CN104119912A

CN104119912A - Method for synthesizing hexagonal-prism-shaped hexagonal-phase YPO4:Eu.0.8H2O luminescent material by using hydrothermal synthesis method

Info

Publication number: CN104119912A
Application number: CN201410342619.0A
Authority: CN
Inventors: 朱晓伟; 宝金荣; 苏焕鹏; 李春柳; 熊立超
Original assignee: Inner Mongolia Medical University
Current assignee: Inner Mongolia Medical University
Priority date: 2014-07-14
Filing date: 2014-07-14
Publication date: 2014-10-29

Abstract

The invention discloses a method for simply synthesizing a hexagonal-prism-shaped hexagonal-phase YPO4:Eu.0.8H2O luminescent material by using a hydrothermal synthesis method at low temperature and low cost, belonging to the field of rare earth phosphate nanomaterials. The method comprises the steps of uniformly mixing a certain quantity of 0.1mol/L Y(NO3)3 solution and a certain quantity of 0.01mol/LEu(NO3)3 solution; adding 1.8-2.8mmol of trisodium citrate, and stirring for 20-30min; then, dropwise adding 10mL of 0.1mol/L H3PO4 to enable the molar ratio of phosphate radicals and rare earth ions in a reactant to be up to 1, and stirring for 20-30min; carrying out hydrothermal reaction within the temperature range of 150-160 DEG C for 10-12h to obtain hexagonal-prism-shaped hexagonal-phase YPO4:Eu.0.8H2O powder with the diameter of about 500nm and the height of about 300nm. The method is low in raw material price and free of expensive surfactant as a template, and has the characteristics of no organic solvent, no environment pollution, low reaction temperature, energy saving, easiness for industrial production and the like.

Description

Hydrothermal Synthesis hexagon six side's phase YPO 4: Eu0.8H 2the synthetic method of O luminescent material

Technical field:

The invention belongs to and belong to rare earth phosphate nano Material Field, relate to a kind of hexagon six side's phase YPO ₄: Eu0.8H ₂the synthetic method of O luminescent material, particularly adopts low temperature, low-cost synthetic hexagon six side's phase YPO ₄: Eu0.8H ₂the method of O luminescent material.

Background technology:

With RE phosphate REPO ₄(RE is rare earth ion) is the fluorescent material of matrix, and because chemical stability is good, luminous efficiency is high, and has good luminosity under ultraviolet excitation, and is applied to the fields such as colour television set, thermoluminescence detection, material for lamp.Wherein, due to Y ³⁺ion has 4f ⁰complete empty structure, does not have f-f transition, and with regard to not producing radiationless transition, consumed energy is widely studied in luminescent material.YPO ₄as a kind of substrate material of excellence, there is stable chemical nature, the advantage such as nontoxic, pollution-free, YPO ₄be the rising vacuum uv phosphor of a class, in this matrix, pass through doping Eu ³⁺, Tb ³⁺, Zr ⁴⁺and Mn ²⁺red-green-blue can be realized luminous.YPO ₄doping Eu ³⁺ion (YPO ₄: Eu) traditional synthetic method is with (NH ₄) ₂hPO ₄with rare earth oxide be that raw material at high temperature reacts, have like this P ₂o ₅evaporation, causes the ratio of phosphate radical and rare earth element uncontrollable.At present, YPO ₄: the synthetic method of Eu mainly contains high temperature solid-state method, spray heating decomposition, high boiling organic solvent method and high temperature hydrothermal method etc., and main synthetic product is Tetragonal YPO ₄: Eu.These methods are the shortcoming such as, complex process high at synthesis temperature, cost of material height mainly, is unfavorable for large-scale production and application.Therefore develop low temperature, the low-cost synthetic six side's phase structure rare earth Eu that have ³⁺the YPO of ion doping ₄method significant.

Summary of the invention:

The object of this invention is to provide a kind of with low temperature, cheaply simple method obtain can handling six strong side's phase YPO ₄: Eu0.8H ₂the synthetic method of O luminescent material.

Six side's phase YPO that a kind of fluorescence property is stronger ₄: the preparation method of Eu luminescent material is structure directing agent by trisodium citrate, and hydrothermal reaction at low temperature synthesizes hexagon six side's phase YPO ₄: Eu0.8H ₂o powder.By Y (NO ₃) ₃6H ₂o and Eu (NO ₃) ₃6H ₂as reaction raw materials, stirring soluble in water is fully dissolved it to O, adds 1.8～2.8mmol trisodium citrate, stirs 20～30 minutes, then adds a certain amount of H ₃pO ₄, stir and put into hydrothermal reaction kettle after 10～20 minutes, in 150～160 ℃ of temperature ranges, react 10～12 hours, products obtained therefrom is dried after 8～12 hours 60～80 ℃ of temperature ranges, obtains hexagon six side's phase YPO ₄: Eu0.8H ₂o luminescent material.

Concrete technology condition is:

H ₃pO ₄concentration in reaction system is 0.1mol/L, Y (NO ₃) ₃6H ₂o and Eu (NO ₃) ₃6H ₂the concentration of O in reaction system is respectively 0.1mol/L and 0.01mol/L, and in reaction system, trisodium citrate is 1.8～2.8mmol, and temperature of reaction is 150～160 ℃.

Material preparation method of the present invention is simple, and equipment is simple, and synthesis temperature is low; Cost of material is cheap, without expensive tensio-active agent, makes template; Have not with an organic solvent, free from environmental pollution, save the energy, transformation efficiency high, be easy to the features such as suitability for industrialized production, can effectively reduce synthesis temperature, be a kind of desirable friendly process, reproducible.

Accompanying drawing explanation:

Fig. 1 is the XRD figure spectrum of product synthetic under different condition, illustrate that acquisition product is six side's phase YPO ₄0.8H ₂o single-phase, illustrates Eu ³⁺ion has entered parent lattice and has replaced Y ³⁺do not change YPO ₄0.8H ₂six side's phase crystalline structure of O.Fig. 1 a is that temperature of reaction is six side's phase YPO synthetic under the condition that in 160 ℃, reaction system, the amount of substance of trisodium citrate is 2.0mmol ₄: Eu0.8H ₂the XRD figure spectrum of O powder, Fig. 1 b is that temperature of reaction is six synthetic side's phase YPO under the condition that in 150 ℃, reaction system, the amount of substance of trisodium citrate is 2.6mmol ₄: Eu0.8H ₂the XRD figure spectrum of O powder.

Fig. 2 is the stereoscan photograph of product synthetic under different condition, illustrates that products therefrom is the hexagon YPO of monodispersity, size homogeneous ₄: Eu0.8H ₂o single-phase.Fig. 2 a is that temperature of reaction is six side's phase YPO synthetic under the condition that in 160 ℃, reaction system, the amount of substance of trisodium citrate is 2.0mmol ₄: Eu0.8H ₂the low multiple stereoscan photograph of O powder, Fig. 2 b is that temperature of reaction is six side's phase YP0 synthetic under the condition that in 160 ℃, reaction system, the amount of substance of trisodium citrate is 2.0mmol ₄: Eu0.8H ₂the high multiple stereoscan photograph of O powder, product has the hexagon that diameter is about 500nm, is highly about 300nm.Fig. 2 c is that temperature of reaction is six side's phase YPO synthetic under the condition that in 150 ℃, reaction system, the amount of substance of trisodium citrate is 2.6mmol ₄: Eu0.8H ₂o powder stereoscan photograph, product has the hexagon that diameter is about 400nm, is highly about 250nm.

Fig. 3 is that temperature of reaction is six side's phase YPO synthetic under the condition that in 160 ℃, reaction system, the amount of substance of trisodium citrate is 2.0mmol ₄: Eu0.8H ₂the fluorescence emission spectrogram of O powder, incident light and utilizing emitted light slit width are 0.5nm, excitation wavelength lambda _eXunder condition for 395nm, measured the utilizing emitted light spectrogram of this sample, as can be seen from the figure this sample has stronger fluorescence property.

Embodiment:

Embodiment mono-

Get 9.5mL0.1 mol/L Y (NO ₃) ₃solution and 5mL0.01mol/L Eu (NO ₃) ₃solution mixes, and adds the trisodium citrate of 2.0mmol, stirs 20 minutes, drips the H of 10mL 0.1mol/L ₃pO ₄, stir 20 minutes, proceed in reactor.160 ℃ of reactions 12 hours, reaction finishes after product respectively washed three times with distilled water and dehydrated alcohol, dries 12h, obtains white powder for 60 ℃.

Embodiment bis-

Get 9.5mLO.1mol/L Y (NO ₃) ₃solution and 5mL0.01mol/L Eu (NO ₃) ₃solution mixes, and adds the trisodium citrate of 2.6mmol, stirs 30 minutes, drips the H of 10mL0.1mol/L ₃pO ₄, stir 20 minutes, proceed in reactor.150 ℃ of reactions 10 hours, reaction finishes after product respectively washed three times with distilled water and dehydrated alcohol, dries 8h, obtains white powder for 80 ℃.

Claims

1. hexagon six side's phase YPO ₄: Eu0.8H ₂the synthetic method of O luminescent material, is characterized in that utilizing hydrothermal reaction at low temperature to synthesize hexagon six side's phase YPO ₄: Eu0.8H ₂o powder; By Y (NO ₃) ₃6H ₂o and Eu (NO ₃) ₃6H ₂o is soluble in water as raw material, obtains 0.1 mol/LY (NO ₃) ₃solution and 0.01 mol/L Eu (NO ₃) ₃solution, adds the trisodium citrate of 1.8～2.8mmol, stirs 20～30 minutes, then is added dropwise to the H of 10mL 0.1mol/L ₃pO ₄make PO in reactant ₄ ^3-/ Y ³⁺, Eu ³⁺mol ratio be 1, stir and it fully mixed in 20～30 minutes, proceed in hydrothermal reaction kettle, in 150～160 ℃ of temperature ranges, react 10～12 hours, obtain hexagon six side's phase YPO ₄: Eu0.8H ₂o powder;

Concrete technology condition is: H ₃pO ₄concentration in reaction system is 0.1mol/L, Y (NO ₃) ₃6H ₂o and Eu (NO ₃) ₃6H ₂the concentration of O in reaction system is respectively 0.1mol/L and 0.01mol/L, and in reaction system, trisodium citrate is 1.8～2.8mmol, and temperature of reaction is 150～160 ℃.

2. a kind of hexagon six side's phase YPO according to claim 1 ₄: Eu0.8H ₂the synthetic method of O luminescent material, is characterized in that: Y (NO ₃) ₃solution and Eu (NO ₃) ₃solution and H ₃pO ₄during 160 ℃ of hydro-thermal reactions, in reactant, the amount of substance of trisodium citrate is 1.8～2.2mmol.

3. a kind of hexagon six side's phase YPO according to claim 1 ₄: Eu0.8H ₂the synthetic method of O luminescent material, is characterized in that: Y (NO ₃) ₃solution and Eu (NO ₃) ₃solution and H ₃pO ₄during 150 ℃ of hydro-thermal reactions, in reactant, the amount of substance of trisodium citrate is 2.2～2.8mmol.