A Pr 3+ doped and Pr 3+ / Gd 3+ co-doped ultraviolet up-conversion multifunctional material and a preparation method thereof

Abstract

This invention provides a Pr-based 3+ Single-doped Pr 3+ / Gd 3+ This invention relates to co-doped ultraviolet upconversion multifunctional materials and their preparation methods, belonging to the field of materials technology. The doping and matrix materials of this invention include silicates and phosphates. The general chemical formula for phosphate-based materials is M0. a Ln(PO4) b xPr 3+ yGd 3+ The general chemical formula for silicates is Ca2Al2SiO7:Pr 3+ / Gd 3+ Ba2Y3(SiO4)3F:Pr 3+ / Gd 3+ and BaY2Si3O 10 :Pr 3+ / Gd 3+ Both types of materials can be prepared via high-temperature solid-state reaction and co-precipitation. These materials can absorb visible photons such as blue and yellow light, and achieve high-energy photon emission in the ultraviolet C and ultraviolet B bands by transmitting blue light or blue + yellow light through a multi-photon upconversion process. This is based on the excellent ultraviolet C and ultraviolet B upconversion luminescence properties of these materials and Pr 3+ Gd 3+ The energy level structure of activator ions can be applied to fields such as fluorescent labeling, food safety, environmental protection, and medical health.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of materials, and particularly relates to a Pr 3+ doped and Pr 3+ / Gd 3+ co-doped ultraviolet up-conversion multifunctional material and a preparation method thereof. BACKGROUND

[0002] The ultraviolet light has the characteristics of short wavelength and high energy, is invisible to the naked eye, is not sensitive to heat radiation, is in the "solar blind" (such as the ultraviolet C band) of the earth's solar spectrum, and can interact well with organisms, optoelectronic materials and devices, so that it has wide applications in fluorescence temperature measurement and sensing, photocatalysis, solar blind labels, bacterial killing, and phototherapy of skin diseases. At present, the common artificial light source in the field of ultraviolet light technology application is a gas discharge type lamp, but this type of light source has the defects of large size, short service life and high bulb temperature during use. The ultraviolet LED appeared in recent years improves the shortcomings of the gas discharge type ultraviolet light source in some aspects, but the preparation process of the ultraviolet LED chip is complex, the production cost is high, and the external quantum efficiency is low, so it is a hot and meaningful topic to develop new materials and new devices through existing commercial and high-efficiency excitation sources (such as LED light sources, sunlight, continuous and pulsed lasers, etc.), obtain effective ultraviolet light emission through up-conversion, and realize the related practical applications. SUMMARY

[0003] The application aims to provide a Pr 3+ doped and Pr 3+ / Gd 3+ co-doped ultraviolet up-conversion multifunctional material. 3+ / Gd 3+ , Ba2Y3(SiO4)3F:Pr 3+ / Gd 3+ and BaY2Si3O 10 :Pr 3+ / Gd 3+ ;

[0004] When the doped matrix material is a phosphate, the chemical general formula of the converted multifunctional material is: M a Ln(PO4) b :xPr 3+ ,yGd 3+Where M is any one of Mg, Ca, Sr, Ba, Zn or Pb, Ln is any one of Y, La, Sc, Lu, Yb or Ce, a = 3, b = 3, x = 0.001-0.20, y = 0-0.80 or a = 9, b = 7, x = 0.001-0.50, y = 0-1.00.

[0005] Furthermore, when Pr 3+ Single doping or Pr 3+ / Gd 3+ Co-doped with Ca2Al2SiO7, the general chemical formula of this material is: Ca 2- x Al2SiO7:xPr 3+ or Ca 2-x-y Al2SiO7:xPr 3+ yGd 3+ Where x = 0.001 - 0.10, y = 0 - 0.30;

[0006] When Pr 3+ When Ba₂Y₃(SiO₄)₃F is doped, the general chemical formula of the material is Ba₂Y. 3-x (SiO4)3F:xPr 3+ Or Ba 2-x Y3(SiO4)3F:xPr 3+ When Pr 3+ / Gd 3+ When co-doped with Ba2Y3(SiO4)3F, the general chemical formula of the material is Ba2Y. 3-x-y (SiO4)3F:xPr 3+ yGd 3+ Or Ba 2-x-y Y3(SiO4)3F:xPr 3+ yGd 3+ , where x = 0.001 - 0.10, y = 0 - 0.60;

[0007] When Pr 3+ Single-doped BaY2Si3O 10 At that time, the general chemical formula of the material was BaY. 2-x Si3O 10 :xPr 3+ Or Ba 1-x Y2Si3O 10 :xPr 3+ When Pr 3+ / Gd 3+ Co-doped BaY2Si3O 10 At that time, the general chemical formula of the material was BaY. 2-x-y Si3O 10 :xPr3+ yGd 3+ or Ba 1-x-y Y2Si3O 10 xPr 3+ yGd 3+ wherein x = 0.001-0.05, y = 0-0.60;

[0008] when Pr 3+ is singly doped into M a Ln(PO4) b , the chemical formula of the material is M3Ln(PO4)3:xPr 3+ or M9Ln(PO4)7:xPr 3+ , and when the chemical formula of the material is M3Ln(PO4)3:xPr 3+ , it is specifically M 3-x Pr x Ln(PO4)3 or M3Ln 1-x Pr x (PO4)3, and x = 0.001-0.20; and when the chemical formula of the material is M9Ln(PO4)7:xPr 3+ , it is specifically M 9-x Pr x Ln(PO4)7 or M9Ln 1-x Pr x (PO4)7, and x = 0.001-0.50;

[0009] when Pr 3+ / Gd 3+ is co-doped into M a Ln(PO4) b , the chemical formula of the material is M3Ln(PO4)3:xPr 3+ ,yGd 3+ or M9Ln(PO4)7:xPr 3+ ,yGd 3+ , and when the chemical formula of the material is M3Ln(PO4)3:xPr 3+ ,yGd 3+ , it is specifically M 3-x- y Pr x Gd y Ln(PO4)3 or M3Ln 1-x-y Pr x Gd y (PO4)3, and x = 0.001-0.20, y = 0-0.80; and when the chemical formula of the material is M9Ln(PO4)7:xPr 3+ ,yGd 3+ , it is specifically M9-x-y Pr x Gd y Ln(PO4)7 or M9Ln 1-x-y Pr x Gd y (PO4)7, and x = 0.001-0.50, y = 0-1.00.

[0010] Further, such materials achieve their function of high-energy photon emission in the ultraviolet C band and ultraviolet B band by multi-photon upconversion process of absorbing visible photons and passing blue light or blue light + yellow light, and when the doped matrix material is phosphate, the luminescent performance of the product material is optimized by introducing alkali metal elements or adding cosolvents.

[0011] Further, the alkali metal element is any one of Li, Na, K and Rb; and the cosolvent is H3BO3 and NH4F.

[0012] Further, when the alkali metal element is Li, then when Pr 3+ Single-doped M a Ln(PO4) b , and the chemical general formula of the material is M3Ln(PO4)3:xPr 3+ or M9Ln(PO4)7:xPr 3+ , then it is also specifically M 3-2x Pr x Li x Ln(PO4)3 or M 9- 2x Pr x Li x Ln(PO4)7;

[0013] When Pr 3+ / Gd 3+ Co-doped M a Ln(PO4) b , and the chemical general formula of the material is M3Ln(PO4)3:xPr 3+ ,yGd 3+ or M9Ln(PO4)7:xPr 3+ ,yGd 3+ , then it is also specifically M 3-2x-2y Pr x Gd y Li x+y Ln(PO4)3 or M 9-2x-2y Pr x Gd y Li x+ y Ln(PO4)7.

[0014] A Pr 3+ doped and Pr 3+ / Gd 3+ doped ultraviolet upconversion multifunctional material preparation method is characterized in that the material is prepared by a high-temperature solid-phase reaction method or a coprecipitation method, wherein, when the doped matrix material is silicate, the material is also prepared by a sol-gel method.

[0015] Further, the material is prepared by a high-temperature solid-phase reaction method, specifically including the following steps:

[0016] S1: Based on the specific composition of the ultraviolet upconversion phosphate multifunctional material, weigh each raw material and add each raw material to a mortar for thorough grinding;

[0017] S2: Transfer the ground product to a vessel, set the temperature increase rate to 5°C / min, take out the product after sintering is completed, and rapidly cool it to room temperature, and finally transfer the cooled product to a mortar for thorough grinding to obtain the final ultraviolet upconversion phosphate multifunctional material.

[0018] Further, each raw material is weighed based on the multifunctional material to be prepared, including basic raw materials and added raw materials, wherein, when the doped matrix material is silicate, the basic raw materials include any combination of CaCO3, BaCO3, Al2O3, Y2O3, SiO2, and NH4F, and the added raw materials include one or both of Pr6O 11 , Pr(NO3)3·6H2O, and Gd2O3;

[0019] When the doped matrix material is phosphate, the basic raw materials include MCO3 or other M-containing compounds, Ln2O3 or other Ln-containing compounds, and NH4H2PO4 or other easily decomposed phosphates, and the added raw materials include one or more combinations of Pr(NO3)3·6H2O or other Pr-containing compounds, Gd2O3 or other Gd-containing compounds, and Li2CO3 or other alkali metal compounds.

[0020] Further, when the chemical formula of the prepared material is Ca 2-x-y Al2SiO7:xPr 3+ ,yGd 3+ , the mass ratio of the weighed raw materials CaCO3, Al2O3, SiO2, Pr6O 11 , and Gd2O3 is 2-x-y:2:1:x:y, x=0.001-0.10, and y=0-0.30;

[0021] When the chemical formula of the prepared material is Ba2Y 3-x-y (SiO4)3F:xPr 3+ ,yGd 3+When the chemical formula of the prepared material is BaY

[0022] When the chemical formula of the prepared material is BaY 2-x-y Si3O 10 :xPr 3+ ,yGd 3+ When the chemical formula of the prepared material is BaY

[0023] When the chemical formula of the prepared material is M 3-x Pr x Ln(PO4)3, the mass ratio of the weighed raw materials MCO3 or other M-containing compounds, Pr(NO3)3·6H2O or other Pr-containing compounds, Ln2O3 or other Ln-containing compounds, and NH4H2PO4 or other easily decomposed phosphate is 3-x:x:1:3, x = 0.001-0.20;

[0024] When the chemical formula of the prepared material is M3Ln 1-x Pr x (PO4)3, the mass ratio of the weighed raw materials MCO3 or other M-containing compounds, Pr(NO3)3·6H2O or other Pr-containing compounds, Ln2O3 or other Ln-containing compounds, and NH4H2PO4 or other easily decomposed phosphate is 3:1-x:x:3, x = 0.001-0.20;

[0025] When the chemical formula of the prepared material is M 3-2x Pr x Li x Ln(PO4)3, the mass ratio of the weighed raw materials MCO3 or other M-containing compounds, Pr(NO3)3·6H2O or other Pr-containing compounds, Li2CO3 or other alkali metal compounds, Ln2O3 or other Ln-containing compounds, and NH4H2PO4 or other easily decomposed phosphate is 3-2x:x:x:1:3, x = 0.001-0.20;

[0026] When the chemical formula of the prepared material is M 3-x-y Pr x Gd yWhen the chemical formula of the prepared material is M3Ln(PO4)3, the mass ratio of the raw materials MCO3 or other M-containing compounds, Pr(NO3)3.6H2O or other Pr-containing compounds, Gd2O3 or other Gd-containing compounds, Ln2O3 or other Ln-containing compounds, and NH4H2PO4 or other easily decomposed phosphate salts is 3-x-y: x: y: 1: 3, x = 0.001-0.20, y = 0-0.80;

[0027] When the chemical formula of the prepared material is M3Ln(PO4)3, the mass ratio of the raw materials MCO3 or other M-containing compounds, Pr(NO3)3.6H2O or other Pr-containing compounds, Gd2O3 or other Gd-containing compounds, Ln2O3 or other Ln-containing compounds, and NH4H2PO4 or other easily decomposed phosphate salts is 3-x-y: x: y: 1: 3, x = 0.001-0.20, y = 0-0.80; 1-x-y Pr x Gd y When the chemical formula of the prepared material is M3Ln(PO4)3, the mass ratio of the raw materials MCO3 or other M-containing compounds, Pr(NO3)3.6H2O or other Pr-containing compounds, Gd2O3 or other Gd-containing compounds, Ln2O3 or other Ln-containing compounds, and NH4H2PO4 or other easily decomposed phosphate salts is 3-x-y: x: y: 1: 3, x = 0.001-0.20, y = 0-0.80;

[0028] When the chemical formula of the prepared material is M3Ln(PO4)3, the mass ratio of the raw materials MCO3 or other M-containing compounds, Pr(NO3)3.6H2O or other Pr-containing compounds, Gd2O3 or other Gd-containing compounds, Ln2O3 or other Ln-containing compounds, and NH4H2PO4 or other easily decomposed phosphate salts is 3-x-y: x: y: 1: 3, x = 0.001-0.20, y = 0-0.80; 3-2x-2y Pr x Gd y Li x+y When the chemical formula of the prepared material is M3Ln(PO4)3, the mass ratio of the raw materials MCO3 or other M-containing compounds, Pr(NO3)3.6H2O or other Pr-containing compounds, Gd2O3 or other Gd-containing compounds, Ln2O3 or other Ln-containing compounds, and NH4H2PO4 or other easily decomposed phosphate salts is 3-x-y: x: y: 1: 3, x = 0.001-0.20, y = 0-0.80;

[0029] When the chemical formula of the prepared material is M3Ln(PO4)3, the mass ratio of the raw materials MCO3 or other M-containing compounds, Pr(NO3)3.6H2O or other Pr-containing compounds, Gd2O3 or other Gd-containing compounds, Ln2O3 or other Ln-containing compounds, and NH4H2PO4 or other easily decomposed phosphate salts is 3-x-y: x: y: 1: 3, x = 0.001-0.20, y = 0-0.80; 9-x Pr x When the chemical formula of the prepared material is M3Ln(PO4)3, the mass ratio of the raw materials MCO3 or other M-containing compounds, Pr(NO3)3.6H2O or other Pr-containing compounds, Gd2O3 or other Gd-containing compounds, Ln2O3 or other Ln-containing compounds, and NH4H2PO4 or other easily decomposed phosphate salts is 3-x-y: x: y: 1: 3, x = 0.001-0.20, y = 0-0.80;

[0030] When the chemical formula of the prepared material is M3Ln(PO4)3, the mass ratio of the raw materials MCO3 or other M-containing compounds, Pr(NO3)3.6H2O or other Pr-containing compounds, Gd2O3 or other Gd-containing compounds, Ln2O3 or other Ln-containing compounds, and NH4H2PO4 or other easily decomposed phosphate salts is 3-x-y: x: y: 1: 3, x = 0.001-0.20, y = 0-0.80; 1-x Pr xWhen the chemical formula of the prepared material is M9Ln(PO4)7, the mass ratio of the raw materials MCO3 or other M-containing compounds, Pr(NO3)3.6H2O or other Pr-containing compounds, Gd2O3 or other Gd-containing compounds, Ln2O3 or other Ln-containing compounds, and NH4H2PO4 or other easily decomposed phosphate is 9-x-y: x: y: 1: 7, x = 0.001-0.50, y = 0-1.00;

[0031] When the chemical formula of the prepared material is M9Ln(PO4)7, the mass ratio of the raw materials MCO3 or other M-containing compounds, Pr(NO3)3.6H2O or other Pr-containing compounds, Gd2O3 or other Gd-containing compounds, Ln2O3 or other Ln-containing compounds, and NH4H2PO4 or other easily decomposed phosphate is 9-x-y: x: y: 1: 7, x = 0.001-0.50, y = 0-1.00; 9-x-y Pr x Gd y When the chemical formula of the prepared material is M9Ln(PO4)7, the mass ratio of the raw materials MCO3 or other M-containing compounds, Pr(NO3)3.6H2O or other Pr-containing compounds, Gd2O3 or other Gd-containing compounds, Ln2O3 or other Ln-containing compounds, and NH4H2PO4 or other easily decomposed phosphate is 9-x-y: x: y: 1: 7, x = 0.001-0.50, y = 0-1.00;

[0032] When the chemical formula of the prepared material is M9Ln(PO4)7, the mass ratio of the raw materials MCO3 or other M-containing compounds, Pr(NO3)3.6H2O or other Pr-containing compounds, Gd2O3 or other Gd-containing compounds, Ln2O3 or other Ln-containing compounds, and NH4H2PO4 or other easily decomposed phosphate is 9-x-y: x: y: 1: 7, x = 0.001-0.50, y = 0-1.00; 1-x-y Pr x Gd y When the chemical formula of the prepared material is M9Ln(PO4)7, the mass ratio of the raw materials MCO3 or other M-containing compounds, Pr(NO3)3.6H2O or other Pr-containing compounds, Gd2O3 or other Gd-containing compounds, Ln2O3 or other Ln-containing compounds, and NH4H2PO4 or other easily decomposed phosphate is 9-x-y: x: y: 1: 7, x = 0.001-0.50, y = 0-1.00;

[0033] When the chemical formula of the prepared material is M9Ln(PO4)7, the mass ratio of the raw materials MCO3 or other M-containing compounds, Pr(NO3)3.6H2O or other Pr-containing compounds, Gd2O3 or other Gd-containing compounds, Ln2O3 or other Ln-containing compounds, and NH4H2PO4 or other easily decomposed phosphate is 9-x-y: x: y: 1: 7, x = 0.001-0.50, y = 0-1.00; 9-2x Pr x Li x When the chemical formula of the prepared material is M9Ln(PO4)7, the mass ratio of the raw materials MCO3 or other M-containing compounds, Pr(NO3)3.6H2O or other Pr-containing compounds, Gd2O3 or other Gd-containing compounds, Ln2O3 or other Ln-containing compounds, and NH4H2PO4 or other easily decomposed phosphate is 9-x-y: x: y: 1: 7, x = 0.001-0.50, y = 0-1.00;

[0034] When the chemical formula of the prepared material is M9Ln(PO4)7, the mass ratio of the raw materials MCO3 or other M-containing compounds, Pr(NO3)3.6H2O or other Pr-containing compounds, Gd2O3 or other Gd-containing compounds, Ln2O3 or other Ln-containing compounds, and NH4H2PO4 or other easily decomposed phosphate is 9-x-y: x: y: 1: 7, x = 0.001-0.50, y = 0-1.00; 9-2x-2y Pr x Gd y Li x+yThe mass ratio of the raw material MCO3 or other M-containing compound, Pr(NO3)3.6H2O or other Pr-containing compound, Gd2O3 or other Gd-containing compound, Li2CO3 or other alkali metal compound, Ln2O3 or other Ln-containing compound and NH4H2PO4 or other decomposable phosphate in the Ln(PO4)7 is 9-2x-2y:x:y:x+y:1:7, x=0.001-0.50, y=0-1.00.

[0035] Further, in S1, when the doped matrix material is silicate, the vessel is a muffle furnace; when the doped matrix material is phosphate, the vessel is an alumina pan;

[0036] In S2, when the doped matrix material is phosphate, before heating, it is also necessary to keep the temperature for a certain time, wherein, when x=0.001-0.20 in the prepared material, the certain temperature is 1350 DEG C; the certain time is 10 hours; when x=0.001-0.50 in the prepared material, the certain temperature is 1250 DEG C; the certain time is 8 hours.

[0037] Compared with the prior art, the beneficial effects of the present application mainly include:

[0038] 1. On the basis of the existing up-conversion luminescent material, the present application provides a kind of phosphate material and a kind of silicate material, the two kinds of materials can convert low-energy blue light or blue light+yellow light excitation energy into ultraviolet high-energy light emission, and realize high-concentration doping and high-efficiency luminescence characteristics of light functional materials under low illumination.

[0039] 2. Based on the excellent ultraviolet C and ultraviolet B up-conversion luminescence performance of the two kinds of materials provided by the present application and the energy level structure of Pr 3+ , Gd 3 + activator ions, the material can be applied to photocatalysis, solar blind label, fluorescent temperature measurement, effective inhibition and killing of bacteria, photodynamic therapy of skin diseases, etc., and ultimately has good application value in the fields of fluorescent labeling, food safety, environmental protection and medical health. BRIEF DESCRIPTION OF DRAWINGS

[0040] Figure 1 The X-ray diffraction pattern of the representative ultraviolet up-conversion material Ca3Y(PO4)3:xPr 3+ and Ca3Y(PO4)3:xPr 3+ , yGd 3+ ;

[0041] Figure 2 The X-ray diffraction pattern of the representative ultraviolet up-conversion material Ca3Y(PO4)3:xPr 3+The fluorescence excitation and emission spectra;

[0042] Figure 3 Ca3Y(PO4)3:xPr is a representative material for ultraviolet upconversion. 3+ The ultraviolet upconversion emission spectrum;

[0043] Figure 4 Ca3Y(PO4)3:xPr is a representative material for ultraviolet upconversion. 3+ Alkaline earth metals Ca, Sr, Ba substitution and Sc 3+ Partially substituted ultraviolet upconversion emission spectra;

[0044] Figure 5 Ca3Y(PO4)3:xPr is a representative material for ultraviolet upconversion. 3+ yGd 3+ The ultraviolet upconversion emission spectrum;

[0045] Figure 6 Ca9Y(PO4)7:xPr is a representative material for ultraviolet upconversion. 3+ and Ca9Y(PO4)7:xPr 3+ yGd 3+ X-ray diffraction pattern;

[0046] Figure 7 Ca9Y(PO4)7:xPr is a representative material for ultraviolet upconversion. 3+ The fluorescence excitation and emission spectra;

[0047] Figure 8 Ca9Y(PO4)7:xPr is a representative material for ultraviolet upconversion. 3+ The ultraviolet upconversion emission spectrum;

[0048] Figure 9 Ca9Y(PO4)7:xPr is a representative material for ultraviolet upconversion. 3+ and alkali metal Li + Comparison of UV upconversion emission spectra of co-doped optimized samples;

[0049] Figure 10 Ca9Y(PO4)7:xPr is a representative material for ultraviolet upconversion. 3+ yGd 3+ The ultraviolet upconversion emission spectrum.

[0050] Figure 11 Ca prepared in Example 5 1.71 Pr 0.04 Gd 0.25 Al2SiO7 and Ca prepared in Example 6 1.96 Pr 0.04X-ray diffraction pattern of Al2SiO7 powder;

[0051] Figure 12 Ca prepared in Example 5 1.71 Pr 0.04 Gd 0.25 Al2SiO7 and Ca prepared in Example 6 1.96 Pr 0.04 Ultraviolet upconversion emission spectrum of Al2SiO7 powder under blue light excitation;

[0052] Figure 13 Ca prepared in Example 5 1.71 Pr 0.04 Gd 0.25 Al2SiO7 powder fluorescence emission spectrum;

[0053] Figure 14 Ba2Y prepared in Example 7 2.593 Pr 0.007 Gd 0.40 (SiO4)3F and Ba2Y prepared in Example 8 2.993 Pr 0.007 X-ray diffraction pattern of (SiO4)3F powder;

[0054] Figure 15 Ba2Y prepared in Example 7 2.593 Pr 0.007 Gd 0.40 (SiO4)3F and Ba2Y prepared in Example 8 2.993 Pr 0.007 Ultraviolet upconversion emission spectrum of (SiO4)3F powder under blue light excitation;

[0055] Figure 16 Ba2Y prepared in Example 8 2.993 Pr 0.007 Fluorescence excitation and emission spectra of (SiO4)3F powder;

[0056] Figure 17 Y prepared in Example 9 1.57 Pr 0.03 Gd 0.40 Si3O 10 BaY prepared in Example 10 1.97 Pr 0.03 Si3O 10 X-ray diffraction pattern of powder;

[0057] Figure 18 Y prepared in Example 9 1.57 Pr 0.03 Gd 0.40 Si3O 10BaY prepared in Example 10 1.97 Pr 0.03 Si3O 10 UV upconversion emission spectrum of the powder under blue excitation;

[0058] Figure 19 BaY prepared in Example 10 1.97 Pr 0.03 Si3O 10 Fluorescence excitation and emission spectrum of the powder. DETAILED DESCRIPTION

[0059] A kind of phosphate M a Ln(PO4) b :xPr 3+ ,yGd 3+ Multifunctional UV upconversion materials and methods for making the same are described in greater detail below, wherein the preferred embodiments of the present application are represented, it should be understood that those skilled in the art can modify the present application described herein while still achieving the advantageous effects of the present application, therefore, the following description should be understood as a broad knowledge to those skilled in the art, and not as a limitation to the present application.

[0060] A Pr 3+ doped and Pr 3+ / Gd 3+ co-doped multifunctional UV upconversion material, the doped matrix material includes phosphate and silicate, the present application will be introduced by two kinds of matrix material respectively prepared by multifunctional material and its preparation method.

[0061] A kind of phosphate M a Ln(PO4) b :xPr 3+ ,yGd 3+ Multifunctional UV upconversion material, specifically Pr 3+ doped and Pr 3+ and Gd 3+ co-doped M a Ln(PO4) b Multifunctional UV upconversion phosphate material, the chemical formula of this kind of material is M a Ln(PO4) b :xPr 3+ ,yGd 3+ , wherein M=Mg, Ca, Sr, Ba, Zn, Pb; Ln=Y, La, Sc, Lu, Yb, Ce; a=3, b=3 or a=9, b=7; x=0.001-0.20, y=0-0.80 or x=0.001-0.50, y=0-1.00.

[0062] Pr3+ Single-doped M a Ln(PO4) b The chemical formula of the multifunctional material for ultraviolet up-conversion is M3Ln(PO4)3:xPr 3+ , and specifically, M 3-x Pr x Ln(PO4)3 or M 3-2x Pr x Li x Ln(PO4)3 or M3Ln 1-x Pr x (PO4)3, wherein M=Mg, Ca, Sr, Ba, Zn, Pb; Ln=Y, La, Sc, Lu, Yb, Ce; x=0.001-0.20, and the preparation method is a high-temperature solid-phase reaction method, a coprecipitation method plus a high-temperature sintering method, etc., wherein the high-temperature solid-phase reaction method mainly includes the following steps:

[0063] M 3-x Pr x The component of Ln(PO4)3 requires a molar ratio of 3-x:x:1:3, and the raw materials are MCO3 or other M-containing compounds, Pr(NO3)3·6H2O or other Pr-containing compounds, Ln2O3 or other Ln-containing compounds, NH4H2PO4 or other easily decomposed phosphates, which are added to a mortar and ground uniformly;

[0064] M 3-2x Pr x Li x The component of Ln(PO4)3 requires a molar ratio of 3-2x:x:x:1:3, and the raw materials are MCO3 or other M-containing compounds, Pr(NO3)3·6H2O or other Pr-containing compounds, Li2CO3 or other alkali metal compounds, Ln2O3 or other Ln-containing compounds, NH4H2PO4 or other easily decomposed phosphates, which are added to a mortar and ground uniformly;

[0065] M3Ln 1-x Pr x The component of (PO4)3 requires a molar ratio of 3:1-x:x:3, and the raw materials are MCO3 or other M-containing compounds, Pr(NO3)3·6H2O or other Pr-containing compounds, Ln2O3 or other Ln-containing compounds, NH4H2PO4 or other easily decomposed phosphates, which are added to a mortar and ground uniformly;

[0066] The ground product is transferred to an alumina crucible, and then heat-treated at about 1350℃ for 10 hours, wherein the heating rate is about 5℃ / min, then wait for the sintering to be completed, take out the product, rapidly cool to room temperature, and then transfer to a mortar again for grinding to obtain the final multifunctional material for ultraviolet up-conversion.

[0067] Pr 3+ / Gd 3+ co-doped M a Ln(PO4) b ultraviolet up-conversion multifunctional material chemical formula is M3Ln(PO4)3:xPr 3+ ,yGd 3+ , specifically M 3-x-y Pr x Gd y Ln(PO4)3 or M 3-2x-2y Pr x Gd y Li x+y Ln(PO4)3 or M3Ln 1-x-y Pr x Gd y (PO4)3, wherein M=Mg, Ca, Sr, Ba, Zn, Pb; Ln=Y, La, Sc, Lu, Yb, Ce; x=0.001-0.20, y=0-0.80. The preparation method is high temperature solid phase reaction method, coprecipitation method and high temperature sintering method, etc., wherein the high temperature solid phase reaction method mainly includes the following steps:

[0068] M 3-x-y Pr x Gd y Ln(PO4)3 component requires weighing the molar ratio of 3-x-y:x:y:1:3 raw materials MCO3 or other M-containing compounds, Pr(NO3)3·6H2O or other Pr-containing compounds, Gd2O3 or other Gd-containing compounds, Ln2O3 or other Ln-containing compounds, NH4H2PO4 or other easily decomposed phosphate, add the raw materials to the mortar and grind evenly;

[0069] M 3-2x-2y Pr x Gd y Li x+y Ln(PO4)3 component requires weighing the molar ratio of 3-2x-2y:x:y:x+y:1:3 raw materials MCO3 or other M-containing compounds, Pr(NO3)3•6H2O or other Pr-containing compounds, Gd2O3 or other Gd-containing compounds, Li2CO3 or other alkali metal compounds, Ln2O3 or other Ln-containing compounds, and NH4H2PO4 or other easily decomposed phosphate, add the raw materials to the mortar and grind evenly;

[0070] M3Ln 1-x-y Pr x Gd y(PO4)3 component requires a weighing molar ratio of 3:1-x-y:x:y:3MCO3 or other M-containing compounds, Pr(NO3)3.6H2O or other Pr-containing compounds, Gd2O3 or other Gd-containing compounds, Ln2O3 or other Ln-containing compounds, and NH4H2PO4 or other easily decomposed phosphates, and the raw materials are added to a mortar and ground uniformly;

[0071] The ground product is transferred to an alumina crucible, then heated at about 1350°C for 10 hours, with a heating rate of about 5°C / min, then waits for sintering to complete, the product is removed and rapidly cooled to room temperature, and then transferred to a mortar and ground thoroughly to obtain the final ultraviolet up-conversion multifunctional material.

[0072] Pr 3+ Single-doped M a Ln(PO4) b The chemical formula of the ultraviolet up-conversion multifunctional material is M9Ln(PO4)7:xPr 3+ , specifically M 9-x Pr x Ln(PO4)7 or M 9-2x Pr x Li x Ln(PO4)7 or M9Ln 1-x Pr x (PO4)7, wherein M=Mg, Ca, Sr, Ba, Zn, Pb; Ln=Y, La, Sc, Lu, Yb, Ce; x=0.001-0.50, and the preparation method is a high-temperature solid-phase reaction method, a coprecipitation method plus a high-temperature sintering method, etc., wherein the high-temperature solid-phase reaction method mainly includes the following steps:

[0073] M 9-x Pr x The Ln(PO4)7 component requires a weighing molar ratio of 9-x:x:1:7, and the raw materials are MCO3 or other M-containing compounds, Pr(NO3)3.6H2O or other Pr-containing compounds, Ln2O3 or other Ln-containing compounds, and NH4H2PO4 or other easily decomposed phosphates, which are added to a mortar and ground uniformly;

[0074] M 9-2x Pr x Li x The Ln(PO4)7 component requires a weighing molar ratio of 9-2x:x:x:1:7, and the raw materials are MCO3 or other M-containing compounds, Pr(NO3)3.6H2O or other Pr-containing compounds, Li2CO3 or other alkali metal compounds, Ln2O3 or other Ln-containing compounds, and NH4H2PO4 or other easily decomposed phosphates, which are added to a mortar and ground uniformly;

[0075] M9Ln 1-x Pr x (PO4)7 component requires a weighing molar ratio of 9:1-x:x:7 The raw materials are MCO3 or other M-containing compounds, Pr(NO3)3·6H2O or other Pr-containing compounds, Ln2O3 or other Ln-containing compounds, and NH4H2PO4 or other easily decomposed phosphates, which are added to a mortar and ground uniformly;

[0076] The ground product is transferred to an alumina crucible, then heated at about 1250°C for 8 hours, with a heating rate of about 5°C / min, and then naturally cooled to room temperature, the product is taken out and transferred to a mortar again for grinding to obtain the final ultraviolet up-conversion multifunctional material.

[0077] Pr 3+ / Gd 3+ Co-doped M a Ln(PO4) b The chemical formula of the ultraviolet up-conversion multifunctional material is M9Ln(PO4)7:xPr 3+ ,yGd 3+ , specifically M 9-x-y Pr x Gd y Ln(PO4)7 or M 9-2x-2y Pr x Gd y Li x+y Ln(PO4)7 or M9Ln 1-x-y Pr x Gd y (PO4)7, wherein M=Mg, Ca, Sr, Ba, Zn, Pb; Ln=Y, La, Sc, Lu, Yb, Ce; x=0.001-0.50, y=0-1.00, and the preparation method is high-temperature solid-phase reaction, coprecipitation plus high-temperature sintering, etc., wherein the high-temperature solid-phase reaction method mainly includes the following steps:

[0078] M 9-x-y Pr x Gd y The (PO4)7 component requires a weighing molar ratio of 9-x-y:x:y:1:7 The raw materials are MCO3 or other M-containing compounds, Pr(NO3)3·6H2O or other Pr-containing compounds, Gd2O3 or other Gd-containing compounds, Ln2O3 or other Ln-containing compounds, and NH4H2PO4 or other easily decomposed phosphates, which are added to a mortar and ground uniformly;

[0079] M 9-2x-2y Pr x Gd y Lix+y The required molar ratio of Ln(PO4)7 is 9-2x-2y:x:y:x+y:1:7. The raw materials are MCO3 or other compounds containing M, Pr(NO3)3·6H2O or other compounds containing Pr, Gd2O3 or other compounds containing Gd, Li2CO3 or other alkali metal compounds, Ln2O3 or other compounds containing Ln, and NH4H2PO4 or other easily decomposed phosphates. The raw materials are added to a mortar and ground thoroughly until uniform.

[0080] M9Ln 1-x-y Pr x Gd y The required molar ratio of (PO4)7 components is 9:1-xy:x:y:7. The raw materials are MCO3 or other compounds containing M, Pr(NO3)3·6H2O or other compounds containing Pr, Gd2O3 or other compounds containing Gd, Ln2O3 or other compounds containing Ln, and NH4H2PO4 or other easily decomposed phosphates. The raw materials are added to a mortar and ground thoroughly until uniform.

[0081] The ground product was transferred to an alumina crucible and held at approximately 1250°C for 8 hours, with a heating rate of about 5°C / minute. It was then allowed to cool naturally to room temperature. The product was then removed and transferred back to a mortar for further grinding to obtain the final UV upconversion multifunctional material.

[0082] Example 1

[0083] First, the required initial raw materials Ca2CO3 (99.99%), Y2O3 (99.999%), NH4H2PO4 (AR, 99%), and Pr(NO3)3·6H2O (99.99%) are used to produce the product according to the chemical formula Ca3Y(PO4)3:xPr 3+ Calculations and weighing were performed, and the precisely weighed raw materials were thoroughly mixed and ground in an agate mortar (for at least 30 minutes; other grinding methods such as a ball mill can also be used). The mixture was then transferred to a corundum crucible and calcined in a muffle furnace at 1350℃ for 10 hours, with a heating rate of approximately 5℃ / min. Upon completion of sintering, the product was removed, rapidly cooled to room temperature, and then thoroughly ground again in a mortar to obtain the final UV upconversion multifunctional material. Subsequently, the material underwent phase characterization and optical property testing. If necessary, fluxes such as alkali metals or charge compensators, such as Li, can be introduced. + Then, simply weigh the Li2CO3 (99.99%) raw material according to the above-mentioned chemical formula stoichiometry, and grind and sinter it using the same method.

[0084] X-ray diffraction analysis of Ca3Y(PO4)3:xPr 3+ , Figure 1It can be seen that the sample material is pure phase, and its fluorescence excitation and emission spectrum is measured by a spectrometer, as shown in Figure 2 The blue light excitation band of the sample is wide (420-496 nm), and the highest excitation peak is about 445 nm. The sample can produce blue light, red light and other visible region spectrum emission, and the highest emission peak is about 602 nm. Under blue light source excitation, the ultraviolet upconversion emission spectrum data of the sample material is as shown in Figure 3 The wide band ultraviolet upconversion emission covers 240-340 nm, and the highest spectral peak is about 250 nm. Further, through composition regulation and substitution method, such as replacing or partially replacing Ca element with Mg, Sr, Ba, Zn and Pb elements or replacing or partially replacing Y element with La, Sc, Lu, Yb and Ce elements, the related samples can also produce similar spectra, as shown in Figure 4 , and the integral intensity can be regulated in the range of 0.5-10. Because these elements have the same valence state, similar physical and chemical properties, and comparable ionic radii, they are often used as doping substitution elements of rare earth elements. The ultraviolet upconversion multifunctional material can be efficiently excited by solar spectrum, xenon lamp, LED light source, continuous and pulsed laser, etc., and has very good application prospect in the fields of solar blind label, sterilization and disinfection, and water and air purification.

[0085] Example 2

[0086] First, the required initial raw materials Ca2CO3 (99.99%), Y2O3 (99.999%), NH4H2PO4 (AR, 99%), Pr(NO3)3·6H2O (99.99%), and Gd2O3 (99.99%) are calculated and weighed according to the chemical formula Ca3Y(PO4)3:xPr 3+ ,yGd 3+ , and the accurately weighed raw materials are thoroughly mixed and ground in an agate mortar (more than about 30 minutes; other grinding methods such as ball milling can also be used), and are calcined in a muffle furnace at 1350°C for 10h, with a heating rate of about 5°C / min. When the sintering is completed, the product is quickly cooled to room temperature, and is again transferred to a mortar for thorough grinding to obtain the final ultraviolet upconversion multifunctional material. If an alkali flux or charge compensator such as Li + is required to be introduced, only Li2CO3 (99.99%) raw material is weighed according to the related chemical formula in the claims, and the same method is used for grinding and sintering.

[0087] The X-ray diffractometer is used to analyze Ca3Y(PO4)3:xPr 3+ ,yGd 3+ , as shown in Figure 1 , and its ultraviolet upconversion emission spectrum is measured by a spectrometer, as shown inFigure 5 .

[0088] As can be seen from Figure 1 , the sample material is a pure phase, Figure 5 , the peak of the ultraviolet B up-conversion emission spectrum is about 312 nm. Further, by adjusting the composition, substitution method and doping concentration, etc., such as replacing or partially substituting Ca element with Mg, Sr, Ba, Zn and Pb elements or replacing or partially substituting Y element with La, Sc, Lu, Yb and Ce elements, the related samples can also produce similar spectra, and the integral intensity can be adjusted within the range of 0.5-30 times. Because the valence states of these elements are the same, the physical and chemical properties are similar, and the ionic radii are comparable, they are often used as doping substitution elements of rare earth elements. The ultraviolet up-conversion multifunctional material can be efficiently excited by solar spectrum, xenon lamp, LED light source, continuous and pulsed laser, etc. It has very good application prospects in the fields of photocatalysis, skin disease phototherapy, cancer photodynamic therapy, fluorescence temperature measurement, secure communication, optical positioning and tracking, etc.

[0089] Example 3

[0090] First, the required initial raw materials Ca2CO3(99.99%), Y2O3(99.999%), NH4H2PO4(AR, 99%), Pr(NO3)3·6H2O(99.99%) are calculated and weighed according to the chemical formula Ca9Y(PO4)7:xPr 3+ , and then sintered in a muffle furnace at 1250°C for 8h, the heating rate is about 5°C / min; when the sintering is completed, the sample is naturally cooled to room temperature, the product is taken out, and then transferred to a mortar for grinding to obtain the final ultraviolet up-conversion multifunctional material. If an alkali flux or charge compensator such as Li + , only needs to be weighed according to the related chemical formula in the claims, and the same method of grinding and sintering is adopted.

[0091] The Ca9Y(PO4)7:xPr 3+ , as shown in Figure 6 , and the fluorescence excitation and emission spectra are measured by a spectrometer, as shown in Figure 7 , and the ultraviolet up-conversion emission spectrum, as shown in Figure 8 .

[0092] Figure 6 As can be seen from the X-ray diffraction pattern of the sample material, the sample material is a pure phase. Figure 7It can be seen that the blue excitation band of the sample is wide (420-496 nm), and the highest excitation peak is about 450 nm, which can produce blue, red and other visible region spectrum emission, and the highest emission peak is about 605 nm. At the same time, the ultraviolet upconversion emission spectrum data of the sample material under blue light source excitation is as follows Figure 8 , and the wide band ultraviolet upconversion emission covers 240-330 nm, and the highest spectral peak is about 250 nm. Further, through the regulation and substitution method, such as replacing or partially replacing Ca element with Mg, Sr, Ba, Zn and Pb element or replacing or partially replacing Y element with La, Sc, Lu, Yb and Ce element, the related samples can also produce similar spectra, and the integral intensity can be regulated in the range of 0.5-10. Because the valence states of these elements are the same, the physical and chemical properties are similar, and the ionic radii are comparable, they are often used as doping substitution elements of rare earth elements. For example, the material is replaced by Pr 3+ instead of Y 3+ , Pr 3+ and Li + instead of two Ca 2+ , which realizes the significant enhancement of ultraviolet upconversion, and the ultraviolet upconversion spectrum is as follows Figure Eight , and through further regulation, the luminescent intensity can be enhanced by several times. It is worth mentioning that the ultraviolet upconversion multifunctional material realizes high concentration doping, and the luminescent intensity of the doped luminescent material is usually maximized at a Pr 3+ concentration of 2-5 mol.%. The ultraviolet upconversion multifunctional material can be efficiently excited by solar spectrum, xenon lamp, LED light source, continuous and pulsed laser, etc., and has very good application prospect in the fields of solar blind label, sterilization and disinfection, and water and air purification.

[0093] Example 4

[0094] First, the required initial raw materials Ca2CO3 (99.99%), Y2O3 (99.999%), NH4H2PO4 (AR, 99%), Pr(NO3)3·6H2O (99.99%), Gd2O3 (99.99%) are calculated and weighed according to the formula Ca9Y(PO4)7:xPr 3+ ,yGd 3+ , the accurately weighed raw materials are thoroughly mixed and ground in an agate mortar (more than about 30 minutes; other grinding methods such as ball mill can also be used), and then calcined in a muffle furnace at 1250℃ for 8h, and the heating rate is about 5℃ / min; when the sintering is completed, the sample is naturally cooled to room temperature, the product is taken out, and then transferred to a mortar for thorough grinding to obtain the final ultraviolet upconversion multifunctional material, and then the material is subjected to phase characterization and optical performance test. If fluxing agents or charge compensators such as Li+ Then, simply weigh the Li2CO3 (99.99%) raw material according to the relevant chemical formula stoichiometric ratio in the claim, and grind and sinter it using the same method.

[0095] X-ray diffraction analysis of Ca9Y(PO4)7:xPr 3+ yGd 3+ ,like Figure 6 As shown. Its ultraviolet upconversion emission spectrum was measured using a spectrometer, with reference to... Figure 10 .

[0096] from Figure 6 It can be seen from this that the sample material is a pure phase. Figure 10 The peak emission spectrum of the mid-ultraviolet B upconversion material is approximately 311.9 nm. Furthermore, by adjusting the composition, substitution method, and doping concentration, such as replacing or partially substituting Ca with Mg, Sr, Ba, Zn, and Pb, or replacing or partially substituting Y with La, Sc, Lu, Yb, and Ce, similar spectra can be produced in related samples, with the integrated intensity adjustable within the range of 0.5-30 times. Because these elements have the same valence state, similar physical and chemical properties, and comparable ionic radii, they are often used as dopants for rare earth elements. This multifunctional ultraviolet upconversion material can be efficiently excited by solar spectroscopy, xenon lamps, LED light sources, continuous and pulsed lasers, and has excellent application prospects in photocatalysis, phototherapy for skin diseases, photodynamic therapy for cancer, fluorescence thermometry, secure communication, and optical positioning and tracking.

[0097] Figure 9 Pr 3+ With Y 3+ and Ca 2+ Since the radii are quite similar, both cells can be replaced. 3+ Heterovalent substitution of Ca 2+ The resulting charge imbalance will lead to the formation of defects and increase the likelihood of nonradiative transitions. Here, to maintain charge balance and eliminate defects, alkali metal ions M are added. + (M = Li, Na, and K). The charge compensation mechanism of alkali metal ions can be described as Pr 3+ +Li + →2Ca 2+ That is, an alkali metal ion and a Pr 3+ Together they replace two Ca 2+ This reduces sample defects and non-radiative transitions, thus increasing light intensity.

[0098] A class of silicate ultraviolet upconversion multifunctional materials, using blue light or blue light + yellow light as excitation source, Pr 3+ The single-doped system can produce broadband ultraviolet C upconversion luminescence, and the ion pair Pr3+ / Gd 3+ Pr 3+ ions will transfer the UV excitation energy to the adjacent Gd 3+ ions efficiently, and finally produce narrow linewidth UV B upconversion luminescence. Among them, blue light (425-495 nm) or blue light (425-495 nm) + yellow light (580-605 nm) are light sources of various forms of LED, solar spectrum, continuous and pulsed laser.

[0099] The matrix materials of silicates are Ca2Al2SiO7, Ba2Y3(SiO4)3F and BaY2Si3O 10 .

[0100] The silicate matrix UV upconversion fluorescent powder is prepared by high-temperature solid phase reaction method, sol-gel, co-precipitation and other methods. The following is a specific description of the preparation by high-temperature solid phase reaction method.

[0101] The UV upconversion fluorescent powder sample is Ca 2-x-y Al2SiO7:xPr 3+ ,yGd 3+ (x = 0.001-0.10, y = 0-0.30), and its representative high-temperature solid phase preparation process includes the following steps:

[0102] a. First, the raw materials Pr6O 11 (99.99%), Al2O3(99.99%), CaCO3(99.99%), SiO2(99.99%) and Gd2O3(99.99%) are calculated according to the chemical formula Ca 2-x-y Al2SiO7:xPr 3+ ,yGd 3+ (x = 0.001-0.10, y = 0-0.30), accurately weighed, and then poured into a mortar and ground for about 30 minutes;

[0103] b. Secondly, the uniformly mixed and completely ground materials are placed in a muffle furnace and calcined, with a heating rate of 5℃ / min to 1200-1400℃ and kept for 24 hours, and then naturally cooled to room temperature;

[0104] c. Finally, the calcined material is taken out and ground for about 20 minutes, and the powder preparation is completed. Then the powder is characterized.

[0105] The UV upconversion fluorescent powder sample is Ba2Y3(SiO4)3F:Pr 3+ ,Gd 3+ , and its representative high-temperature solid phase preparation process is as follows:

[0106] a. First, the raw materials BaCO3(99.95%), Y2O3(99.999%), SiO2(99.99%), NH4F(98%), Pr(NO3)3·6H2O(99.99%), Gd2O3(99.99%) are calculated according to the formula Ba2Y 3-x-y (SiO4)3F:xPr 3+ ,yGd 3+ or Ba 2-x-y Y3(SiO4)3F:xPr 3+ ,yGd 3+ (x=0.001-0.10, y=0-0.60) are calculated, accurately weighed, and then poured into a mortar and ground for about 30 minutes;

[0107] b. Next, the uniformly mixed and completely ground materials are placed in a muffle furnace and calcined at a heating rate of 5°C / min to 1300°C for 4 hours, and then naturally cooled to room temperature;

[0108] c. Finally, the calcined materials are removed and ground for about 20 minutes, and the powder preparation is completed. The powder is then characterized for performance.

[0109] The UV upconversion fluorescent powder sample is BaY2Si3O 10 :Pr 3+ ,Gd 3+ doped UV upconversion fluorescent powder preparation method, specifically comprising the following steps:

[0110] a. First, the raw materials BaCO3(99.95%), Y2O3(99.999%), SiO2(99.99%), Pr(NO3)3·6H2O(99.99%), Gd2O3(99.99%) are calculated according to the formula BaY 2-x-y Si3O 10 :xPr 3+ ,yGd 3+ or Ba 1-x-y Y2Si3O 10 :xPr 3+ ,yGd 3+ (x=0.001-0.05, y=0-0.60) are calculated, accurately weighed, and then poured into a mortar and ground for about 30 minutes;

[0111] b. Next, the uniformly mixed and completely ground materials are placed in a muffle furnace and calcined at a heating rate of 5°C / min to 1350°C for 4 hours, and then naturally cooled to room temperature;

[0112] c. Finally, the calcined materials are removed and ground for about 20 minutes, and the powder preparation is completed. The powder is then characterized for performance.

[0113] The following further illustrates the present application based on the matrix material silicate doped with Pr 3+ / Gd 3 + The preparation of the multifunctional material is described.

[0114] Example 5

[0115] Preparation of the powder sample Ca2Al2SiO7:0.04Pr 3+ ,0.25Gd 3+ (i.e. Ca 1.71 Pr 0.04 Gd 0.25 Al2SiO7):

[0116] a. First, 0.1362g Pr6O 11 , 2.038g Al2O3, 3.4231g CaCO3, 1.2016g SiO2and 0.9063g Gd2O3raw materials are weighed, and then the weighed raw materials are poured into a mortar and mixed and ground for about 30 minutes;

[0117] b. Next, the mixed and uniform raw materials are poured into a crucible, and then placed in a muffle furnace for calcination, with a temperature increasing rate of 5℃ per minute to 1400℃ for 24 hours, and then waiting for natural cooling to room temperature;

[0118] c. Finally, the calcined material is taken out and ground for about 20 minutes, and the powder preparation is completed. Then the powder is characterized for performance.

[0119] The powder sample Ca2Al2SiO7:0.04Pr 3+ ,0.25Gd 3+ is analyzed by X-ray diffractometer, as shown in Figure 11 . Its ultraviolet upconversion emission spectrum is measured by a spectrometer, as shown in Figure 12 .

[0120] As can be seen from Figure 11 , the sample material is a pure phase, Figure 12 , and the peak value of the ultraviolet B upconversion emission spectrum is about 312nm. The ultraviolet upconversion material can be efficiently excited by solar spectrum, xenon lamp, LED light source, continuous and pulsed laser, etc., and has very good application prospects in the fields of photocatalysis, skin disease phototherapy, cancer photodynamic therapy, fluorescence temperature measurement, secret communication, optical positioning and tracking, etc.

[0121] Example 6

[0122] Preparation of the powder sample Ca2Al2SiO7:0.04Pr 3+ (i.e. Ca 1.96 Pr0.04 Preparation of Ca2Al2SiO7:

[0123] a. First, 0.1360 g Pr6O 11 , 3.9236 g CaCO3 and 1.2016 g SiO2 raw materials were weighed and then poured into a mortar for mixing and grinding for about 30 minutes;

[0124] b. Second, the mixed and uniform materials were poured into a crucible and calcined in a muffle furnace, with a temperature rising rate of 5°C per minute, rising to 1200-1400°C and keeping for 24 hours, and then waiting for natural cooling to room temperature;

[0125] c. Finally, the calcined materials were taken out and ground for about 20 minutes, and the powder preparation was completed. Then, the powder was characterized.

[0126] The Ca2Al2SiO7:0.04Pr 3+ was analyzed by an X-ray diffractometer, as shown in Figure 11 , and its fluorescence emission spectrum was measured by a spectrometer, as shown in Figure 13 , and its ultraviolet up-conversion emission spectrum, as shown in Figure 12 .

[0127] Figure 11 It can be seen that the sample material is a pure phase. Figure 13 It can be seen that the sample can produce blue light, red light and other visible region spectrum emission, with a highest emission peak of about 485 nm. At the same time, under the excitation of a blue light source, the ultraviolet up-conversion emission spectrum data of the sample material are as shown in Figure 12 , with a wide-band ultraviolet up-conversion emission covering 245-370 nm, and a highest spectrum peak of about 271 nm. The ultraviolet up-conversion material can be efficiently excited by solar spectrum, xenon lamp, LED light source, continuous and pulsed laser, etc., and has a very good application prospect in the fields of solar blind label, sterilization and disinfection, and water and air purification.

[0128] Example 7

[0129] Preparation of powder sample Ba2Y3(SiO4)3F:0.007Pr 3+ , 0.40 Gd 3+ (i.e. Ba2Y 2.593 Pr 0.007 Gd 0.40 (SiO4)3F):

[0130] a. First, 1.9734 g of BaCO3, 1.4638 g of Y2O3, 0.0152 g of Pr(NO3)3·6H2O, 0.3625 g of Gd2O3, 0.9012 g of SiO2 and 0.3704 g of NH4F raw materials are weighed, and then the weighed raw materials are poured into a mortar and mixed and ground for about 30 minutes;

[0131] b. Secondly, the uniformly mixed materials are placed in a muffle furnace for calcination under the condition of a temperature rising rate of 5 ℃ per minute to 1300 ℃ for 4 hours, and natural cooling to room temperature is waited;

[0132] c. Finally, the calcined materials are taken out and ground for about 20 minutes, and the powder preparation is completed. Then, the powder is subjected to performance characterization.

[0133] The Ba2Y3(SiO4)3F:0.007Pr 3+ ,0.40Gd 3+ material is analyzed by an X-ray diffractometer, as shown in Figure 14 . Its ultraviolet up-conversion emission spectrum is measured by a spectrometer, as shown in Figure 15 .

[0134] As can be seen from Figure 14 , the sample material is a pure phase, Figure 15 , and the peak value of the ultraviolet B up-conversion emission spectrum is about 312 nm. The ultraviolet up-conversion material can be efficiently excited by solar spectrum, xenon lamp, LED light source, continuous and pulsed laser, etc., and has very good application prospects in the fields of photocatalysis, skin disease phototherapy, cancer photodynamic therapy, fluorescent temperature measurement, secret communication, optical positioning and tracking, etc.

[0135] Example 8

[0136] Preparation of the powder sample Ba2Y3(SiO4)3F:0.007Pr 3+ (i.e. Ba2Y 2.993 Pr 0.007 (SiO4)3F):

[0137] a. First, 1.9734 g of BaCO3, 1.6896 g of Y2O3, 0.0152 g of Pr(NO3)3·6H2O, 0.9012 g of SiO2 and 0.3704 g of NH4F raw materials are weighed, and then the weighed raw materials are poured into a mortar and mixed and ground for about 30 minutes;

[0138] b. Secondly, the uniformly mixed materials are placed in a muffle furnace for calcination under the condition of a temperature rising rate of 5 ℃ per minute to 1300 ℃ for 4 hours, and natural cooling to room temperature is waited;

[0139] c. Finally, the calcined material is taken out and re-milled for about 20 minutes, and the powder preparation is completed. The powder is then characterized.

[0140] Ba2Y3(SiO4)3F:0.007Pr 3+ , as shown in Figure 14 , and its fluorescence excitation and emission spectra are measured by a spectrometer, as shown in Figure 16 , and its ultraviolet upconversion emission spectrum, as shown in Figure 15 .

[0141] Figure 14 It can be seen that the sample material is a pure phase. Figure 16 It can be seen that the blue light excitation band of the sample is wide (420-500 nm), and the highest excitation peak is about 450 nm. The sample can produce blue light, red light and other visible region spectral emissions, and the highest emission peak is about 607 nm. At the same time, under the excitation of a blue light source, the ultraviolet upconversion emission spectrum data of the sample material are as shown in Figure 15 , and the wide-band ultraviolet upconversion emission covers 250-360 nm, and the highest spectral peak is about 280 nm. The ultraviolet upconversion material can be efficiently excited by solar spectrum, xenon lamp, LED light source, continuous and pulsed laser, etc., and has very good application prospects in the fields of solar blind label, sterilization and disinfection, and water and air purification.

[0142] Example 9

[0143] Preparation of powder sample BaY2Si3O 10 :0.03Pr 3+ ,0.40Gd 3+ (i.e. BaY 1.57 Pr 0.03 Gd 0.40 Si3O 10 ):

[0144] a. First, 0.9867 g of BaCO3, 0.8863 g of Y2O3, 0.0653 g of Pr(NO3)3·6H2O, 0.3625 g of Gd2O3 and 0.9012 g of SiO2 raw materials are weighed, and then the weighed raw materials are poured into a mortar and mixed and milled for about 30 minutes;

[0145] b. Secondly, the uniformly mixed material is placed in a muffle furnace for calcination, with a temperature rising rate of 5℃ per minute to 1350℃ for 4 hours, and then naturally cooled to room temperature;

[0146] c. Finally, the calcined material is taken out and re-milled for about 20 minutes, and the powder preparation is completed. The powder is then characterized.

[0147] X-ray diffractometer was used to analyze the BaY2Si3O 10 :0.03Pr 3+ ,0.40Gd 3+ , as shown in Figure 17 . The ultraviolet upconversion emission spectrum was measured by a spectrometer, as shown in Figure 18 .

[0148] It can be seen from Figure 17 that the sample material is a pure phase. Figure 18 The peak of the ultraviolet B upconversion emission spectrum is about 313.5 nm. The ultraviolet upconversion material can be efficiently excited by solar spectrum, xenon lamp, LED light source, continuous and pulsed laser, etc., and has very good application prospects in the fields of photocatalysis, skin disease phototherapy, cancer photodynamic therapy, fluorescence temperature measurement, secure communication, and optical positioning and tracking.

[0149] Example 10

[0150] Preparation of the powder sample BaY2Si3O 10 :0.03Pr 3+ (i.e. BaY 1.97 Pr 0.03 Si3O 10 ):

[0151] a. First, weigh 0.9867 g of BaCO3, 1.1121 g of Y2O3, 0.0653 g of Pr(NO3)3•6H2O, and 0.9012 g of SiO2 raw materials, and then pour the weighed raw materials into a mortar and mix and grind for about 30 minutes;

[0152] b. Second, place the uniformly mixed material in a muffle furnace and calcine it at a temperature increasing rate of 5 ℃ per minute to 1350 ℃ for 4 hours, and wait for natural cooling to room temperature;

[0153] c. Finally, take out the calcined material and grind it for about 20 minutes, which completes the preparation of the powder. Then, the powder is characterized.

[0154] X-ray diffractometer was used to analyze the BaY2Si3O 10 :0.03Pr 3+ , as shown in Figure 17 , and a spectrometer was used to measure the fluorescence excitation and emission spectrum, as shown in Figure 19 , and the ultraviolet upconversion emission spectrum, as shown in Figure 18 .

[0155] Figure 17 It can be seen that the sample material is a pure phase. Figure 19It can be seen that the blue excitation band of the sample is wide (415-510 nm), the highest excitation peak is about 467 nm, and the visible region spectrum emission such as blue light and red light can be generated, and the highest emission peak is about 617 nm. At the same time, the ultraviolet up-conversion emission spectrum data of the sample material under blue light source excitation is as follows Figure 18 The wide-band ultraviolet up-conversion emission covers 250-360 nm, and the highest spectral peak is about 284 nm. The ultraviolet up-conversion material can be efficiently excited by solar spectrum, xenon lamp, LED light source, continuous and pulsed laser, etc., and has very good application prospect in the fields of solar blind label, sterilization and disinfection, and water and air purification.

[0156] The above are only preferred embodiments of the present application, and do not have any limiting effect on the present application. Any person skilled in the art can make any form of equivalent replacement, modification or change of the technical solutions and technical contents disclosed by the present application without departing from the scope of the technical solutions of the present application, and still belongs to the protection scope of the present application.

Claims

1. A method based on Single blending Co-doping The ultraviolet upconversion multifunctional material is characterized by, The doped matrix material includes silicates or phosphates. When the doped matrix material is a silicate, the general chemical formula of the converted multifunctional material is: , and ; When the doped matrix material is a phosphate, the general chemical formula of the converted multifunctional material is: ,in, for , , , , or Any one of them, for , , , , or Any one of them, , , , or , , , ; when Single doping or Co-doping The general chemical formulas of this material are as follows: or ,in, , ; when Single doping At that time, the general chemical formula of the material is or ,when Co-doping At that time, the general chemical formula of the material is or ,in , ; when Co-doping At that time, the general chemical formula of the material is or ,in, , ; when Single doping At that time, the general chemical formula of the material is: or When the general chemical formula of the material is Specifically, when: or ,and When the general chemical formula of the material is Specifically, when: or ,and ; when Co-doping At that time, the general chemical formula of the material is: or When the general chemical formula of the material is Specifically, when: or ,and , When the general chemical formula of the material is Specifically, when: or ,and , ; These materials absorb visible photons and then emit high-energy photons in the ultraviolet C and ultraviolet B bands by multi-photon upconversion of blue light or blue light + yellow light. When the doped matrix material is phosphate, the charge balance is maintained and defects are eliminated by introducing the charge compensation mechanism of alkali metal elements, thereby optimizing the luminescence performance of the product material. The alkali metal element is , , and Any one of them.

2. The method based on claim 1 Single blending Co-doping The ultraviolet upconversion multifunctional material is characterized by, The alkali metal element is ,when Single doping At that time, the general chemical formulas of the material are respectively or ; when Co-doping The general chemical formulas of this material are as follows: or .

3. A method based on Single blending Co-doping A method for preparing ultraviolet upconversion multifunctional materials, used to prepare the materials based on the method described in claim 1 or 2. Single blending Co-doping The ultraviolet upconversion multifunctional material is characterized by, The material is prepared by high-temperature solid-state reaction or co-precipitation. When the doped matrix material is silicate, the material is also prepared by sol-gel method.

4. The method based on claim 3 Single blending Co-doping The preparation method of ultraviolet upconversion multifunctional materials is characterized by the following: The preparation method involves a high-temperature solid-state reaction, specifically including the following steps: S1: Based on the specific composition of the ultraviolet upconversion multifunctional material, weigh each raw material and add each raw material into a mortar and grind it thoroughly and evenly; S2: Transfer the ground product to a vessel, set the heating rate to 5℃ / min, and after sintering, remove the product and allow it to cool rapidly to room temperature. Finally, transfer the cooled product to a mortar and grind it thoroughly to obtain the final UV upconversion phosphate multifunctional material.

5. The method based on claim 4 Single blending Co-doping The preparation method of ultraviolet upconversion multifunctional materials is characterized by the following: The raw materials are weighed based on the multifunctional material to be prepared, including basic raw materials and additive raw materials. When the doped matrix material is silicate, the basic raw materials include: , , , , and Any combination of the above, the added raw materials include , and One or two of them; When the doped matrix material is phosphate, the basic raw material includes: or other contents Compounds or other contents Compounds and Other easily decomposable phosphates, the added raw materials include or other contents compounds, or other contents Compounds and or one or more combinations of other alkali metal compounds.

6. The method based on claim 5 Single blending Co-doping The preparation method of ultraviolet upconversion multifunctional materials is characterized by the following: When the chemical formula of the prepared material is At that time, raw materials or other contents Compounds or other contents compounds, , or other contents Compounds and The mass ratios of the other easily decomposable phosphates are 3-2x:x:x:1:

3. ; When the chemical formula of the prepared material is At that time, raw materials or other contents Compounds or other contents compounds, or other contents Compounds , or other contents Compounds and The mass ratios of the other easily decomposable phosphates are: 3-2x-2y:x:y:x+y:1:

3. , ; When the chemical formula of the prepared material is At that time, raw materials or other contents Compounds or other contents compounds, , or other contents Compounds and The mass ratios of the other easily decomposable phosphates are: 9-2x:x:x:1:

7. ; When the chemical formula of the prepared material is At that time, raw materials or other contents Compounds or other contents compounds, or other contents Compounds , or other contents Compounds and The mass ratios of the other easily decomposable phosphates are: 9-2x-2y:x:y:x+y:1:

7. , .

7. The method based on claim 5 Single blending Co-doping The preparation method of ultraviolet upconversion multifunctional materials is characterized by the following: When the chemical formula of the prepared material is At that time, raw materials , , , and The mass ratio of the weighed items is: , ; When the chemical formula of the prepared material is At that time, raw materials , , , , and The mass ratio of the weighed items is: , ; When the chemical formula of the prepared material is At that time, raw materials , , , and The mass ratio of the weighed items is: , ; When the chemical formula of the prepared material is At that time, raw materials or other contents Compounds or other contents compounds, or other contents Compounds and The mass ratios of other easily decomposable phosphates are as follows: 3- x : x :1:3, ; When the chemical formula of the prepared material is At that time, raw materials or other contents Compounds or other contents compounds, or other contents Compounds and The mass ratio of other easily decomposable phosphates is 3:1- x : x 3, ; When the chemical formula of the prepared material is At that time, raw materials or other contents Compounds or other contents compounds, or other contents Compounds or other contents Compounds and The mass ratios of other easily decomposable phosphates are as follows: 3- x - y : x : y :1:3, , ; When the chemical formula of the prepared material is At that time, raw materials or other contents Compounds or other contents compounds, or other contents Compounds or other contents Compounds and The mass ratios of the other easily decomposable phosphates are 3:1 - xy:x:y:

3. , ; When the chemical formula of the prepared material is At that time, raw materials or other contents Compounds or other contents compounds, or other contents Compounds and The mass ratios of the other easily decomposable phosphates are: 9-x:x:1:

7. ; When the chemical formula of the prepared material is At that time, raw materials or other contents Compounds or other contents compounds, or other contents Compounds and The mass ratios of the other easily decomposable phosphates are 9:1 to x:x:

7. ; When the chemical formula of the prepared material is At that time, raw materials or other contents Compounds or other contents compounds, or other contents Compounds or other contents Compounds and The mass ratios of the other easily decomposable phosphates are: 9-xy:x:y:1:

7. , ; When the chemical formula of the prepared material is At that time, raw materials or other contents Compounds or other contents compounds, or other contents Compounds or other contents Compounds and The mass ratios of the other easily decomposable phosphates are 9:1 - xy:x:y:

7. , .

8. The method based on claim 4 Single blending Co-doping The preparation method of ultraviolet upconversion multifunctional materials is characterized by the following: In S1, when the doped matrix material is silicate, the vessel is a muffle furnace; when the doped matrix material is phosphate, the vessel is an alumina crucible.

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