CN101220266A - Process for producing beta-diketone functionalization rare earth mesoporous hybridisation luminescent material - Google Patents
Process for producing beta-diketone functionalization rare earth mesoporous hybridisation luminescent material Download PDFInfo
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Abstract
The invention belongs to the technical field of manufacturing nano mesoporous material, in particular to a novel synthesis technology of Beta to diketone functionalized rare earth mesoporous hybrization and luminescent material. The invention first adopts a method of organic modification and synthesis to covalently graft an organic ligand molecule with Beta to diketone structure in a main body framework of an inorganic mesoporous, then rare earth europium or terbium ion is introduced to synthesize the high ordered mesoporous hybrization and luminescent material with steady chemistry and thermodynamic performance. The method and experimenting condition of the invention are moderate, the whole manufacturing system is easy to be established, the operation is easy, and the condition is easy for controlling, so the obtained products has steady quality. .
Description
Technical field
The invention belongs to the mesoporous material preparing technical field, be specifically related to a kind of preparation method of beta-diketone functionalization rare earth mesoporous hybridisation luminescent material.
Background technology
The mesoporous nano material is with its special mesoscopic structure and character, superelevation specific surface (＞2000m
2/ g), the pore volume (～2cm of super large
3/ g), big and the adjustable aperture (2-50nm) of homogeneous in high-tech areas such as microelectronics, bioprotein isolation identification, useful for drug delivery, transmitter, photoelectromagnetism materials, especially has broad application prospects at aspects such as cracking of oil, catalysis, absorption, separation.Its discovery is photochemical catalysis simultaneously, solar cell, and new vitality has been injected in the research in fields such as fuel cell, is the core technology that has market potential.The synthetic chemistry that with the supramolecule is template mesoporous nano material has obtained fast development in recent years, various new compositions, the mesoporous material of new texture continue to bring out, mesoporous nano material new property, new research of using obtain the extensive attention of international each major company, R﹠D institution, have become the forward position and the focus of international research.
Rare earth beta-diketon class organic coordination compound is the very important optical active substance of a class, particularly as highly efficient luminous substance, is familiar with by people more for a long time.Although rare earth compounding has good luminescent properties, the unstable of its light and heat has limited their application space.Practice shows, rare earth organic complex is incorporated in the mesoporous host matrix, can improve the stability of its light and heat, can make its influence of avoiding external environment such as moisture again, thereby has improved its luminescent properties.At present, the preparation method that the hybrid mesoporous material of organic-inorganic nano is commonly used has direct doping method, grafting and copolycondensation method.Directly doping method is that rare earth compounding is doped among the inorganic matrix, owing to be that a kind of simple physics is compound, only has more weak interaction between rare earth compounding and the matrix between the two.Like this, unavoidably some problems can occur, if any machine component skewness, the doping of rare earth compounding is not high, and the rare earth compounding instability is separated out or the like from matrix easily.Although the research worker also explores new technology of preparing constantly, up to now, also do not report about the synthetic technology of beta-diketone functionalization rare earth mesoporous hybridisation luminescent material.
Summary of the invention
The object of the present invention is to provide a kind of preparation method of novel beta-diketone functionalization rare earth mesoporous hybridisation luminescent material.It passes through the covalent linkage grafting in inorganic mesoporous SBA-15 material of main part with organic beta-diketon rare earth compounding, thereby in the grafting that has realized on the level of molecule between organic and the inorganic matrix, prepared luminous good hybrid mesoporous material, and performances such as rare earth compounding luminous, quantum yield have therein been studied.
The preparation method of the beta-diketone functionalization rare earth mesoporous hybridisation luminescent material that the present invention proposes, concrete steps are as follows:
(1) intermediate is synthetic: with beta-diketon organic ligand molecular melting in tetra oxygen furyl or pyridine, to wherein being incorporated in NaH, reacted 1.5-2 hour, the tetrahydrofuran (THF) or the pyridine solution that then add the silica-based isocyanic ester of propyl group three ethoxies, reaction is 10-15 hour under 60-75 ℃ of temperature, rotary evaporation is removed organic solvent tetra oxygen furyl or pyridine, promptly gets the siloxanes intermediate of beta-diketon modification; Wherein: the mol ratio of beta-diketon organic ligand and NaH is 1: 1-1: 2, and the mol ratio of beta-diketon organic ligand molecule and the silica-based isocyanic ester of propyl group three ethoxies is 1: 2;
(2) building-up reactions of the mesoporous SBA-15 of beta-diketone functionalization: the siloxanes intermediate and the tetraethoxy (TEOS) of the beta-diketon modification of step (1) gained are mixed; The P123 tensio-active agent is added in the deionized water, stir and make it dissolving, add hydrochloric acid again, mix under the room temperature condition; In whipping process, drip the mixed solution of the siloxanes intermediate of tetraethoxy (TEOS) and beta-diketon modification, stirred 18-30 hour under the room temperature; Wherein, the mol ratio of the siloxanes intermediate of beta-diketon modification and tetraethoxy is 0.94: 0.06-0.96: 0.04; The mass ratio of P123 tensio-active agent, deionized water and hydrochloric acid is 1: (7-8): (2-2.5);
(3) hydrothermal synthesis reaction: it is the stainless steel cauldron of lining that step (2) products therefrom is placed tetrafluoroethylene, under 90-110 ℃ of temperature condition crystallization 24-50 hour;
(4) filtration washing: to neutral, oven dry obtains the not light yellow powder of template agent removing with deionized water wash step (3) products therefrom;
(5) removal of template: step (4) products therefrom is used extraction using alcohol 18-28 hour in apparatus,Soxhlet's, drying obtains buff powder;
(6) luminous mesoporous material is synthetic: the nitrate of rare-earth europium or terbium is dissolved in the ethanolic soln, then step (5) products therefrom is added wherein, stirred backflow 10-15 hour down, the pressed powder that finally obtains filters to be collected, with washing with alcohol (3-5 time), vacuum-drying promptly gets required product; Wherein, the mol ratio of rare-earth europium or terbium and step (5) products therefrom is 1: 3.
Among the present invention, beta-diketon organic ligand molecule described in the step (1) is any of diphenylpropane-1,3-dione(DPPO), methyl ethyl diketone, furoyltrifluoroacetone(FTA, or benzoyl acetone.
Among the present invention, can add the second organic ligand phenanthroline in the ethanolic soln of rare-earth europium or terbium described in the step (6).Wherein, the mol ratio of phenanthroline and rare earth ion is 1: 1.
Among the present invention, the vacuum-drying temperature is 55-65 ℃ described in the step (6).
Utilize structure, pattern, the composition of the inventive method products therefrom can adopt X-ray small angle powdery diffractometry (SAXRD), high-resolution-ration transmission electric-lens (HRTEM), fourier transform infrared spectroscopy (FTIR) and fluorescence spectrum etc. to characterize respectively.
The invention has the advantages that:
1, the beta-diketone functionalization rare earth mesoporous hybridisation luminescent material fluorescence lifetime of being produced by the inventive method is long and luminous quantum efficiency is high, and microscopic appearance is regular in order.
2, technology of the present invention is simple, and whole preparation system makes up easily, and easy and simple to handle, condition is easily controlled, and product is handled convenient simple and direct.
3, mild condition of the present invention need not to use any additives and catalyzer etc., and therefore, the inventive method has the characteristics of economy, cost cheapness.Be the organic and inorganic component to be fitted together by covalent linkage, thereby overcome the relatively poor weakness of small molecules luminescent material mechanicalness and stability deficiency and high-molecular luminous material luminescent properties, and it is regular to obtain the surface, is situated between to see orderly mesoporous nano luminescent material.
Description of drawings
Fig. 1 is the small angle X-ray diffraction spectrogram of the mesoporous luminescent material of the embodiment of the invention 1 gained rare-earth europium.
Fig. 2 is the high-resolution-ration transmission electric-lens figure of the embodiment of the invention 1 gained rare-earth europium mesoporous red light material.
Fig. 3 is the fluorescent exciting spectrogram of the embodiment of the invention 1 gained rare-earth europium mesoporous red light material.
Fig. 4 is the fluorescence emission spectrogram of the embodiment of the invention 1 gained rare-earth europium mesoporous red light material.
Embodiment
Further specify the present invention below by embodiment, but protection scope of the present invention is not limited to these embodiment.
(1) the diphenylpropane-1,3-dione(DPPO) intermediate is synthetic
The 1mmol diphenylpropane-1,3-dione(DPPO) is dissolved in the 20mL anhydrous tetrahydro furan and adds 2mmolNaH to solution system, the violent bubbling of reaction solution, after one and a half hours, in above-mentioned phegma, drip the tetrahydrofuran solution that contains 2.2mmol propyl-triethoxysilicane base propyl isocyanate, reacted 12 hours down at 65 ℃, rotary evaporation removes and desolvates, and gets the yellow oil droplet shape of unusual heavy-gravity product.
(2) diphenylpropane-1,3-dione(DPPO) functionalization binary hybrid mesoporous luminescent material is synthetic
At first, take by weighing the hydrochloric acid 30g that the 1.0gPluronicP123 tensio-active agent adds 7.5g deionized water and 2mol/L, heated and stirred makes it dissolving.Under the room temperature condition, slowly drip the mixed solution of TEOS and diphenylpropane-1,3-dione(DPPO) intermediate, mol ratio is 0.94: 0.06, stirs 24 hours.Put into the stainless steel cauldron that tetrafluoroethylene is a lining then, crystallization is 48 hours under 100 ℃ of conditions.Extremely neutral with the deionized water wash product.60 ℃ of oven dry down, obtain the not faint yellow powder of template agent removing.Then, use dehydrated alcohol extraction 24 hours in apparatus,Soxhlet's, drying obtains the buff powder sample; At last, with 1mmol rare-earth europium (Eu
3+) nitrate be dissolved in the ethanolic soln, add the above-mentioned buff powder sample of 3mmol, stir down and refluxed 12 hours, the pressed powder that finally obtains filters to be collected, with ethanol repetitive scrubbing 3 times, vacuum-drying under 60 ℃ of conditions promptly gets required product.
(1) the diphenylpropane-1,3-dione(DPPO) intermediate is synthetic
The 1.5mmol diphenylpropane-1,3-dione(DPPO) is dissolved in the 25mL anhydrous tetrahydro furan and adds 3mmolNaH to solution system, the violent bubbling of reaction solution, after about one and a half hours, in above-mentioned phegma, drip the tetrahydrofuran solution that contains 3.3mmol propyl-triethoxysilicane base propyl isocyanate, reacted 12 hours down at 70 ℃, rotary evaporation removes and desolvates, and gets the yellow oil droplet shape of unusual heavy-gravity product.
(2) diphenylpropane-1,3-dione(DPPO) functionalization ternary hybrid mesoporous luminescent material is synthetic
Take by weighing the hydrochloric acid 45g of 1.5gPluronicP123 tensio-active agent adding 11g deionized water and 2mol/L, heated and stirred makes it dissolving.Under the room temperature condition, slowly drip the mixed solution of TEOS and diphenylpropane-1,3-dione(DPPO) intermediate, mol ratio is 0.96: 0.04, stirs 24 hours.Put into the stainless steel cauldron that tetrafluoroethylene is a lining then, crystallization is 50 hours under 110 ℃ of conditions.Extremely neutral with the deionized water wash product.60 ℃ of oven dry down, obtain the not faint yellow powder of template agent removing.In apparatus,Soxhlet's, use dehydrated alcohol extraction 48 hours, drying.At last, will add the above-mentioned sample of 6mmol in the mixed ethanol solution of 2mmol europium nitrate and 2mmol phenanthroline, stir down and refluxed 15 hours, the pressed powder that finally obtains filters to be collected, use the ethanol repetitive scrubbing, vacuum-drying under 60 ℃ of conditions promptly gets required product.
(1) the methyl ethyl diketone intermediate is synthetic
The 1mmol methyl ethyl diketone is dissolved in the 15mL anhydrous pyridine and adds 2mmolNaH to solution system, the violent bubbling of reaction solution, after about one and a half hours, in above-mentioned phegma, drip the tetrahydrofuran solution that contains 2.2mmol propyl-triethoxysilicane base propyl isocyanate, reacted 12 hours down at 65 ℃, rotary evaporation removes and desolvates, and gets the yellow oil droplet shape of unusual heavy-gravity product.
(2) the functional mesoporous hybrid luminescent materials of methyl ethyl diketone is synthetic
Take by weighing the hydrochloric acid 36g of 1.2gPluronicP123 tensio-active agent adding 9.0g deionized water and 2mol/L, heated and stirred makes it dissolving.Under the room temperature condition, slowly drip the mixed solution of TEOS and methyl ethyl diketone intermediate, mol ratio is 0.94: 0.06, stirs 24 hours.Put into the stainless steel cauldron that tetrafluoroethylene is a lining then, crystallization is 48 hours under 100 ℃ of conditions.Extremely neutral with the deionized water wash product.60 ℃ of oven dry down, obtain the not faint yellow powder of template agent removing.Use dehydrated alcohol extraction 24 hours in apparatus,Soxhlet's, drying obtains sample.At last, with 1mmol rare earth terbium (Tb
3+) nitrate be dissolved in the ethanolic soln, add the above-mentioned buff powder sample of 3mmol, stir down and refluxed 12 hours, the pressed powder that finally obtains filters to be collected, and uses the ethanol repetitive scrubbing, vacuum-drying under 60 ℃ of conditions promptly gets required product.
(1) the furoyltrifluoroacetone(FTA, intermediate is synthetic
The 2mmol furoyltrifluoroacetone(FTA, is dissolved in the 35mL anhydrous tetrahydro furan and adds 4mmolNaH to solution system, the violent bubbling of reaction solution, after about one and a half hours, in above-mentioned phegma, drip the tetrahydrofuran solution that contains 4.0mmol propyl-triethoxysilicane base isocyanic acid, reacted 12 hours down at 65 ℃, rotary evaporation removes and desolvates, and gets the yellow oil droplet shape of unusual heavy-gravity product.
(2) the functional mesoporous hybrid luminescent materials of furoyltrifluoroacetone(FTA, is synthetic
Take by weighing the hydrochloric acid 60g of 2.0gPluronicP123 tensio-active agent adding 15g deionized water and 2mol/L, heated and stirred makes it dissolving.Under the room temperature condition, slowly drip the mixed solution of TEOS and furoyltrifluoroacetone(FTA, intermediate, ratio is 0.94: 0.06, stirs 24 hours.Put into the stainless steel cauldron that tetrafluoroethylene is a lining then, crystallization is 48 hours under 100 ℃ of conditions.Extremely neutral with the deionized water wash product.60 ℃ of oven dry down, obtain the not faint yellow powder of template agent removing.Use dehydrated alcohol extraction 24 hours in apparatus,Soxhlet's, drying obtains sample.At last, with 1.5mmol rare-earth europium (Eu
3+) nitrate be dissolved in the ethanolic soln, add the above-mentioned buff powder sample of 4.5mmol, stir down and refluxed 12 hours, the pressed powder that finally obtains filters to be collected, and uses the ethanol repetitive scrubbing, vacuum-drying under 60 ℃ of conditions promptly gets required product.
(1) the benzoyl acetone intermediate is synthetic
The 1mmol benzoyl acetone is dissolved in the 20mL anhydrous tetrahydro furan and adds 2mmolNaH to solution system, the violent bubbling of reaction solution, after about one and a half hours, in above-mentioned phegma, drip the tetrahydrofuran solution that contains the silica-based propyl isocyanate of 2.2mmol triethoxy, reacted 12 hours down at 65 ℃, rotary evaporation removes and desolvates, and gets the yellow oil droplet shape of unusual heavy-gravity product.
(2) the functional mesoporous hybrid luminescent materials of benzoyl acetone is synthetic
Take by weighing the hydrochloric acid 30g of 1.0gPluronicP123 tensio-active agent adding 7.5g deionized water and 2mol/L, heated and stirred makes it dissolving.Under the room temperature condition, slowly drip the mixed solution of TEOS and benzoyl acetone intermediate, mol ratio is 0.96: 0.04, stirs 24 hours.Put into the stainless steel cauldron that tetrafluoroethylene is a lining then, crystallization is 48 hours under 100 ℃ of conditions.Extremely neutral with the deionized water wash product.60 ℃ of oven dry down, obtain the not faint yellow powder of template agent removing.Use dehydrated alcohol extraction 24 hours in apparatus,Soxhlet's, drying obtains sample.At last, with the rare-earth europium (Eu of 1mmol
3+) nitrate be dissolved in the ethanolic soln, add the above-mentioned buff powder sample of 3mmol, stir down and refluxed 12 hours, the pressed powder that finally obtains filters to be collected, and uses the ethanol repetitive scrubbing, vacuum-drying under 60 ℃ of conditions promptly gets required product.
The above-mentioned description to embodiment is can understand and apply the invention for the ease of those skilled in the art.The person skilled in the art obviously can easily make various improvement to these embodiment, and needn't pass through performing creative labour being applied in the General Principle of this explanation among other embodiment.Therefore, the invention is not restricted to the embodiment here, those skilled in the art should be within protection scope of the present invention for improvement and modification that the present invention makes according to announcement of the present invention.
Claims (4)
1. the preparation method of a beta-diketone functionalization rare earth mesoporous hybridisation luminescent material is characterized in that concrete steps are as follows:
(1) intermediate is synthetic: with beta-diketon organic ligand molecular melting in tetra oxygen furyl or pyridine, to wherein being incorporated in NaH, reacted 1.5-2 hour, the tetrahydrofuran solution that then adds the silica-based isocyanic ester of propyl group three ethoxies, reaction is 10-15 hour under 60-75 ℃ of temperature, rotary evaporation is removed organic solvent tetra oxygen furyl or pyridine, promptly gets the siloxanes intermediate of beta-diketon modification; Wherein: the mol ratio of beta-diketon organic ligand and NaH is 1: 1-1: 2, and the mol ratio of beta-diketon organic ligand molecule and the silica-based isocyanic ester of propyl group three ethoxies is 1: 2;
(2) building-up reactions of the mesoporous SBA-15 of beta-diketone functionalization: the siloxanes intermediate and the tetraethoxy of the beta-diketon modification of step (1) gained are mixed; The P123 tensio-active agent is added in the deionized water, stir and make it dissolving, add hydrochloric acid again, mix under the room temperature condition; In whipping process, drip the mixed solution of the siloxanes intermediate of tetraethoxy and beta-diketon modification, stirred 18-30 hour under the room temperature; Wherein, the mol ratio of the siloxanes intermediate of beta-diketon modification and tetraethoxy is 0.94: 0.06-0.96: 0.04; The mass ratio of P123 tensio-active agent, deionized water and hydrochloric acid is 1: (7-8): (2-2.5);
(3) hydrothermal synthesis reaction: it is the stainless steel cauldron of lining that step (2) products therefrom is placed tetrafluoroethylene, under 90-110 ℃ of temperature condition crystallization 24-50 hour;
(4) filtration washing: to neutral, oven dry obtains the not light yellow powder of template agent removing with deionized water wash step (3) products therefrom;
(5) removal of template: step (4) products therefrom is used extraction using alcohol 18-28 hour in apparatus,Soxhlet's, drying obtains buff powder;
(6) luminous mesoporous material is synthetic: the nitrate of rare-earth europium or terbium is dissolved in the ethanolic soln, then step (5) products therefrom is added wherein, stirred backflow 10-15 hour down, the pressed powder that finally obtains filters to be collected, use washing with alcohol, vacuum-drying promptly gets required product; Wherein, the mol ratio of rare-earth europium or terbium and step (5) products therefrom is 1: 3.
2. the preparation method of beta-diketone functionalization rare earth mesoporous hybridisation luminescent material according to claim 1 is characterized in that beta-diketon organic ligand molecule described in the step (1) is any of diphenylpropane-1,3-dione(DPPO), methyl ethyl diketone, furoyltrifluoroacetone(FTA, or benzoyl acetone.
3. the preparation method of beta-diketone functionalization rare earth mesoporous hybridisation luminescent material according to claim 1 is characterized in that adding the second organic ligand phenanthroline in the ethanolic soln of rare-earth europium described in the step (6) or terbium; Wherein, the mol ratio of phenanthroline and rare earth ion is 1: 1.
4. the preparation method of beta-diketone functionalization rare earth mesoporous hybridisation luminescent material according to claim 1 is characterized in that the vacuum-drying temperature is 55-65 ℃ described in the step (6).
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