CN102618275B - Method for preparing rare-earth organic and inorganic zinc oxide semiconductor nanopore composite luminescent material based on hydroxyl functionalization - Google Patents
Method for preparing rare-earth organic and inorganic zinc oxide semiconductor nanopore composite luminescent material based on hydroxyl functionalization Download PDFInfo
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Abstract
The invention belongs to the technical field of rare-earth fluorescent nano composite materials, and relates to a method for preparing a rare-earth organic and inorganic zinc oxide semiconductor nanopore luminescent material based on hydroxyl functionalization. The method comprises the following steps of: modifying zinc oxide semiconductor nano particles by an organic synthesis method by using hydroxyl-containing organic matter, and modifying hydroxyl further to obtain a functionalized zinc oxide precursor; connecting the precursor to a silica network by hydrolytic polycondensation reaction by a sol-gel method; and assembling coordination groups on the silica network and rare-earth ions to form a rare-earth complex, and finally obtaining the rare-earth functionalized zinc oxide semiconductor nanopore composite luminescent material which is regular in surface appearance, stable in chemical and thermodynamic property and high in luminescent intensity and fluorescent efficiency. The method is high in operability and reproducibility, and experimental conditions are mild and controllable.
Description
Technical field
The invention belongs to the fluorescent material technical field, be specifically related to a kind of preparation method of the rare earth organic-inorganic zinc oxide semi-conductor nanoporous composite luminescent material based on hydroxyl functionalization.
Background technology
Nanoparticle refers to the particle of granularity between 1-100 nm, claims ultrafine particulate again, is between microsystem and the meta system, can predict, and nanoparticle has strange physics-chem characteristic.The characteristics that nanoparticle is different from the macro object structure are, its surface-area accounts for very big proportion, and surface atom had not both had the amorphous layer that long-range order does not have short-range order.Can think the state of nanoparticle surface atom more near gaseous state, and the atom of particle inside may be orderly arrangement.This constitutional features of nanoparticle makes it have the effect of four aspects such as volume effect, quantum effect, surface effects and macro quanta tunnel effect.Nano zine oxide is a kind of novel high function fine inorganic product geared to the 21st century, shows many special nature, as non-migrating, fluorescence, piezoelectricity, absorption and scatters ultraviolet ability etc.It shows many specific functions at aspects such as catalysis, optics, magnetics, mechanics discovered in recent years, make it have important use to be worth in many fields such as pottery, chemical industry, electronics, optics, biology, medicine, have common zinc oxide singularity and the purposes that can't compare.
Rare earth luminous to have receptivity strong, and the efficiency of conversion height can be launched the spectrum from the ultraviolet ray to the infrared light, at visible region very strong advantages such as emissive power is arranged especially.But simple rare-earth salts molar absorptivity is low, and effectively the excitation rare-earth ion is luminous, simultaneously luminously is easy to cancellation.Rare earth compounding effectively absorbs energy and gives the center rare earth ion in the mode of non-radiative de excitation with transmission ofenergy by organic ligand, sends the rare earth ion characteristic spectrum by the f-f transition then, and its luminous characteristics is that the spectral line of emission is narrow, and fluorescence lifetime is long.Yet because the photo and thermal stability of rare earth organic complex itself is relatively poor, and is positioned over it in air, because the non-radiative multipole phonon that the stretching vibration of quencher such as oh group brings around the solvation water etc. decays, its emissive porwer is reduced gradually.In recent years, the rare earth organic/inorganic hybridization material has caused greatly interest of people, polycomponent rare earth function hybrid systems such as rare earth compounding/nano composite material, mesoporous material, macromolecular material have appearred, reach the polymer that has bonding action with rare earth ion by the small molecules part of choosing a series of triplet and rare earth ion coupling, prepared the good rare-earth hybridized luminescent material of luminescent properties.In order to improve the luminescent properties of this kind material, can choose different hydridization matrix, prepare a series of hybrid luminescent materials thereby design different synthetic routes, and performance such as, quantum yield luminous to it is studied.
At present, research report about rare earth organic inorganic hybridization luminescent material is numerous both at home and abroad, for organic-inorganic semiconductor nano composite hybridization luminescent material, relevant bibliographical information had also been arranged in recent years both at home and abroad, increasing researchist begins to go deep into systematic research, make this field that development widely arranged, and partial results realized commercial applications, especially shows great application prospect in fields such as information storage medium, nonlinear optical material, microelectronic device, chemical biosensors.Yet yet there are no report with semiconductor oxide zinc hydroxyl modified and with synthetic technology that the effect of silica network by covalent linkage forms rare earth organic-inorganic semiconductor nano composite luminescent material.
Summary of the invention
Purpose of the present invention aims to provide a kind of preparation method of novel rare earth organic-inorganic zinc oxide semi-conductor nanoporous composite luminescent material based on hydroxyl functionalization.It is modified semiconductor oxide zinc by the organism parcel of hydroxyl, and become the silica network with tetraethoxy by hydrolysis condensation reaction, last rare earth organic complex is connected with it by coordinate bond, thereby realized between rare earth, nano zine oxide, silica network and the organic ligand compound on molecular level, prepared rare earth functionalization zinc oxide semi-conductor nanoporous composite luminescent material, and performances such as its pattern, thermostability, luminous, quantum yield have been studied.
The preparation method based on the rare earth organic-inorganic zinc oxide semi-conductor nanoporous composite luminescent material of hydroxyl functionalization that the present invention proposes, concrete steps are as follows:
(1) preparation of zinc oxide semi-conductor nanoparticle and modification:
By zinc dimethacrylate and LiOH prepared in reaction zinc oxide nano-particle, the organism with hydroxyl further wraps up and modifies it then;
(2) preparation of functionalization presoma:
The zinc oxide nano-particle that will be contained the organism modified of hydroxyl is dissolved in organic solvent, place flask, add sodium hydride and slough proton hydrogen, dropwise add the coupling agent with organic solvent dissolution, the temperature of reaction of solution is 65-75 ℃ in the control flask, and under nitrogen atmosphere back flow reaction 12 h, cooling, rotary evaporation is removed organic solvent, namely gets the functionalized nano zinc oxide precursor; Wherein: the mol ratio of sodium hydride and coupling agent is 1:1;
(3) preparation of nano zine oxide functional mesoporous material:
The functionalized nano zinc oxide precursor of step (2) gained and the mixed solution of tetraethoxy are dropwise added in the deionized water that is dissolved with template Pluronic P123, the pH value of hydrochloric acid conditioning solution, at 20-40 ℃ of following hydrolysis condensation reaction 24 h, transfer in the tetrafluoroethylene reactor, 100 ℃ of following crystallization 48 h, products therefrom after filtration and the washing, dry air; Obtain the nano zine oxide functional mesoporous material; Wherein: the mol ratio of template P123, tetraethoxy, functionalized nano zinc oxide precursor, hydrochloric acid, water is 0.0172:0.96:0.04: 6:208.33;
(4) template is removed:
The nano zine oxide functional mesoporous material of step (3) gained was removed template in 2 days with extraction using alcohol in the Soxhlet extractor, filter the back and use absolute ethanol washing, drying gets final product;
(5) mesoporous material of nano zine oxide functionalization and rare-earth ion coordination reaction:
The nano zine oxide functional mesoporous material of removing template of step (4) gained is dissolved in organic solvent, drip the ethanolic soln of small molecules part earlier, drip the ethanolic soln of rare earth nitrate again, make it that coordination reaction take place and obtain rare earth compounding, temperature of reaction is 20-35 ℃, reaction times is 3-5 h, removes the nano zine oxide functional mesoporous material of template: the small molecules part: the mol ratio of rare earth nitrate is 1:3:1.
Among the present invention, the initiator described in the step (2) is benzoyl peroxide.
Among the present invention, the organism of the two keys of the hydroxyl described in the step (1) is hydroxyethyl methylacrylate.
Among the present invention, the coupling agent described in the step (3) is the silica-based propyl isocyanate of triethoxy.
Among the present invention, organic solvent is tetrahydrofuran (THF) described in the step (2).
Among the present invention, template described in the step (4) is triblock polymer Pluronic P123.
Among the present invention, drying temperature is 60-70 ℃ described in the step (4).
Among the present invention, rare earth nitrate is europium nitrate or Terbium trinitrate described in the step (5).
Among the present invention, the small molecules part described in the step (5) is a kind of in thenoyltrifluoroacetone, benzoyltrifluoroacetone, diphenylpropane-1,3-dione(DPPO) or the nicotinic acid.
Among the present invention, the organic solvent described in the step (5) is N, dinethylformamide.
Among the present invention, the zinc oxide semi-conductor nanometer particle process method is in the step (1): the ethanolic soln of lithium hydroxide is joined in the ethanolic soln of zinc dimethacrylate, and 80 ℃ of 3 h that reflux revolve the inspissation contracting, centrifugal purification, 60 ℃ of vacuum-dryings then; The zinc oxide nano-particle that 1 mmol is made is dissolved in dehydrated alcohol, adds the organic molecule that 0.005 g initiator and 1 ml contain the two keys of hydroxyl, and with the mixture mechanical stirring, the control temperature of reaction is 60-75 ℃, reaction times 6 h.
Utilize the hydroxyl functional rare earth organic-inorganic zinc oxide semi-conductor nanoporous composite luminescent material compound with regular structure of present method preparation, Heat stability is good, the luminous efficiency height, life-span is long, and its structure, pattern, composition, thermostability and luminous intensity can adopt X-ray powder diffraction (SAXRD), scanning electron microscope (SEM), fourier transform infrared spectroscopy (FTIR), differential thermal analysis (TGA) and fluorescence spectrophotometer (PL) etc. to characterize respectively.
The preparation method of the present invention proposes a kind of rare earth organic-inorganic zinc oxide semi-conductor nanoporous composite luminescent material based on hydroxyl functionalization, the zinc oxide semi-conductor nanoparticle of preparation is linked to each other with the organism of hydroxyl by interpolymerization, behind its hydroxyl modified, receive in the Si-O inorganic network with the method for covalent linkage grafting by the hydrolytie polycondensation process with tetraethoxy, connect together by coordinate bond with rare earth ion and organic molecule then, thereby realized grafting between the organic and inorganic phase at molecular level, effectively avoided the generation of the phenomenon of phase separation of inorganic organic phase.In prepared system, organic ligand effectively transmits energy and gives rare earth ion, and the introducing of inorganic system simultaneously makes it have good thermostability and mechanical property again.The gained luminescent material has high-quantum efficiency, high brightness, purity of color and ductility etc.; And the gentle easily control of experiment condition makes preparation cost cheap, and can regulate and control the flexible design of implementation structure and cut out by molecular designing.In addition, the quality of material is frivolous and snappiness is good, is easier to make large-sized display panel and photodiode; The inventive method workable, favorable reproducibility meets the Principles of Economy of Green Chemistry and products obtained therefrom steady quality.
Description of drawings
Fig. 1 is the cross-sectional transmission electron microscope figure of the rare earth organic-inorganic zinc oxide semi-conductor nanoporous composite luminescent material of the embodiment of the invention 1 gained hydroxyl functionalization.
Fig. 2 is the fluorescence curve of the rare earth organic-inorganic zinc oxide semi-conductor nanoporous composite luminescent material of the embodiment of the invention 2 gained hydroxyl functionalizations.
Embodiment
Further set forth the present invention below by embodiment, but protection scope of the present invention is not limited to these embodiment.Raw material in the embodiment of the invention is analytical pure available from Shanghai traditional Chinese medicines group.
Embodiment 1
5 mmol zinc dimethacrylates are dissolved in 20 ml dehydrated alcohols, drip 17.5 mmol lithium hydroxide ethanolic solns then, 80 ℃ of 3 h that reflux, products obtained therefrom after the centrifugation, in 60 ℃ of vacuum-dryings, namely gets white powder through revolving the inspissation contracting.Getting its 1 mmol is dissolved in the ethanol solution that contains 0.005 g benzoyl peroxide, and in this solution, add 1 ml hydroxyethyl methylacrylate, in 60 ℃ of reaction 6 h, product obtains after centrifugal purification by the zinc oxide nano-particle of the organism of hydroxyl modification under the mechanical stirring.The nanoparticle by behind the modified that makes is dissolved in the 20 ml tetrahydrofuran solutions; add 2 mmol sodium hydrides; the control temperature of reaction is 65 ℃; after reacting 2 h; dropwise add the silica-based propyl isocyanate of 2 mmol triethoxies again; this mixed solution reacts 12 h under nitrogen protection, through revolving the inspissation contracting, obtain a kind of viscous liquid.Taking by weighing 1.0 g template P123 is dissolved in the 7.5 g deionized waters, hydrochloric acid soln 30 g that add 2 mol/L again, be heated to 35-40 ℃, mixed solution with 9.6 mmol tetraethoxys and 0.4 mmol silicon decorated nanometer zinc oxide dropwise adds then, 35-40 ℃ of control temperature of reaction, reaction times 24 h, afterwards, it is transferred in the autoclave that tetrafluoroethylene is liner, and temperature of reaction is to carry out hydro-thermal reaction 48 h under 100 ℃, and products obtained therefrom is through washing, after the filtration, 60 ℃ of dry air a whole nights, extract two days removal template with the dehydrated alcohol Soxhlet, namely get the SBA-15 mesoporous material of functionalization, be placed in the 100 ml round-bottomed flasks, add 20 ml N, dinethylformamide adds 6 mmol nicotinic acid then, and Terbium trinitrate ethanolic soln 5 ml with 2 mmol add afterwards, be to stir 4 h under 25 ℃ the situation in temperature, product is through centrifugal, 60 ℃ of vacuum-dryings behind the absolute ethanol washing, just the rare earth organic-inorganic zinc oxide semi-conductor nanoporous composite luminescent material of hydroxyl functionalization.
As can be known from Fig. 1, the gained material has regular orderly structure, and the mesoporous material aperture that obtains is about 10 nm.
Embodiment 2
5 mmol zinc dimethacrylates are dissolved in 20 ml dehydrated alcohols, drip 17.5 mmol lithium hydroxide ethanolic solns then, 80 ℃ of 3 h that reflux, products obtained therefrom after the centrifugation, in 60 ℃ of vacuum-dryings, namely gets white powder through revolving the inspissation contracting.Getting its 1 mmol is dissolved in the ethanol solution that contains 0.005 g benzoyl peroxide, and in this solution, add 1 ml hydroxyethyl methylacrylate, in 60 ℃ of reaction 6 h, product obtains after centrifugal purification by the zinc oxide nano-particle of the organism of hydroxyl modification under the mechanical stirring.The nanoparticle by behind the modified that makes is dissolved in the 20 ml tetrahydrofuran solutions; add 2 mmol sodium hydrides; the control temperature of reaction is 65 ℃; after reacting 2 h; dropwise add the silica-based propyl isocyanate of 2 mmol triethoxies again; this mixed solution reacts 12 h under nitrogen protection, through revolving the inspissation contracting, obtain a kind of viscous liquid.Taking by weighing 1.0 g template P123 is dissolved in the 7.5 g deionized waters, hydrochloric acid soln 30 g that add 2 mol/L again, be heated to 35-40 ℃, mixed solution with 9.6 mmol tetraethoxys and 0.4 mmol silicon decorated nanometer zinc oxide dropwise adds then, 35-40 ℃ of control temperature of reaction, reaction times 24 h, afterwards, it is transferred in the autoclave that tetrafluoroethylene is liner, temperature of reaction is to carry out hydro-thermal reaction 48 h under 100 ℃, products obtained therefrom is through washing, after the filtration, 60 ℃ of dry air a whole nights, extract two days removal template with the dehydrated alcohol Soxhlet, namely get the SBA-15 mesoporous material of functionalization, be placed in the 100 ml round-bottomed flasks, add 20 ml N, dinethylformamide, add 6 mmol thenoyltrifluoroacetones then, europium nitrate ethanolic soln 5 ml with 2 mmol add afterwards, be to stir 4 h under 25 ℃ the situation in temperature, product is through centrifugal, 60 ℃ of vacuum-dryings behind the absolute ethanol washing, just the rare earth organic-inorganic zinc oxide semi-conductor nanoporous composite luminescent material of hydroxyl functionalization.The aperture of gained mesoporous material is about 10 nm.
As can be known from Fig. 2, the gained material has shown the feature emission of europium ion, and luminous intensity is higher.
Description to above-described embodiment is can understand and apply the invention for ease of those skilled in the art.The person skilled in the art obviously can easily make various modifications 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 (3)
1. preparation method based on the rare earth organic-inorganic zinc oxide semi-conductor nanoporous composite luminescent material of hydroxyl functionalization is characterized in that concrete steps are as follows:
(1) preparation of zinc oxide semi-conductor nanoparticle and modification:
By zinc dimethacrylate and LiOH prepared in reaction zinc oxide nano-particle, the organism with hydroxyl further wraps up and modifies it then;
(2) preparation of functionalization presoma:
The zinc oxide nano-particle that will be contained the organism modified of hydroxyl is dissolved in organic solvent, place flask, add sodium hydride and slough proton hydrogen, dropwise add the coupling agent with organic solvent dissolution, the temperature of reaction of solution is 65-75 ℃ in the control flask, and under nitrogen atmosphere back flow reaction 12 h, cooling, rotary evaporation is removed organic solvent, namely gets the functionalized nano zinc oxide precursor; Wherein: the mol ratio of sodium hydride and coupling agent is 1:1;
(3) preparation of nano zine oxide functional mesoporous material:
The functionalized nano zinc oxide precursor of step (2) gained and the mixed solution of tetraethoxy are dropwise added in the deionized water that is dissolved with template Pluronic P123, the pH value of hydrochloric acid conditioning solution, at 20-40 ℃ of following hydrolysis condensation reaction 24 h, transfer in the tetrafluoroethylene reactor, 100 ℃ of following crystallization 48 h, products therefrom after filtration and the washing, dry air; Obtain the nano zine oxide functional mesoporous material; Wherein: the mol ratio of template P123, tetraethoxy, functionalized nano zinc oxide precursor, hydrochloric acid, water is 0.0172:0.96:0.04:6:208.33;
(4) template is removed:
The nano zine oxide functional mesoporous material of step (3) gained was removed template in 2 days with extraction using alcohol in the Soxhlet extractor, filter the back and use absolute ethanol washing, drying gets final product;
(5) mesoporous material of nano zine oxide functionalization and rare-earth ion coordination reaction:
The nano zine oxide functional mesoporous material of removing template of step (4) gained is dissolved in organic solvent, drip the ethanolic soln of small molecules part earlier, drip the ethanolic soln of rare earth nitrate again, make it that coordination reaction take place and obtain rare earth compounding, temperature of reaction is 20-35 ℃, reaction times is 3-5 h, removes the nano zine oxide functional mesoporous material of template: the small molecules part: the mol ratio of rare earth nitrate is 1:3:1;
Wherein:The organism of the hydroxyl described in the step (1) is hydroxyethyl methylacrylate; The coupling agent that adds in the step (2) is the silica-based propyl isocyanate of triethoxy; The described organic solvent of step (2) is tetrahydrofuran (THF); Rare earth nitrate is europium nitrate or Terbium trinitrate described in the step (3); Small molecules part described in the step (5) is a kind of in thenoyltrifluoroacetone, benzoyltrifluoroacetone, diphenylpropane-1,3-dione(DPPO) or the nicotinic acid; Organic solvent is N described in the step (5), dinethylformamide.
2. the preparation method of the rare earth organic-inorganic zinc oxide semi-conductor nanoporous composite luminescent material based on hydroxyl functionalization according to claim 1 is characterized in that drying temperature is 60-70 ℃ described in the step (4).
3. the preparation method of the rare earth organic-inorganic zinc oxide semi-conductor nanoporous composite luminescent material based on hydroxyl functionalization according to claim 1, it is characterized in that the zinc oxide semi-conductor nanometer particle process method is in the step (1): the ethanolic soln of lithium hydroxide is joined in the ethanolic soln of zinc dimethacrylate, 80 ℃ of 3 h that reflux, revolve the inspissation contracting, centrifugal purification, 60 ℃ of vacuum-dryings then; The zinc oxide nano-particle that 1 mmol is made is dissolved in dehydrated alcohol, adds the organic molecule that 0.005 g initiator and 1 ml contain the two keys of hydroxyl, and with the mixture mechanical stirring, the control temperature of reaction is 60-75 ℃, reaction times 6 h.
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