified will directly or indirectly participate in chemiluminescence reaction at electrode in order to expand the Application Areas of electrochemiluminescence.Because electrochemical luminous sensor has reduced the use of valuable reagent to a certain extent, and experimental installation is oversimplified or microminiaturization, come into one's own day by day in recent years.Based on this, electrochemiluminescence molecule tris (bipyridine) ruthenium molecule is introduced hydrotalcite layers can obtain the good electrochemiluminescence matrix material of luminescent properties.Still the document and the patent report that have nothing to do and combine with the tris (bipyridine) ruthenium molecule both at home and abroad at present in the hydrotalcite stratified material.
Summary of the invention
The object of the present invention is to provide a kind of metal luminescent organic molecule terpyridyl ruthenium chloride (II) and hydrotalcite compound electrochemiluminescence ultrathin membrane and preparation method thereof.Terpyridyl ruthenium chloride (II) i.e. is three (2, the 2-dipyridyl) ruthenium chloride (II) title complex.The present invention introduces hydrotalcite layers with metal luminescent organic molecule tris (bipyridine) ruthenium molecule; In conjunction with the confinement effect of LDHs laminate, make the tris (bipyridine) ruthenium molecular dispersion even, be orientated single; Reach the unit molecule illumination effect, thereby obtained the good electrochemiluminescence matrix material of luminescent properties.The present invention is applied to hydrotalcite in the assembling of electrochemiluminescence molecule the scheme of solution to be provided for the homodisperse of electrochemiluminescence molecule on molecular scale as a kind of type material.
Technical scheme of the present invention is that metal luminescent organic molecule terpyridyl ruthenium chloride (II) and the hydrotalcite nano piece of in organic solvent, peeling off are formed structurally ordered terpyridyl ruthenium chloride (II)/hydrotalcite supramolecule stratified material through layer assembly; This matrix material has made full use of the rigid structure of hydrotalcite and the confinement effect and the host-guest interaction of two-dimensional space, has realized the immobilization of electrochemiluminescence molecule.
The metal luminescent organic molecule and the luminous ultrathin membrane of hydrotalcite composite electrochemical of the present invention's preparation are the electrochemiluminescence film; Three layers of object layer that it is made up of Lewatit, terpyridyl ruthenium chloride (II), Lewatit successively and inorganic component hydrotalcite nano piece three-dimensional space alternately assembling form; Has the laminate structure characteristic; According to the difference of the assembling number of plies, film thickness can be in several nanometers to evenly regulation and control between the hundreds of nanometer simultaneously; The molecular weight of Lewatit is 50000-80000.
The concrete preparation method of the present invention is:
1) preparation of carbonate hydrotalcite precursor:
A. prepare the mixing salt solution of solubility divalence Xiao Suangu and solubility trivalent aluminum nitrate, the concentration of cobalt ion is 0.01-2.00mol/L, and cobalt ion and aluminum ion molar ratio range are 2-3;
B. compound concentration is the urea soln of 0.01-0.05mol/L, and wherein the mol ratio of urea and cobalt ion is 0.5-2;
C. the mixing salt solution with step a preparation changes in the three-necked bottle, and slowly drips the urea soln of step b configuration; Use mass percentage concentration to regulate the pH value at 7-10 then as the ammonia soln of 10%-25%; 95-105 ℃ was stirred 30-60 hour down; Adopt the deionized water centrifuge washing to neutral, 20-100 ℃ dry 12-24 hour, obtain the cobalt aluminum hydrotalcite of carbonate intercalation;
2) preparation of nitrate radical hydrotalcite precursor:
I) the cobalt aluminum hydrotalcite of the carbonate intercalation of 1g step 1) preparation is scattered in the CO that removes of 500-2000mL
2Deionized water in;
II) to step I) in add SODIUMNITRATE and 0.1-0.3mL concentrated nitric acid, the mass ratio of the cobalt aluminum hydrotalcite of SODIUMNITRATE and carbonate intercalation is 100: 1-500: 1, under protection of inert gas, carried out the normal temperature ion exchange reaction 12-24 hour; Adopt and remove CO
2The deionized water centrifuge washing to neutral, 50-70 ℃ dry 12-24 hour, obtain the cobalt aluminum hydrotalcite of nitrate radical intercalation;
3) the cobalt aluminum hydrotalcite of getting the nitrate radical intercalation of 0.1g was peeled off in the formamide solvent of 50-200 milliliter 30-60 hour, nitrogen protection, and stirring velocity is 3000-5000 rev/min; Hydrotalcite solution centrifugal with after peeling off discards throw out, obtains clear colloidal solution B;
4) the Lewatit solution C of configuration 0.5-2mg/mL, the molecular weight of Lewatit is 50000-80000;
5) terpyridyl ruthenium chloride (II) solution D of configuration 0.0001-0.0005mol/L;
6) the indium tin oxide transparent electropane after the hydrophilicity-imparting treatment was soaked in solution B 10-20 minute; After fully cleaning with deionized water, place in the solution C, soak and used washed with de-ionized water in 10-20 minute once more; Be placed in the solution D afterwards; Soak after 10-20 minute and clean, be placed at last to soak after 10-20 minute in the solution C and fully clean, obtain a round-robin terpyridyl ruthenium chloride (II) and the luminous ultrathin membrane of hydrotalcite composite electrochemical;
7) repeating step 6) 1-30 time, the terpyridyl ruthenium chloride (II) and the luminous ultrathin membrane of hydrotalcite composite electrochemical of the assembling that repeatedly circulated.
The described method of hydrophilizing of step 6) is: the indium tin oxide transparent electropane successively at acetone, ethanol, deionized water for ultrasonic 10-20 minute, is fully cleaned to pH=7 with deionized water then.
The invention has the advantages that: utilize the confinement effect of the rigid structure and the two-dimensional space of hydrotalcite laminate; The immobilization of photolytic activity title complex and the ordered arrangement on molecular scale have been realized; Reduce the red shift and the fluorescent quenching that produce because of intermolecular gathering, simplified electrochemiluminescence analysis experimental installation and the loss that reduces solvent simultaneously.This film preparation process easy handling, the luminous intensity of film and film thickness all can be realized accurately controlled through changing the assembling number of times.
Description of drawings
Fig. 1 is 2-14 circulate the terpyridyl ruthenium chloride (II) of assembling and the uv absorption spectra of the luminous ultrathin membrane of hydrotalcite composite electrochemical that the embodiment of the invention 1 obtains, and carries out a UV spectrum test for every at a distance from 2 assemblings that circulate among the figure.
Fig. 2 is the changing conditions that 291 and 457 nanometers absorbancys increase with circulation assembling number of times among Fig. 1.
Fig. 3 is 14 circulate the terpyridyl ruthenium chloride (II) of assembling and the electrochemiluminescence figure of the luminous ultrathin membrane of hydrotalcite composite electrochemical that the embodiment of the invention 2 obtains.
Embodiment
Embodiment 1
1. Wyler's process prepares carbonate hydrotalcite precursor:
Steps A: with the solid Co (NO of 2.91g (0.01mol)
3)
26H
2Solid Al (the NO of O and 1.9g (0.005mol)
3)
39H
2O is dissolved in the deionized water of 500mL (solution I);
Step B: 3g (0.009mol) urea is dissolved in the deionized water of 500mL (solution II);
Step C: the solution I of steps A configuration is placed four-hole bottle, on one side vigorous stirring, slowly be added dropwise to solution II in the solution I on one side; About 0.5h drips off; Using mass percentage concentration then is that 20% ammonia soln is regulated pH to 8,95 ℃ of oil baths reactions 48 hours, with the deionized water centrifuge washing to neutrality; 70 ℃ of dryings 24 hours obtain the cobalt aluminum hydrotalcite of carbonate intercalation;
2. the hydrochlorate exchange process prepares nitrate radical hydrotalcite precursor:
Take by weighing the cobalt aluminum hydrotalcite and the solid NaNO of the carbonate intercalation of 1g step 1 preparation
3Remove CO 127.5g be dissolved in 1000mL
2Deionized water in, behind the homodisperse, add the 0.225mL concentrated nitric acid after, stir under the nitrogen atmosphere condition, normal temperature carry out ion exchange reaction after 24 hours with removing CO
2The deionized water centrifuge washing to neutral, 70 ℃ of dry 12h obtain the cobalt aluminum hydrotalcite of nitrate radical intercalation;
3. get the cobalt aluminum hydrotalcite of the above-mentioned nitrate radical intercalation of 0.1g, under the nitrogen atmosphere condition, stirred 48 hours in 100 milliliters of formamide solvent; Stirring velocity is 4000 rev/mins; Hydrotalcite solution centrifugal with after peeling off discards throw out, obtains clear colloidal solution B;
4. dispose the Lewatit solution C of 1mg/mL, the molecular weight of Lewatit is 60000;
5. dispose terpyridyl ruthenium chloride (II) solution D of 0.0003mol/L;
With the indium tin oxide transparent electropane successively in acetone, ethanol, deionized water for ultrasonic 15 minutes; Fully clean to pH=7 with deionized water, place then in the solution C, soak and used washed with de-ionized water in 15 minutes once more; Be placed in the solution D afterwards; Soak after 15 minutes and clean, be placed at last to soak after 15 minutes in the solution C and fully clean, obtain a round-robin terpyridyl ruthenium chloride (II) and the luminous ultrathin membrane of hydrotalcite composite electrochemical;
7. repeating step is 6,25 times, the terpyridyl ruthenium chloride (II) and the luminous ultrathin membrane of hydrotalcite composite electrochemical of the assembling that repeatedly circulated.
Terpyridyl ruthenium chloride (II) and the luminous ultrathin membrane of hydrotalcite composite electrochemical are characterized: can know by Fig. 1; Terpyridyl ruthenium chloride (II) and of the increase of the luminous ultrathin membrane of hydrotalcite composite electrochemical along with circulation assembling number of times; The maximum absorption band of its uv absorption spectrum presents continuous rising tendency; As shown in Figure 2, absorbancy is assembled number of times near linear relationship with circulation, shows that the amount of the terpyridyl ruthenium chloride (II) of each assembling is a fixed value.
Embodiment 2
1. with embodiment 1;
2. with embodiment 1;
3. with embodiment 1, obtain clear colloidal solution B;
4. dispose the Lewatit solution C of 1mg/mL, the molecular weight of Lewatit is 70000;
5. dispose terpyridyl ruthenium chloride (II) solution D of 0.0001mol/L;
With the indium tin oxide transparent electropane successively in acetone, ethanol, deionized water for ultrasonic 10 minutes; Fully clean to pH=7 with deionized water then, then it was soaked in solution B 10 minutes, after fully cleaning with deionized water; Place in the solution C; Soak and used washed with de-ionized water once more in 10 minutes, be placed on afterwards in the solution D, soak after 10 minutes and clean; Be placed at last to soak after 10 minutes in the solution C and fully clean, obtain a round-robin terpyridyl ruthenium chloride (II) and the luminous ultrathin membrane of hydrotalcite composite electrochemical;
7. repeating step is 6,14 times, the terpyridyl ruthenium chloride (II) and the luminous ultrathin membrane of hydrotalcite composite electrochemical of the assembling that repeatedly circulated.
Utilizing electrochemical workstation is reference electrode with silver/Silver monochloride; Platinum filament is a counter electrode; The terpyridyl ruthenium chloride (II) of 14 circulation assemblings that step 7 obtains is a working electrode with the luminous ultrathin membrane of hydrotalcite composite electrochemical; Phosphate buffer solution with 0.1 mol is an ionogen; In the scope of 0.5-1.2 volt, carry out cyclic voltammetry scan, can know that by the electrochemiluminescence figure sign of Fig. 3 terpyridyl ruthenium chloride (II) has obtained stable electrochemiluminescence signal with the luminous ultrathin membrane of hydrotalcite composite electrochemical.
Embodiment 3
1. with embodiment 1;
2. with embodiment 1;
3. with embodiment 1, obtain clear colloidal solution B;
4. dispose the Lewatit solution C of 1mg/mL, the molecular weight of Lewatit is 80000;
5. dispose terpyridyl ruthenium chloride (II) solution D of 0.0005mol/L;
With the indium tin oxide transparent electropane successively in acetone, ethanol, deionized water for ultrasonic 20 minutes; Fully clean to pH=7 with deionized water then, then it was soaked in solution B 20 minutes, after fully cleaning with deionized water; Place in the solution C; Soak and used washed with de-ionized water once more in 20 minutes, be placed on afterwards in the solution D, soak after 20 minutes and clean; Be placed at last to soak after 20 minutes in the solution C and fully clean, obtain a round-robin terpyridyl ruthenium chloride (II) and the luminous ultrathin membrane of hydrotalcite composite electrochemical;
7. repeating step is 6,20 times, the terpyridyl ruthenium chloride (II) and the luminous ultrathin membrane of hydrotalcite composite electrochemical of the assembling that repeatedly circulated.
Claims (3)
1. metal luminescent organic molecule and the luminous ultrathin membrane of hydrotalcite composite electrochemical; It is characterized in that: said ultrathin membrane is the electrochemiluminescence film; Three layers of object layer that it is made up of Lewatit, terpyridyl ruthenium chloride (II), Lewatit successively and inorganic component hydrotalcite nano piece three-dimensional space alternately assembling form; Have the laminate structure characteristic, according to the difference of the assembling number of plies, film thickness can be in several nanometers to evenly regulation and control between the hundreds of nanometer simultaneously; The molecular weight of Lewatit is 50000-80000.
2. a metal luminescent organic molecule and the luminous ultrathin membrane of hydrotalcite composite electrochemical and preparation method thereof is characterized in that its concrete operations step is following:
1) preparation of carbonate hydrotalcite precursor:
A. prepare the mixing salt solution of solubility divalence Xiao Suangu and solubility trivalent aluminum nitrate, the concentration of cobalt ion is 0.01-2.00mol/L, and cobalt ion and aluminum ion molar ratio range are 2-3;
B. compound concentration is the urea soln of 0.01-0.05mol/L, and wherein the mol ratio of urea and cobalt ion is 0.5-2;
C. the mixing salt solution with step a preparation changes in the three-necked bottle, and slowly drips the urea soln of step b configuration; Use mass percentage concentration to regulate the pH value at 7-10 then as the ammonia soln of 10%-25%; 95-105 ℃ was stirred 30-60 hour down; Adopt the deionized water centrifuge washing to neutral, 20-100 ℃ dry 12-24 hour, obtain the cobalt aluminum hydrotalcite of carbonate intercalation;
2) preparation of nitrate radical hydrotalcite precursor:
I) the cobalt aluminum hydrotalcite of the carbonate intercalation of 1g step 1) preparation is scattered in the CO that removes of 500-2000mL
2Deionized water in;
II) to step I) in add SODIUMNITRATE and 0.1-0.3mL concentrated nitric acid, the mass ratio of the cobalt aluminum hydrotalcite of SODIUMNITRATE and carbonate intercalation is 100: 1-500: 1, under protection of inert gas, carried out the normal temperature ion exchange reaction 12-24 hour; Adopt and remove CO
2The deionized water centrifuge washing to neutral, 50-70 ℃ dry 12-24 hour, obtain the cobalt aluminum hydrotalcite of nitrate radical intercalation;
3) the cobalt aluminum hydrotalcite of getting the nitrate radical intercalation of 0.1g was peeled off in the formamide solvent of 50-200 milliliter 30-60 hour, nitrogen protection, and stirring velocity is 3000-5000 rev/min; Hydrotalcite solution centrifugal with after peeling off discards throw out, obtains clear colloidal solution B;
4) the Lewatit solution C of configuration 0.5-2mg/mL, the molecular weight of Lewatit is 50000-80000;
5) terpyridyl ruthenium chloride (II) solution D of configuration 0.0001-0.0005mol/L;
6) the indium tin oxide transparent electropane after the hydrophilicity-imparting treatment was soaked in solution B 10-20 minute; After fully cleaning with deionized water, place in the solution C, soak and used washed with de-ionized water in 10-20 minute once more; Be placed in the solution D afterwards; Soak after 10-20 minute and clean, be placed at last to soak after 10-20 minute in the solution C and fully clean, obtain a round-robin terpyridyl ruthenium chloride (II) and the luminous ultrathin membrane of hydrotalcite composite electrochemical;
7) repeating step 6) 1-30 time, the terpyridyl ruthenium chloride (II) and the luminous ultrathin membrane of hydrotalcite composite electrochemical of the assembling that repeatedly circulated.
3. preparation method according to claim 2; It is characterized in that; The described method of hydrophilizing of step 6) is: the indium tin oxide transparent electropane successively at acetone, ethanol, deionized water for ultrasonic 10-20 minute, is fully cleaned to pH=7 with deionized water then.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102874747A (en) * | 2012-10-12 | 2013-01-16 | 北京化工大学 | Method for preparing multilevel structural material by performing epitaxial growth of layered double hydroxide (LDH) based on guiding of electric field of metallic oxide nano array |
| CN105419075A (en) * | 2015-12-23 | 2016-03-23 | 江苏道勤新材料科技有限公司 | Magnetic 3D printing material |
| WO2016078220A1 (en) * | 2014-11-17 | 2016-05-26 | 京东方科技集团股份有限公司 | Blue light polarizing thin film and preparation method therefor, as well as blue light backlight source and liquid crystal display device |
| CN112300404A (en) * | 2020-11-02 | 2021-02-02 | 北京化工大学 | Preparation method of active supramolecular polymer based on layered double hydroxide bionic confinement driving |
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2011
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102874747A (en) * | 2012-10-12 | 2013-01-16 | 北京化工大学 | Method for preparing multilevel structural material by performing epitaxial growth of layered double hydroxide (LDH) based on guiding of electric field of metallic oxide nano array |
| CN102874747B (en) * | 2012-10-12 | 2015-02-18 | 北京化工大学 | Method for preparing multilevel structural material by performing epitaxial growth of layered double hydroxide (LDH) based on guiding of electric field of metallic oxide nano array |
| WO2016078220A1 (en) * | 2014-11-17 | 2016-05-26 | 京东方科技集团股份有限公司 | Blue light polarizing thin film and preparation method therefor, as well as blue light backlight source and liquid crystal display device |
| CN105419075A (en) * | 2015-12-23 | 2016-03-23 | 江苏道勤新材料科技有限公司 | Magnetic 3D printing material |
| CN112300404A (en) * | 2020-11-02 | 2021-02-02 | 北京化工大学 | Preparation method of active supramolecular polymer based on layered double hydroxide bionic confinement driving |
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Application publication date: 20120620 |