CN104069847B

CN104069847B - Rare-earth europium dopen Nano TiO2The preparation method of hollow glass micropearl

Info

Publication number: CN104069847B
Application number: CN201410143092.9A
Authority: CN
Inventors: 张辉; 杨振威
Original assignee: Xian Polytechnic University
Current assignee: Xian Polytechnic University
Priority date: 2014-04-10
Filing date: 2014-04-10
Publication date: 2016-05-25
Anticipated expiration: 2034-04-10
Also published as: CN104069847A

Abstract

Rare-earth europium dopen Nano TiO disclosed by the invention₂The preparation method of hollow glass micropearl, first uses ferric sulfate, sodium thiosulfate, urea, PEG-6000 in hollow glass micropearl surface coated magnetic nanometer Fe₃O₄, then use ethyl orthosilicate coated Si O₂Intermediate layer, is finally used titanium sulfate, urea, polyvinylpyrrolidone and europium nitrate to be coated europium dopen Nano TiO₂Photochemical catalyst, prepares a kind of rare earth doped magnetic photocatalytic hollow glass micropearl of nucleocapsid structure that has. Rare-earth europium dopen Nano TiO of the present invention₂The preparation method of hollow glass micropearl, has realized and has not reduced TiO₂Under the prerequisite of photocatalytic activity, give the magnetic property of hollow glass micropearl excellence.

Description

Rare-earth europium dopen Nano TiO2The preparation method of hollow glass micropearl

Technical field

The invention belongs to function Inorganic Non-metallic Materials preparation method technical field, relate to the method for the coated modification of a kind of hollow glass micropearl, be specifically related to a kind of rare-earth europium dopen Nano TiO₂The preparation method of hollow glass micropearl.

Background technology

There are two key issues in the development of solid, liquid photocatalysis system and application: the one, how to improve the catalytic activity of catalyst; The 2nd, the separation of catalyst, reclaim and reuse. As widely used TiO₂Catalysis material, people have carried out in depth research from many aspects such as titanium source category, preparation condition, crystal type, interplanar distance, grain size, rear-earth-doped and dye sensitizations. Research shows, rare earth doped TiO₂Its photo absorption performance, electric charge diffusion, surface reaction, particle diameter and crystal formation etc. are exerted an influence. This be because: 1. formed trap center, rare earth element is the metal ion of valence state lower than+4 valencys, can effectively catch hole, suppresses the compound of electronics and hole; 2. form doped energy-band, make electronics and the hole of catching on photon excitation doped energy-band that energy is less, improve the utilization rate of photon; 3. cause the diffusion length of carrier to increase, thereby extend the life-span in electronics and hole, suppress compound; 4. cause lattice defect, be conducive to form more Ti⁴⁺Oxidation center. The rare earth element of doping is mainly the LREE of group of the lanthanides, at TiO₂The rare earth element of middle doping variety classes and variable concentrations, the variation difference causing.

Nanometer Fe₃O₄Magnetic-particle, as important functional material, demonstrates excellent performance at aspects such as magnetic fluid material, microwave absorbing material, special catalyst raw materials, becomes one of hot fields of materialogy. At present, nanometer Fe₃O₄Preparation method mainly contain hydrothermal synthesis method, neutralization precipitation method, microemulsion method, coprecipitation and oxidation-precipitation method etc., wherein hydro-thermal method is prepared nanometer Fe₃O₄Particle has significant advantage, and the one, relatively high temperature is conducive to the raising of product magnetic property and crystallization degree; The 2nd, in closed container, produce relatively high pressure and avoided component volatilization, improve product purity, reduce pollution. Utilize the key of hydro-thermal method synthesizing nano-scale oxide to be, under HTHP, the solubility of the corresponding hydroxide of oxide in water must be greater than the originally solubility in water of oxide, so hydroxide while precipitated oxide soluble in water, the process of a dissolving, crystallization has only been experienced in the formation of oxide like this, prepared nanocrystalline growth is comparatively complete, crystallite dimension is little, narrow particle size distribution, reunion degree is low, and do not need high-temperature calcination pretreatment, avoided the introducing of grain growth, defect formation and impurity. In addition, due to the hyperbaric environment that system itself forms, it is very even that reaction is carried out. Under hydrothermal condition, by controlling the conditions such as reaction temperature, reaction time and raw material proportioning, can obtain the product of different crystal structure, composition, pattern and particle size, uniform particles, favorable dispersibility, need not high-temperature roasting, and process is polluted little, simple to operate, easily realize the advantages such as suitability for industrialized production.

Hollow glass micropearl is the small hollow glass spheres of a kind of size, having the advantages such as light weight, low heat conduction, resistance to compression, high dispersive, sound insulation, electrical insulating property and Heat stability is good, is the novel light material of a kind of of many uses, the excellent performance that gets up of development in recent years. Utilize the feature of hollow glass micropearl light weight, hollow, it is carried out to surface modification treatment, can obtain having the new material of specific function.

Use at present ferric sulfate, sodium thiosulfate and urea to adopt hydro-thermal method to hollow glass micropearl coated magnetic nanometer Fe₃O₄Particle, then uses ethyl orthosilicate to be coated flower ball-shaped SiO₂Intermediate layer, is finally used titanium sulfate, urea and europium nitrate to be coated europium dopen Nano TiO₂The composite modifying method of photocatalysis layer does not also have.

Summary of the invention

The object of this invention is to provide a kind of rare-earth europium dopen Nano TiO₂The preparation method of hollow glass micropearl, has realized and has not reduced TiO₂Under the prerequisite of photocatalytic activity, give the magnetic property of hollow glass micropearl excellence.

The technical solution adopted in the present invention is, rare-earth europium dopen Nano TiO₂The preparation method of hollow glass micropearl, specifically implements according to following steps:

Step 1, to hollow glass micropearl clean, flotation and pretreatment;

Step 2, preparation coupling modification mixed solution, utilize coupling modification mixed solution to carry out rich surface amination processing to the hollow glass micropearl obtaining through step 1;

Step 3, the amidized hollow glass micropearl of the rich surface obtaining through step 2 is carried out to clad nano Fe₃O₄Modification;

Step 4, to the clad nano Fe obtaining through step 3₃O₄Hollow glass micropearl carries out coated Si O₂Process;

Step 5, by the coated flower ball-shaped SiO obtaining through step 4₂Magnetic hollow glass microballoon be coated rare-earth europium dopen Nano TiO₂Process, obtain rare-earth europium dopen Nano TiO₂Magnetic photocatalytic hollow glass micropearl.

Feature of the present invention is also:

Step 1 is specifically implemented according to following steps:

Step 1.1, get respectively hollow glass micropearl and running water, first the temperature of running water is warming up to 35 DEG C～45 DEG C, then hollow glass micropearl is added in running water, by the hollow glass micropearl that adds 10g～20g in every liter of running water, speed with 100rpm～200rpm stirs the hollow glass micropearl 5min～10min in running water, the temperature of running water is risen to 70 DEG C～90 DEG C again, constant temperature soaks hollow glass micropearl 50min～70min, leave standstill until naturally cool to room temperature, after hollow glass micropearl layering, the hollow glass micropearl swimming on running water liquid level is fished for out, separately get clean running water and rinse the hollow glass micropearl fishing for out 1 time～3 times, drain deionized water, complete flotation and cleaning to hollow glass micropearl, obtain clean hollow glass micropearl,

Step 1.2, take respectively for 1:0.8～1.2 the clean hollow glass micropearl, the NaOH that obtain through step 1.1 in mass ratio, the NaOH taking is added in deionized water, be mixed with 10g/L～20g/L sodium hydroxide solution;

Step 1.3, first sodium hydroxide solution that step 1.2 is made is warming up to 40 DEG C～80 DEG C, again the clean hollow glass micropearl taking through step 1.2 is poured in sodium hydroxide solution and soaked, speed with 100rpm～200rpm stirs 10min～30min, then the hollow glass micropearl soaking in sodium hydroxide solution is fished for out, wash by deionized water, until the pH value of the deionized water after washing is neutrality, complete the pretreatment to hollow glass micropearl;

Step 1.4, will be through the pretreated hollow glass micropearl of step 1.3 drying 2h～4h under 110 DEG C～150 DEG C conditions.

Step 2 is specifically implemented according to following steps:

Step 2.1, measure respectively absolute ethyl alcohol and deionized water for 1:8～10 by volume, absolute ethyl alcohol and deionized water are hybridly prepared into ethanolic solution;

Step 2.2, take the hollow glass micropearl obtaining through step 1, measure the ethanolic solution of preparing through step 2.1, get the ethanolic solution of 0.025L～0.05L by the hollow glass micropearl of every gram;

Take silane resin acceptor kh-550, the quality of silane resin acceptor kh-550 is 10%～30% of the hollow glass micropearl quality that takes;

Step 2.3, the silane resin acceptor kh-550 taking in step 2.2 is dropwise added in the ethanolic solution that step 2.2 measures, first stir the ethanolic solution of silane resin acceptor kh-550 with the speed of 100rmp～200rpm, form mixed solution, then regulating the pH value of mixed solution with glacial acetic acid is 3.5～5.5, obtains coupling modification mixed solution;

Step 2.4, the hollow glass micropearl taking through step 2.2 is added in the coupling modification mixed solution obtaining through step 2.3, stir the hollow glass micropearl in coupling modification mixed solution with the speed of 100rpm～200rpm, after again coupling modification mixed solution being warming up to 20 DEG C～40 DEG C, constant temperature leaves standstill 8h～12h, then carry out vacuum filtration processing, hollow glass micropearl after coupling modification is separated from coupling modification mixed solution, obtain the hollow glass micropearl after coupling modification, then the hollow glass micropearl after coupling modification is cleaned 1 time～3 times with absolute ethyl alcohol,

Step 2.5, will be through dispersed the coming of step 2.4 hollow glass micropearl after treatment, be placed under the ultraviolet lamp that dominant wavelength is 365nm and irradiate 30min～60min, then the hollow glass micropearl irradiating through ultraviolet lamp is positioned under the temperature conditions of 70 DEG C～90 DEG C and carries out preliminary drying, the preliminary drying time is 2h～4h, be positioned over again under the temperature conditions of 110 DEG C～130 DEG C and bake 1min～3min, obtain the amidized hollow glass micropearl of rich surface.

Step 3 is specifically implemented according to following steps:

Step 3.1, get respectively ferric sulfate, sodium thiosulfate, urea and PEG-6000 for 1:0.25～1.5:3～30:0.5～6 in molar ratio;

First ferric sulfate is added in the deionized water of 30 DEG C～60 DEG C of temperature, be mixed with the ferrum sulfuricum oxydatum solutum that molar concentration is 0.03mol/L～0.1mol/L, again by the ferrum sulfuricum oxydatum solutum preparing through sonic oscillation 5min～10min, being dissolved in deionized water completely until ferric sulfate is after yellow transparent solution, add sodium thiosulfate and fully stir, solution colour becomes pitch black purple, continue to stir and become achromaticity and clarification, now add urea, PEG-6000, continue to stir until solution is white in color colloidal suspension, prepare modified solution;

Step 3.2, take the amidized hollow glass micropearl of the rich surface obtaining through step 2, measure the modified solution of preparing through step 3.1, get the modified solution of 0.05L～0.1L by every gram of amidized hollow glass micropearl of rich surface; Amidized rich surface hollow glass micropearl is added in modified solution, more amidized rich surface hollow glass micropearl is transferred to together with modified solution in the stainless steel cauldron of inner liner polytetrafluoroethylene;

After step 3.3, sealing stainless steel cauldron, stainless steel cauldron is placed in to homogeneous reactor, be warming up to 120 DEG C～180 DEG C with 1 DEG C/min～2 DEG C/min speed, isothermal reaction 3h～8h, after stainless steel cauldron is naturally cooling, take out the hollow glass micropearl that is black, utilize the floatability of hollow glass micropearl that hollow glass micropearl is separated with remaining waste liquid after reaction, obtain the hollow glass micropearl after modification;

Step 3.4, the hollow glass micropearl after the modification obtaining through step 3.3 is first used to deionized water rinsing 1 time～3 times, then use absolute ethanol washing 1 time～3 times, finally, in 60 DEG C～80 DEG C vacuum drying 12～24h, obtain clad nano Fe₃O₄Hollow glass micropearl.

Step 4 is specifically implemented according to following steps:

Step 4.1, be that 1:4～6 measure respectively deionized water and absolute ethyl alcohol according to volume ratio, the deionized water measuring is mixed with absolute ethyl alcohol, make ethanolic solution, re-using mass percent concentration and be 24%～26% ammoniacal liquor, to regulate the pH value of ethanolic solution be 7.8～8.2, formation mixed solution;

Step 4.2, measure respectively absolute ethyl alcohol and ethyl orthosilicate for 1:1.7～1.8 by volume, the absolute ethyl alcohol measuring is mixed with ethyl orthosilicate, make ethyl orthosilicate alcohol mixed solution;

Step 4.3, take the clad nano Fe obtaining through step 3₃O₄Hollow glass micropearl, measure in step 4.1 mixed solution of preparation, by every gram of clad nano Fe₃O₄Hollow glass micropearl get 0.025L～0.05L mixed solution, by the clad nano Fe taking₃O₄Hollow glass micropearl adds in the mixed solution measuring, and under 40 DEG C～60 DEG C conditions, stirs 5min～10min with the speed of 200r/min～500r/min, then dropwise adds the ethyl orthosilicate alcohol mixed solution in step 4.2, by every gram of clad nano Fe₃O₄Hollow glass micropearl is got 0.02L～0.04L ethyl orthosilicate alcohol mixed solution, continue to stir 6h～12h, after reaction finishes by hollow glass micropearl with react afterwards remaining fluid separation applications, the hollow glass micropearl of separating is first used to washed with de-ionized water 1 time～3 times, then use absolute ethanol washing 1 time～3 times, again in 75 DEG C～85 DEG C vacuum drying 1h～3h, finally bake 5min～10min in 140 DEG C～160 DEG C, obtain coated flower ball-shaped SiO₂Magnetic hollow glass microballoon.

Step 5.1, get respectively titanium sulfate, urea, polyvinylpyrrolidone and europium nitrate for 1:0.2～20:0.0004～0.006:0.0005～0.01 in molar ratio, titanium sulfate is dissolved in the deionized water of 55 DEG C～65 DEG C, through sonic oscillation 5min～10min, then add successively urea, polyvinylpyrrolidone and europium nitrate, fully stir it is fully dissolved, obtain modified solution A;

Step 5.2, will obtain coated flower ball-shaped SiO through step 4₂Magnetic hollow glass microballoon add in the modified solution A obtaining through step 5.1, by every gram of coated flower ball-shaped SiO₂Magnetic hollow glass microballoon add the modified solution A of 0.025L～0.05L, will be coated flower ball-shaped SiO₂Magnetic hollow glass microballoon be transferred to together with modified solution A in the stainless steel cauldron of inner liner polytetrafluoroethylene, sealing stainless steel cauldron;

Step 5.3, by sealing after stainless steel cauldron be placed in homogeneous reactor, be warming up to 110 DEG C～160 DEG C with 1 DEG C/min～2 DEG C/min speed, isothermal reaction 2h～5h, after stainless steel cauldron is naturally cooling, utilize the floatation characteristic of hollow glass micropearl that reacted hollow glass micropearl is separated with remaining solution after reaction, the hollow glass micropearl of separating is first used to deionized water rinsing 1 time～3 times, absolute ethanol washing 1～3 time again, finally dry, obtain rare-earth europium dopen Nano TiO₂Magnetic photocatalytic hollow glass micropearl.

In step 5.3 by the hollow glass micropearl of separating vacuum drying under 60 DEG C～80 DEG C conditions.

The invention has the beneficial effects as follows:

(1) rare-earth europium dopen Nano TiO of the present invention₂The preparation method of hollow glass micropearl adopts hydro-thermal method preparing magnetic Nano Fe₃O₄When particle, the directly surface of the hollow glass micropearl after coupling modification coated magnetic nanometer Fe₃O₄Film, gives hollow glass micropearl magnetic property; By controlling reaction temperature and time, the technological parameters such as the consumption of predecessor, precipitating reagent and surfactant, optimize modified technique, and the method is saved raw material, easy and simple to handle.

(2) rare-earth europium dopen Nano TiO of the present invention₂In the preparation method of hollow glass micropearl, taking ethyl orthosilicate as raw material, ammoniacal liquor is hydrolytic accelerating agent, adopts the precipitation method at the coated flower ball-shaped SiO in magnetic hollow glass microballoon surface₂Intermediate layer, not only can be by Fe₃O₄With outer TiO₂Keep apart, prevent that light induced electron is by Fe₃O₄Catch reduction photocatalytic activity, and flower ball-shaped SiO₂Surface has increased the specific area of hollow glass micropearl, is photochemical catalyst TiO₂Larger space is provided.

(3) rare-earth europium dopen Nano TiO of the present invention₂In the preparation method of hollow glass micropearl, taking titanium sulfate and urea as predecessor, polyvinylpyrrolidone is surfactant, and europium nitrate is rear-earth-doped element, by controlling reaction condition and material proportion, and coated europium dopen Nano TiO₂, improve nano-TiO₂Photocatalytic activity under ultraviolet ray and radiation of visible light.

(4) adopt rare-earth europium dopen Nano TiO of the present invention₂The hollow glass micropearl that the preparation method of hollow glass micropearl obtains, result shows after tested, nanometer Fe₃O₄Coated hollow glass bead is even, binding strength good, has superparamagnetism, and saturation magnetization reaches 13.12emug^-1; The rare earth doped TiO that makes₂Absorb light generation red shift, under ultraviolet ray and visible ray irradiation, photocatalytic activity improves, and saturation magnetization is at 8.73emug^-1, under low-intensity magnetic field condition, be convenient to reclaim, recycle stability high, reuse 10 photocatalytic activities and reduce less than 10%.

Brief description of the drawings

Fig. 1 is the stereoscan photograph of the common hollow glass micropearl processed without preparation method of the present invention;

Fig. 2 adopts preparation method of the present invention to hollow glass micropearl coated magnetic nanometer Fe₃O₄After stereoscan photograph;

Fig. 3 adopts preparation method of the present invention to the coated flower ball-shaped SiO of hollow glass micropearl₂The stereoscan photograph in intermediate layer;

Fig. 4 adopts preparation method of the present invention to the coated rare-earth europium dopen Nano TiO of hollow glass micropearl₂After stereoscan photograph;

Fig. 5 is the B-H loop that adopts the hollow glass micropearl prepared in different phase of preparation method of the present invention;

Fig. 6 adopts the rare-earth europium doped magnetic photocatalysis hollow glass micropearl prepared of preparation method of the present invention and the X-ray diffraction spectrogram of doped magnetic photocatalysis hollow glass micropearl not;

Fig. 7 adopts rare-earth europium doping prepared by the inventive method and the ln (C of doped magnetic photocatalysis hollow glass micropearl ultraviolet irradiation photocatalytic degradation methylene blue solution not₀/C_t)-t curve.

Detailed description of the invention

Below in conjunction with the drawings and specific embodiments, the present invention is described in detail.

Rare-earth europium dopen Nano TiO of the present invention₂The preparation method of hollow glass micropearl, first uses ferric sulfate, sodium thiosulfate, urea, PEG-6000 in hollow glass micropearl surface coated magnetic nanometer Fe₃O₄, then use ethyl orthosilicate coated Si O₂Intermediate layer, is finally used titanium sulfate, urea, polyvinylpyrrolidone and europium nitrate to be coated europium dopen Nano TiO₂Photochemical catalyst, prepares a kind of rare earth doped magnetic photocatalytic hollow glass micropearl of nucleocapsid structure that has; Specifically implement according to following steps:

Step 1, to hollow glass micropearl clean, flotation and pretreatment:

Although the compression strength of hollow glass micropearl is higher, but in producing, store and dividing process of assembling, likely there is breakage or introduce impurity, therefore be necessary to hollow glass micropearl clean, flotation also will carry out pretreatment to clean hollow glass micropearl, to facilitate modification below;

Step 2, preparation coupling modification mixed solution, utilize coupling modification mixed solution to carry out rich surface amination processing to the hollow glass micropearl obtaining through step 1:

Step 3, the amidized hollow glass micropearl of the rich surface obtaining through step 2 is carried out to clad nano Fe₃O₄Modification:

Step 4, to the clad nano Fe obtaining through step 3₃O₄Hollow glass micropearl carries out coated Si O₂Process:

Step 4.3, take the clad nano Fe obtaining through step 3₃O₄Hollow glass micropearl, measure in step 4.1 mixed solution of preparation, by every gram of clad nano Fe₃O₄Hollow glass micropearl get 0.025L～0.05L mixed solution, by the clad nano Fe taking₃O₄Hollow glass micropearl adds in the mixed solution measuring, and under 40 DEG C～60 DEG C conditions, stirs 5min～10min with the speed of 200r/min～500r/min, then dropwise adds the ethyl orthosilicate alcohol mixed solution in step 4.2, by every gram of clad nano Fe₃O₄Hollow glass micropearl is got 0.02L～0.04L ethyl orthosilicate alcohol mixed solution, continue to stir 6h～12h, reaction finish the rear floatability of utilizing hollow glass micropearl by its with react remaining fluid separation applications afterwards, the hollow glass micropearl of separating is first used to washed with de-ionized water 1 time～3 times, then use absolute ethanol washing 1 time～3 times, again in 75 DEG C～85 DEG C vacuum drying 1h～3h, finally bake 5min～10min in 140 DEG C～160 DEG C, obtain coated flower ball-shaped SiO₂Magnetic hollow glass microballoon.

Step 5, by the coated flower ball-shaped SiO obtaining through step 4₂Magnetic hollow glass microballoon be coated rare-earth europium dopen Nano TiO₂Process rare-earth europium dopen Nano TiO₂Magnetic photocatalytic hollow glass micropearl:

Step 5.3, by sealing after stainless steel cauldron be placed in homogeneous reactor, be warming up to 110 DEG C～160 DEG C with 1 DEG C/min～2 DEG C/min speed, isothermal reaction 2h～5h, after stainless steel cauldron is naturally cooling, utilize the floatation characteristic of hollow glass micropearl that reacted hollow glass micropearl is separated with remaining solution after reaction, the hollow glass micropearl of separating is first used to deionized water rinsing 1 time～3 times, absolute ethanol washing 1～3 time again, finally, in 60 DEG C～80 DEG C vacuum dryings, obtain rare-earth europium dopen Nano TiO₂Hollow glass micropearl, this rare-earth europium dopen Nano TiO₂Hollow glass micropearl is the magnetic photocatalytic hollow glass micropearl that europium doping has nucleocapsid structure.

Fig. 1 is the stereoscan photograph of coated hollow glass bead not, and as seen from Figure 1, the surface of unmodified hollow glass micropearl is very clean, does not have other materials to adhere to; Fig. 2 is hollow glass micropearl clad nano Fe₃O₄After stereoscan photograph, as seen from Figure 2, hollow glass micropearl has been coated the granular material of one deck, show through high power electromicroscopic photograph, this clad is that the spheric granules that is 40nm left and right by average grain diameter forms, and particle size distribution is even, and bead surface is coated complete; Fig. 3 is the coated flower ball-shaped SiO of hollow glass micropearl₂The stereoscan photograph in intermediate layer, as seen from Figure 3, coated Si O₂After hollow glass micropearl surface become very coarse, be flower ball-shaped, through high power electromicroscopic photograph show, these flower ball-shaped projections are made up of particle diameter 200nm particle, outward appearance presents " ridge-mountain valley " special appearance; Fig. 4 is the coated rare-earth europium dopen Nano TiO of hollow glass micropearl₂After stereoscan photograph, as seen from Figure 4, coated europium doped Ti O₂After " ridge-mountain valley " pattern become fuzzyyer, relatively smooth, surperficial most of groove is filled up by some tiny particles, through high power electromicroscopic photograph show, surface formed by the less particle of particle diameter.

Fig. 5 is the B-H loop of the hollow glass micropearl prepared of different phase, as seen from Figure 5, and clad nano Fe₃O₄After hollow glass micropearl magnetic the strongest, saturation magnetization is 13.12emu/g; Coated Si O₂After the saturation magnetization of hollow glass micropearl drop to some extent 7.37emu/g, this is because coated Si O₂Rear hollow glass micropearl quality obviously increases, magnetic Nano Fe₃O₄Due to proportion reduces; Coated europium dopen Nano TiO again₂After the saturation magnetization of hollow glass micropearl be increased to 8.73emug^-1, this is that hysteresis is obvious because rare-earth europium element has certain magnetic.

Fig. 6 is the X-ray diffraction spectrogram of the hollow glass micropearl prepared of different phase. Test result shows, clad nano Fe₃O₄Rear hollow glass micropearl at 30.2 °, 2 θ angle, 35.6 °, 43.3 °, 57.2 ° and 63.0 ° locate to have occurred obvious diffraction maximum, respectively corresponding (220), (311), (400), (511) and (404) crystal face, JCPDSNo.03-0863 is consistent with standard diagram, is inverse spinel magnetic iron ore structure; Coated Si O₂After hollow glass micropearl diffraction maximum there is no significant change; Coated europium dopen Nano TiO again₂Hollow glass micropearl at 25.3 °, 2 θ angle, 37.0 °, 48.2 °, 52.8 ° and 54.9 ° locate to have occurred anatase TiO₂Diffraction maximum, respectively corresponding (101), (004), (200), (105) and (211) crystal face, JCPDSNo.21-1167 is consistent with standard diagram.

Fig. 7 is not doping and the rare-earth europium dopen Nano TiO that adopts the inventive method to prepare₂Ln (the C of magnetic photocatalytic hollow glass micropearl photocatalytic degradation methylene blue under ultraviolet ray is irradiated₀/C_t)-t curve. As seen from Figure 7, the europium doped Ti O that the inventive method obtains₂The photocatalysis effect of nucleocapsid structure hollow glass micropearl is obviously better than not doped Ti O₂Nucleocapsid structure hollow glass micropearl.

Being determined as follows of photocatalytic degradation methylene blue dye activity:

Take 0.03g hollow glass micropearl, added to 50mL, mass concentration is in the methylene blue solution of 5mg/L, being placed in darkroom 90min reaches after adsorption equilibrium, the glass culture dish (diameter 8cm) that methylene blue solution is housed is placed on to quartz ultraviolet lamp (power 40W, dominant wavelength 254nm) under carry out irradiation, light source distance liquid level 10cm, measure the absorbance A of solution at 664nm place every 1h with UV-1600 type ultraviolet-uisible spectrophotometer, according to methylene blue solution absorbance and concentration standard curve (regression equation: A=0.0012+0.0958C, coefficient R=0.9996), calculate the concentration of methylene blue solution, draw ln (c₀/c_t)-t curve, and according to the degradation rate D of formula (1) calculating methylene blue dye.

D = \frac{C_{0} - C_{t}}{C_{0}} \times 100 % - - - (1);

Wherein C₀The initial concentration of the saturated rear methylene blue solution of absorption, C_tBe the concentration of methylene blue solution after irradiation certain hour, t is the ultraviolet irradiation time.

Measure the hysteresis curve of coated hollow glass bead with VSM multifunction vibration sample magnetometer (QuantumDesign company of the U.S.), calculate saturation magnetization.

Beneficial effect of the present invention place is described from principle aspect:

1. the present invention is by controlling coupling agent consumption, and reaction temperature and time, regulator solution pH value, makes hollow glass micropearl surface grafting amino as much as possible, is beneficial to clad nano Fe₃O₄Particle, improves binding strength; After silane resin acceptor kh-550 consumption is pretreatment, 10%～30% of hollow glass micropearl quality time, coupling modified effect is better; After silane resin acceptor kh-550 consumption is lower than pretreatment, when hollow glass micropearl quality 10%, hollow glass micropearl surface grafting amount is little, and coupling modified effect is poor; After silane resin acceptor kh-550 consumption is higher than pretreatment 30% of hollow glass micropearl quality time, poly-reaction in occurring between the large molecule of coupling agent, coupling modified effect is poor, causes waste.

Coupling reaction temperature affects the hydrolysis rate of silane resin acceptor kh-550, and temperature is higher, and coupling agent hydrolysis rate is just faster. In the time that temperature is controlled at 20～40 DEG C, can obtain good modified effect; When temperature during lower than 20 DEG C hydrolysis rate slower, the reaction time is long, production efficiency is low; When temperature is during higher than 40 DEG C, hydrolysis rate is too fast, and the silane coupler after hydrolysis is not able to do in time, with bead surface hydroxy combining, self condensation just occurs, and causes coupling agent waste.

Along with the prolongation of coupling reaction time, coupling agent increases gradually at bead surface covering amount; In the time that the reaction time is less than 8h, coupling agent can not be fully used; In the time that the reaction time is greater than 12h, coupling agent fundamental reaction is complete, then time expand does not improve modified effect.

The pH value of coupling modification mixed solution affects the association rate of Si-OH and the silane resin acceptor kh-550 on hollow glass micropearl surface: when the pH value of coupling modification mixed solution is 3.5～5.5 time, silane resin acceptor kh-550 is combined well with hollow glass micropearl surface Si-OH, can make full use of silane resin acceptor kh-550, Reaction time shorten; When the pH value of coupling modification mixed solution is less than 3.5 or while being greater than 5.5, coupling modified effect all declines.

2. the consumption of ferric sulfate, sodium thiosulfate and urea, ratio, the loading ratio of hollow glass micropearl, dosage of surfactant, the factors such as reaction temperature and time, all affect nanometer Fe₃O₄Purity, crystallization degree, pattern and the particle size of clad; When the molar concentration of ferric sulfate is during at 0.015mol/L～0.05mol/L, hollow glass micropearl surface can be coated certain thickness magnetic Nano Fe₃O₄Film, particle generation agglomeration obviously reduces, and can not deposit too many nano particle in solution simultaneously, is combined firmly with hollow glass micropearl; In the time that the molar concentration of ferric sulfate is less than 0.015mol/L, Fe in solution³⁺Very little, hollow glass micropearl surface is coated imperfect for ion; In the time that the molar concentration of ferric sulfate is greater than 0.05mol/L, Fe³⁺Concentration is excessive, the too thick hollow glass micropearl precipitation that easily causes of clad, and nano particle also easily comes off.

Urea provides an alkaline reaction environment, when ferric sulfate and urea mol ratio are during in 1:3～30, can generate magnetic Nano Fe₃O₄; In the time that ferric sulfate and urea mol ratio are greater than 1:30, product color is slightly partially red; In the time that ferric sulfate and urea mol ratio are less than 1:3, product color is partially blue.

In the time that ferric sulfate and sodium thiosulfate mol ratio are 1:0.25～1.5, can generate magnetic Nano Fe₃O₄, hollow glass micropearl surface is coated continuous, complete, and nano particle is combined with hollow glass micropearl firmly; In the time that ferric sulfate and sodium thiosulfate mol ratio are greater than 1:1.5, Fe³⁺Consumption reduces relatively, contains a large amount of sulphur simple substance in product, not only can reduce nanometer Fe₃O₄Purity, and increased the weight of hollow glass micropearl; In the time that ferric sulfate and sodium thiosulfate mol ratio are less than 1:0.25, the Fe that reduction obtains²⁺Measure very little the Fe of generation₃O₄Complicated component, may contain part Fe₂O₃, crystallization degree is low, and hollow glass micropearl surface is coated imperfect, and color is yellowish-brown or khaki.

Reaction temperature and reaction time major effect Fe₃O₄Crystallization degree, crystal morphology and size: when reaction temperature is during at 120 DEG C～180 DEG C, can generate magnetic Nano Fe₃O₄; When reaction temperature is during lower than 120 DEG C, generate taupe or celadon material, there is no magnetic; When reaction temperature is during higher than 180 DEG C, nanometer particle size enlarges markedly, and high temperature also can cause silane resin acceptor kh-550 to decompose, and causes covering amount to reduce, and instrument security reduces; In the time that the reaction time is controlled at 3h～8h, can be in hollow glass micropearl coated with uniform one deck nanometer Fe₃O₄Film; In the time that the reaction time is less than 3h, nano particle crystallization degree reduces, with hollow glass micropearl binding strength variation; In the time that the reaction time is greater than 8h, nano particle is reunited, and particle diameter obviously increases, hollow glass micropearl rough surface injustice, and particle easily comes off.

The kind of surfactant and consumption, not only affect the size of nanocrystal, and proterties and coated state to product also has a significant impact. Use surfactant polyethylene-1000 can obviously improve the coated pattern of bead surface. When ferric sulfate and PEG-6000 mol ratio are during in 1:0.5～6, hollow glass micropearl surface is coated complete, even; In the time that ferric sulfate and PEG-6000 mol ratio are less than 1:0.5, nanocrystalline grain size increases, and covered effect is bad; In the time that ferric sulfate and PEG-6000 mol ratio are greater than 1:6, the magnetic of product reduces or disappears.

The loading of hollow glass micropearl is than the utilization ratio and the covered effect that directly affect product. In the time that hollow glass micropearl consumption is 10g/L～20g/L, microballon color is black, and sedimentation does not occur, and cladding ratio is more even; In the time that hollow glass micropearl consumption is less than 10g/L, total concentration of iron is excessive, and clad is too thick, and hollow glass micropearl major part is deposited in container bottom and can not be floating; In the time that hollow glass micropearl consumption is greater than 20g/L, clad attenuation, color shoals, coated inhomogeneous.

3. hollow glass micropearl coated Si O₂In process, reaction temperature, reaction time and loading ratio affect SiO₂The pattern of clad and bonding state. When reaction temperature is at 40 DEG C～60 DEG C, when reaction time 6h～12h, hollow glass micropearl surface can form the clad that certain thickness outward appearance is flower ball-shaped, can be by Fe₃O₄With TiO₂Keep apart; When reaction temperature is during lower than 40 DEG C, reaction can not normally be carried out; When reaction temperature is during higher than 60 DEG C, ethanol rate of volatilization is obviously accelerated, and causes solvent waste, and reacting material concentration increases. In the time that the reaction time is less than 6h, the SiO of generation₂On the low side, coated imperfect, easily come off; In the time that the reaction time exceedes 12h, clad is blocked up. When hollow glass micropearl useful load is during at 20g/L～40g/L, covered effect is better, and outward appearance is flower ball-shaped; In the time that useful load is less than 20g/L, clad is blocked up, and smooth surface loses flower ball-shaped structure, easily precipitates; In the time that useful load is greater than 40g/L, clad is too thin, can not form complete clad.

4. the rare earth doped atom that can make rare earth element directly enters nano-TiO₂Crystal structure inside, because doping is very small, to nano-TiO₂Coated hollow glass bead surface topography, color and appearance effects are little, major effect TiO₂Photocatalytic activity. When titanium sulfate and europium nitrate mol ratio are during in 1:0.0005～0.01, europium dopen Nano TiO₂The photocatalytic activity of coated hollow glass bead significantly improves; In the time that titanium sulfate and europium nitrate mol ratio are less than 1:0.0005 or are greater than 1:0.01, photocatalytic activity changes not obvious or photocatalytic activity and disappears.

Embodiment 1

Take the hollow glass micropearl of 10g, add 1L, temperature to and be in the running water of 40 DEG C, stir 5min with 100rpm speed, then running water is warming up to 70 DEG C, constant temperature immersion treatment 1h, allow it leave standstill until naturally cool to room temperature, after hollow glass micropearl layering, the hollow glass micropearl that swims in running water liquid level upper strata is pulled out, separately take from water and rinse 1 time, complete flotation and cleaning to hollow glass micropearl, obtain clean hollow glass micropearl; The NaOH of 10g is added in the deionized water of 1L to the sodium hydroxide solution that preparation mass concentration is 10g/L; Getting the clean hollow glass micropearl floatingly selecting, to add temperature to be that 40 DEG C, mass concentration are in 10g/L sodium hydroxide solution, with the hollow glass micropearl 10min in the speed stir process sodium hydroxide solution of 100rpm, then hollow glass micropearl is fished for out, wash the hollow glass micropearl of fishing for out by clean deionized water, until the pH value of the deionized water after washing is neutrality, complete the pretreatment to hollow glass micropearl; By the hollow glass micropearl drying 4h under 110 DEG C of conditions after filtering;

Measure respectively absolute ethyl alcohol and deionized water for 1:9 by volume, absolute ethyl alcohol and deionized water are hybridly prepared into the ethanolic solution of 1L, take the pretreated hollow glass micropearl that drying is crossed, take aminopropyl triethoxysilane KH-550 coupling agent according to 10% of this hollow glass micropearl quality, aminopropyl triethoxysilane KH-550 coupling agent is dropwise added in the ethanolic solution of preparation, first stir with the speed of 100rpm, form mixed solution, then regulating the pH value of mixed solution with glacial acetic acid is 3.5, obtains coupling modification mixed solution; Pretreated hollow glass micropearl is added in coupling modification mixed solution, speed with 100rpm stirs, immersion treatment 12h under 20 DEG C of conditions, carry out after vacuum filtration, hollow glass micropearl after coupling modification is separated from coupling modification mixed solution, the hollow glass micropearl after coupling modification is cleaned 3 times with absolute ethyl alcohol; Come dispersed the hollow glass micropearl after coupling modification, be placed under the ultraviolet lamp that dominant wavelength is 365nm and irradiate 60min, then the hollow glass micropearl irradiating through ultraviolet lamp is positioned over to 70 DEG C of preliminary drying 4h, then be positioned over 110 DEG C and bake 3min;

Get respectively ferric sulfate, sodium thiosulfate, urea and PEG-6000 for 1:0.25:3:0.5 in molar ratio, in the deionized water that first ferric sulfate to be added to temperature and be 30 DEG C, volume be 1L, adopt sonic oscillation 5min, being dissolved in deionized water completely until ferric sulfate is after yellow transparent solution, add sodium thiosulfate and fully stir, solution colour becomes pitch black purple, continue to stir and become achromaticity and clarification, now add urea, PEG-6000, continue to stir until solution is white in color colloidal suspension, prepare modified solution; The amidized hollow glass micropearl of rich surface of getting 10g adds in modified solution, and amidized rich surface hollow glass micropearl is transferred to together with modified solution in the stainless steel cauldron of inner liner polytetrafluoroethylene; After sealing stainless steel cauldron, stainless steel cauldron is placed in to homogeneous reactor, be warming up to 120 DEG C with 1 DEG C/min speed, isothermal reaction 3h, the naturally cooling rear taking-up of question response still is the hollow glass micropearl of black, utilize the floatability of hollow glass micropearl that hollow glass micropearl is separated with remaining waste liquid after reaction, obtain the hollow glass micropearl after modification; Hollow glass micropearl after modification is first used to deionized water rinsing 1 time, then use absolute ethanol washing 1 time, finally, in 60 DEG C of vacuum drying 12h, obtain clad nano Fe₃O₄Hollow glass micropearl;

Be that 1:5 measures respectively deionized water and absolute ethyl alcohol according to volume ratio, the deionized water measuring is mixed with absolute ethyl alcohol, make ethanolic solution, re-using mass percent concentration and be 25% ammoniacal liquor, to regulate the pH value of ethanolic solution be 8, formation mixed solution; Measure respectively absolute ethyl alcohol and ethyl orthosilicate for 1:1.75 by volume, the absolute ethyl alcohol measuring is mixed with ethyl orthosilicate, make ethyl orthosilicate alcohol mixed solution; Take clad nano Fe₃O₄Hollow glass micropearl, by every gram of clad nano Fe₃O₄Hollow glass micropearl is got the mixed solution of 0.05L, by clad nano Fe₃O₄Hollow glass micropearl adds in mixed solution, under 40 DEG C of conditions, stirs 5min with the speed of 200r/min, then dropwise adds ethyl orthosilicate alcohol mixed solution, by every gram of clad nano Fe₃O₄Hollow glass micropearl is got 0.02L ethyl orthosilicate alcohol mixed solution, continue to stir 6h, reaction finish the rear floatability of utilizing hollow glass micropearl by its with react remaining fluid separation applications afterwards, by the hollow glass micropearl of separating washed with de-ionized water 1 time, with absolute ethanol washing 1 time, in 80 DEG C of vacuum drying 1h, 150 DEG C bake 5min, obtain coated flower ball-shaped SiO₂Magnetic hollow glass microballoon;

Get respectively titanium sulfate, urea, polyvinylpyrrolidone and europium nitrate for 1:0.2:0.0004:0.0005 in molar ratio, it is 60 DEG C that titanium sulfate is dissolved in to temperature, volume is in the deionized water of 1L, sonic oscillation 5min, then add successively urea, polyvinylpyrrolidone and europium nitrate, fully stir it is dissolved completely, make modified solution, then add coated flower ball-shaped SiO₂Magnetic hollow glass microballoon, hollow glass micropearl is transferred to together with modified solution in the stainless steel cauldron of inner liner polytetrafluoroethylene, after sealed reactor, reactor is placed in to homogeneous reactor, be warming up to 110 DEG C with 1 DEG C/min speed, isothermal reaction 2h, the reacted hollow glass micropearl of the naturally cooling rear taking-up of question response still, utilize the floatation characteristic of hollow glass micropearl that reacted hollow glass micropearl is separated with remaining solution after reaction, with deionized water rinsing 1 time, absolute ethanol washing 1 time, 60 DEG C of vacuum dryings, obtain rare-earth europium dopen Nano TiO₂The preparation method of hollow glass micropearl.

Photocatalytic degradation methylene blue dye test result shows, by 0.03g rare-earth europium dopen Nano TiO₂Hollow glass micropearl adds in the methylene blue solution of 50mL, mass concentration 5mg/L, be placed in irradiation under the ultraviolet lamp that is placed on 40W, dominant wavelength 254nm after the 90min of darkroom, light source distance liquid level 10cm, through 8h ultraviolet irradiation, methylene blue dye photocatalytic activity is 87.5%. Determine rare-earth europium dopen Nano TiO with VSM multifunction vibration sample magnetic strength instrumentation₂The B-H loop of hollow glass micropearl, calculating saturation magnetization is 1.86emu/g.

Embodiment 2

Take the hollow glass micropearl of 20g, add 1L, temperature to and be in the running water of 70 DEG C, stir 10min with 200rpm speed, then running water is warming up to 90 DEG C, constant temperature immersion treatment 1h, allow it leave standstill until naturally cool to room temperature, after hollow glass micropearl layering, the hollow glass micropearl that swims in running water liquid level upper strata is pulled out, separately take from water and rinse 3 times, complete flotation and cleaning to hollow glass micropearl, obtain clean hollow glass micropearl; The NaOH of 20g is added in the deionized water of 1L to the sodium hydroxide solution that preparation mass concentration is 20g/L; Getting clean hollow glass micropearl, to add temperature to be that 80 DEG C, mass concentration are in 10g/L sodium hydroxide solution, with the hollow glass micropearl 30min in the speed stir process sodium hydroxide solution of 200rpm, then hollow glass micropearl is fished for out, wash the hollow glass micropearl of fishing for out by clean deionized water, until the pH value of the deionized water after washing is neutrality, complete the pretreatment to hollow glass micropearl; By the hollow glass micropearl drying 2h under 150 DEG C of conditions after filtering;

Measure respectively absolute ethyl alcohol and deionized water for 1:8 by volume, absolute ethyl alcohol and deionized water are hybridly prepared into the ethanolic solution of 1L, take the pretreated hollow glass micropearl that drying is crossed, according to 30% of the hollow glass micropearl quality obtaining, take silane KH-550 coupling agent, silane KH-550 coupling agent is dropwise added in absolute ethyl alcohol deionized water mixed solution, first stir with the speed of 200rpm, then regulating the pH value of mixed solution with glacial acetic acid is 5.5, pretreated hollow glass micropearl is added in coupling modification mixed solution, stir with 200rpm speed, immersion treatment 8h under 40 DEG C of conditions, carry out after vacuum filtration, hollow glass micropearl after coupling modification is separated from coupling modification mixed solution, hollow glass micropearl after coupling modification is cleaned 3 times with absolute ethyl alcohol, come dispersed the hollow glass micropearl after coupling modification, be placed under the ultraviolet lamp that dominant wavelength is 365nm and irradiate 30min, then the hollow glass micropearl irradiating through ultraviolet lamp is positioned over to 90 DEG C of preliminary drying 2h, be positioned over again 130 DEG C and bake 1min,

Get respectively ferric sulfate, sodium thiosulfate, urea and PEG-6000 for 1:1.5:30:6 in molar ratio, in the deionized water that first ferric sulfate to be added to temperature and be 60 DEG C, volume be 1L, adopt sonic oscillation 10min, being dissolved in deionized water completely until ferric sulfate is after yellow transparent solution, add sodium thiosulfate and fully stir, solution colour becomes pitch black purple, continue to stir and become achromaticity and clarification, now add urea, PEG-6000, continue to stir until solution is white in color colloidal suspension, prepare modified solution; The amidized hollow glass micropearl of rich surface of getting 20g adds in modified solution, and amidized rich surface hollow glass micropearl is transferred to together with modified solution in the stainless steel cauldron of inner liner polytetrafluoroethylene; After sealing stainless steel cauldron, stainless steel cauldron is placed in to homogeneous reactor, be warming up to 180 DEG C with 2 DEG C/min speed, isothermal reaction 8h, the naturally cooling rear taking-up of question response still is the hollow glass micropearl of black, utilize the floatability of hollow glass micropearl that hollow glass micropearl is separated with remaining waste liquid after reaction, obtain the hollow glass micropearl after modification; Hollow glass micropearl after modification is first used to deionized water rinsing 3 times, then use absolute ethanol washing 3 times, finally, in 80 DEG C of vacuum drying 24h, obtain clad nano Fe₃O₄Hollow glass micropearl;

Be that 1:4 measures respectively deionized water and absolute ethyl alcohol according to volume ratio, the deionized water measuring is mixed with absolute ethyl alcohol, make ethanolic solution, re-using mass percent concentration and be 24% ammoniacal liquor, to regulate the pH value of ethanolic solution be 7.8, formation mixed solution; Measure respectively absolute ethyl alcohol and ethyl orthosilicate for 1:1.7 by volume, the absolute ethyl alcohol measuring is mixed with ethyl orthosilicate, make ethyl orthosilicate alcohol mixed solution; Take clad nano Fe₃O₄Hollow glass micropearl, by every gram of clad nano Fe₃O₄Hollow glass micropearl is got the mixed solution of 0.025L, by clad nano Fe₃O₄Hollow glass micropearl adds in mixed solution, under 60 DEG C of conditions, stirs 10min with the speed of 500r/min, then dropwise adds ethyl orthosilicate alcohol mixed solution, by every gram of clad nano Fe₃O₄Hollow glass micropearl is got 0.04L ethyl orthosilicate alcohol mixed solution, continue to stir 12h, reaction finish the rear floatability of utilizing hollow glass micropearl by its with react remaining fluid separation applications afterwards, by the hollow glass micropearl of separating washed with de-ionized water 3 times, with absolute ethanol washing 3 times, in 80 DEG C of vacuum drying 1h, bake 10min in 150 DEG C, obtain coated flower ball-shaped SiO₂Magnetic hollow glass microballoon;

Get respectively titanium sulfate, urea, polyvinylpyrrolidone and europium nitrate for 1:20:0.006:0.01 in molar ratio, it is 60 DEG C that titanium sulfate is dissolved in to temperature, volume is in the deionized water of 1L, sonic oscillation 10min, then add successively urea, polyvinylpyrrolidone and europium nitrate, fully stir it is fully dissolved, make modified solution, then add coated flower ball-shaped SiO₂Magnetic hollow glass microballoon, hollow glass micropearl is transferred to together with modified solution in the stainless steel cauldron of inner liner polytetrafluoroethylene, after sealed reactor, reactor is placed in to homogeneous reactor, be warming up to 160 DEG C with 2 DEG C/min speed, isothermal reaction 5h, the reacted hollow glass micropearl of the naturally cooling rear taking-up of question response still, utilize the floatation characteristic of hollow glass micropearl that reacted hollow glass micropearl is separated with remaining solution after reaction, with deionized water rinsing 3 times, absolute ethanol washing 3 times, in 80 DEG C of vacuum dryings, obtain rare-earth europium dopen Nano TiO₂Hollow glass micropearl.

Photocatalytic degradation methylene blue dye test result shows, by 0.03g rare-earth europium dopen Nano TiO₂Hollow glass micropearl adds in the methylene blue solution of 50mL, mass concentration 5mg/L, be placed in irradiation under the ultraviolet lamp that is placed on 40W, dominant wavelength 254nm after the 90min of darkroom, light source distance liquid level 10cm, through 8h ultraviolet irradiation, methylene blue dye photocatalytic activity is 99.2%. Determine rare-earth europium dopen Nano TiO with VSM multifunction vibration sample magnetic strength instrumentation₂The B-H loop of hollow glass micropearl, calculating saturation magnetization is 8.73emu/g.

Embodiment 3

Take the hollow glass micropearl of 15g, add 1L, temperature to and be in the running water of 45 DEG C, stir 7min with 150rpm speed, then running water is warming up to 80 DEG C, constant temperature immersion treatment 1h, allow it leave standstill until naturally cool to room temperature, after hollow glass micropearl layering, the hollow glass micropearl that swims in running water liquid level upper strata is pulled out, separately take from water and rinse 2 times, complete flotation and cleaning to hollow glass micropearl, obtain clean hollow glass micropearl; The NaOH of 15g is added in the deionized water of 1L to the sodium hydroxide solution that preparation mass concentration is 15g/L; Getting the clean hollow glass micropearl floatingly selecting, to add temperature to be that 60 DEG C, mass concentration are in 15g/L sodium hydroxide solution, with the hollow glass micropearl 20min in the speed stir process sodium hydroxide solution of 150rpm, then hollow glass micropearl is fished for out, wash the hollow glass micropearl of fishing for out by clean deionized water, until the pH value of the deionized water after washing is neutrality, complete the pretreatment to hollow glass micropearl; By the hollow glass micropearl drying 3h under 130 DEG C of conditions after filtering;

Measure respectively absolute ethyl alcohol and deionized water according to volume ratio 1:10, absolute ethyl alcohol and deionized water are hybridly prepared into the ethanolic solution of 1L, get pretreated hollow glass micropearl, according to 20% of the hollow glass micropearl quality obtaining, take aminopropyl triethoxysilane KH-550 coupling agent, aminopropyl triethoxysilane KH-550 coupling agent is dropwise added in the ethanolic solution of preparation, first stir with 150rpm speed, form mixed solution, then regulating the pH value of mixed solution with glacial acetic acid is 4.5, obtains coupling modification mixed solution; Pretreated hollow glass micropearl is added in coupling modification mixed solution, stir with 150rpm speed, immersion treatment 12h under 30 DEG C of conditions, carry out after vacuum filtration, hollow glass micropearl after coupling modification is separated from coupling modification mixed solution, the hollow glass micropearl after coupling modification is cleaned 2 times with absolute ethyl alcohol; Come dispersed the hollow glass micropearl after coupling modification, be placed under the ultraviolet lamp that dominant wavelength is 365nm and irradiate 40min, 80 DEG C of preliminary drying 3h, 120 DEG C bake 2min;

Get respectively ferric sulfate, sodium thiosulfate, urea and PEG-6000 for 1:0.8:15:3 in molar ratio, in the deionized water that first ferric sulfate to be added to temperature and be 45 DEG C, volume be 1L, adopt sonic oscillation 7min, being dissolved in deionized water completely until ferric sulfate is after yellow transparent solution, add sodium thiosulfate and fully stir, solution colour becomes pitch black purple, continue to stir and become achromaticity and clarification, now add urea, PEG-6000, continue to stir until solution is white in color colloidal suspension, prepare modified solution; The amidized hollow glass micropearl of rich surface of getting 15g adds in modified solution, and amidized rich surface hollow glass micropearl is transferred to together with modified solution in the stainless steel cauldron of inner liner polytetrafluoroethylene; After sealing stainless steel cauldron, stainless steel cauldron is placed in to homogeneous reactor, be warming up to 160 DEG C with 1.5 DEG C/min speed, isothermal reaction 5h, the naturally cooling rear taking-up of question response still is the hollow glass micropearl of black, utilize the floatability of hollow glass micropearl that hollow glass micropearl is separated with remaining waste liquid after reaction, obtain the hollow glass micropearl after modification; Hollow glass micropearl after modification is first used to deionized water rinsing 2 times, then use absolute ethanol washing 2 times, finally, in 70 DEG C of vacuum drying 18h, obtain clad nano Fe₃O₄Hollow glass micropearl;

Be that 1:6 measures respectively deionized water and absolute ethyl alcohol according to volume ratio, the deionized water measuring is mixed with absolute ethyl alcohol, make ethanolic solution, re-using mass percent concentration and be 26% ammoniacal liquor, to regulate the pH value of ethanolic solution be 8.2, formation mixed solution; Measure respectively absolute ethyl alcohol and ethyl orthosilicate for 1:1.8 by volume, the absolute ethyl alcohol measuring is mixed with ethyl orthosilicate, make ethyl orthosilicate alcohol mixed solution; Take clad nano Fe₃O₄Hollow glass micropearl, by every gram of clad nano Fe₃O₄Hollow glass micropearl is got the mixed solution of 0.03L, by clad nano Fe₃O₄Hollow glass micropearl adds in mixed solution, under 50 DEG C of conditions, stirs 5min with the speed of 400r/min, then dropwise adds ethyl orthosilicate alcohol mixed solution, by every gram of clad nano Fe₃O₄Hollow glass micropearl is got 0.03L ethyl orthosilicate alcohol mixed solution, continue to stir 9h, reaction finish the rear floatability of utilizing hollow glass micropearl by its with react remaining fluid separation applications afterwards, by the hollow glass micropearl of separating washed with de-ionized water 2 times, with absolute ethanol washing 2 times, in 80 DEG C of vacuum drying 2h, 150 DEG C bake 8min, obtain coated flower ball-shaped SiO₂Magnetic hollow glass microballoon;

Get respectively titanium sulfate, urea, polyvinylpyrrolidone and europium nitrate for 1:10:0.002:0.005 in molar ratio, it is 60 DEG C that titanium sulfate is dissolved in to temperature, volume is in the deionized water of 1L, sonic oscillation 7min, then add successively urea, polyvinylpyrrolidone and europium nitrate, fully stir it is fully dissolved, make modified solution, then add coated flower ball-shaped SiO₂Magnetic hollow glass microballoon, hollow glass micropearl is transferred to together with modified solution in the stainless steel cauldron of inner liner polytetrafluoroethylene, after sealed reactor, reactor is placed in to homogeneous reactor, be warming up to 140 DEG C with 1.5 DEG C/min speed, isothermal reaction 4h, the reacted hollow glass micropearl of the naturally cooling rear taking-up of question response still, utilize the floatation characteristic of hollow glass micropearl that reacted hollow glass micropearl is separated with remaining solution after reaction, with deionized water rinsing 2 times, absolute ethanol washing 2 times, 70 DEG C of vacuum dryings, obtain rare-earth europium dopen Nano TiO₂Hollow glass micropearl.

Photocatalytic degradation methylene blue dye test result shows, by 0.03g rare-earth europium dopen Nano TiO₂Hollow glass micropearl adds in the methylene blue solution of 50mL, mass concentration 5mg/L, be placed in irradiation under the ultraviolet lamp that is placed on 40W, dominant wavelength 254nm after the 90min of darkroom, light source distance liquid level 10cm, through 8h ultraviolet irradiation, methylene blue dye photocatalytic activity is 92.3%. Determine rare-earth europium dopen Nano TiO with VSM multifunction vibration sample magnetic strength instrumentation₂The B-H loop of hollow glass micropearl, calculating saturation magnetization is 11.46emu/g.

Claims

1. rare-earth europium dopen Nano TiO₂The preparation method of hollow glass micropearl, is characterized in that,Specifically implement according to following steps:

Step 1, to hollow glass micropearl clean, flotation and pretreatment;

Step 2, preparation coupling modification mixed solution, utilize coupling modification mixed solution to through stepRapid 1 hollow glass micropearl obtaining carries out rich surface amination processing, specifically according to following stepsImplement:

Step 2.1, measure respectively absolute ethyl alcohol and deionized water for 1:8～10 by volume,Absolute ethyl alcohol and deionized water are hybridly prepared into ethanolic solution;

Step 2.2, take the hollow glass micropearl obtaining through step 1, measure through step 2.1The ethanolic solution of preparation, the ethanol of getting 0.025L～0.05L by the hollow glass micropearl of every gram is moltenLiquid;

Take silane resin acceptor kh-550, the quality of silane resin acceptor kh-550 is what take10%～30% of hollow glass micropearl quality;

Step 2.3, dropwise add the silane resin acceptor kh-550 taking in step 2.2 to stepIn rapid 2.2 ethanolic solutions that measure, first stir silane with the speed of 100rpm～200rpm evenThe ethanolic solution of connection agent KH-550, forms mixed solution, then regulates mixing molten with glacial acetic acidThe pH value of liquid is 3.5～5.5, obtains coupling modification mixed solution;

Step 2.4, the hollow glass micropearl taking through step 2.2 is added to through step 2.3To coupling modification mixed solution in, stir coupling modification with the speed of 100rpm～200rpmHollow glass micropearl in mixed solution, then by coupling modification mixed solution be warming up to 20 DEG C～After 40 DEG C, constant temperature leaves standstill 8h～12h, then carries out vacuum filtration processing, by after coupling modificationHollow glass micropearl is separated from coupling modification mixed solution, obtains the sky after coupling modificationHeart glass microballoon, then cleans 1 by the hollow glass micropearl after coupling modification with absolute ethyl alcoholInferior～3 time;

Step 2.5, will be through dispersed the coming of step 2.4 hollow glass micropearl after treatment,Be placed under the ultraviolet lamp that dominant wavelength is 365nm and irradiate 30min～60min, then will be throughThe hollow glass micropearl that ultraviolet lamp irradiated is positioned under the temperature conditions of 70 DEG C～90 DEG CRow preliminary drying, the preliminary drying time is 2h～4h, then is positioned under the temperature conditions of 110 DEG C～130 DEG CBake 1min～3min, obtain the amidized hollow glass micropearl of rich surface;

Step 3, the amidized hollow glass micropearl of the rich surface obtaining through step 2 is wrappedCover nanometer Fe₃O₄Modification, specifically implement according to following steps:

Step 3.1, get respectively sulfuric acid for 1:0.25～1.5:3～30:0.5～6 in molar ratioIron, sodium thiosulfate, urea and PEG-6000;

First ferric sulfate is added in the deionized water of 30 DEG C～60 DEG C of temperature, be mixed with moleConcentration is the ferrum sulfuricum oxydatum solutum of 0.03mol/L～0.1mol/L, then by the ferric sulfate solution preparingLiquid, through sonic oscillation 5min～10min, treats that ferric sulfate is dissolved in deionized water completely and is thoroughly yellowAfter bright solution, add sodium thiosulfate and fully stir, solution colour becomes pitch black purple, continuesContinuous stirring becomes achromaticity and clarification, now adds urea, PEG-6000, continues to stir straightTo the solution colloidal suspension that is white in color, prepare modified solution;

Step 3.2, take the amidized hollow glass micropearl of the rich surface obtaining through step 2,Measure the modified solution of preparing through step 3.1, micro-by every gram of amidized hollow glass of rich surfacePearl is got the modified solution of 0.05L～0.1L; Amidized rich surface hollow glass micropearl is addedIn modified solution, then by amidized rich surface hollow glass micropearl together with modified solutionBe transferred in the stainless steel cauldron of inner liner polytetrafluoroethylene;

After step 3.3, sealing stainless steel cauldron, stainless steel cauldron is placed in to homogeneous reactionIn device, be warming up to 120 DEG C～180 DEG C with 1 DEG C/min～2 DEG C/min speed, isothermal reaction 3h～8h takes out the hollow glass micropearl that is black after stainless steel cauldron is naturally cooling, utilizes emptyThe floatability of heart glass microballoon separates hollow glass micropearl with remaining waste liquid after reaction, obtainHollow glass micropearl after modification;

Step 3.4, by the hollow glass micropearl after the modification obtaining through step 3.3 first spend fromSub-water rinses 1 time～3 times, then uses absolute ethanol washing 1 time～3 times, finally in 60 DEG C～80 DEG C of vacuum drying 12～24h, obtain clad nano Fe₃O₄Hollow glass micropearl;

Step 4, to the clad nano Fe obtaining through step 3₃O₄Hollow glass micropearl wrapsCover SiO₂Process, specifically implement according to following steps:

Step 4.1, be that 1:4～6 measure respectively deionized water and absolute ethyl alcohol according to volume ratio,The deionized water measuring is mixed with absolute ethyl alcohol, make ethanolic solution, re-use quality hundredDividing the pH value of the ammoniacal liquor adjusting ethanolic solution that specific concentration is 24%～26% is 7.8～8.2, shapeBecome mixed solution;

Step 4.2, by volume for 1:1.7～1.8 measure respectively absolute ethyl alcohol and positive silicic acid secondEster, mixes the absolute ethyl alcohol measuring with ethyl orthosilicate, make ethyl orthosilicate ethanol mixedClose solution;

Step 4.3, take the clad nano Fe obtaining through step 3₃O₄Hollow glass micropearl,Measure the mixed solution of preparation in step 4.1, by every gram of clad nano Fe₃O₄Hollow glassMicroballon is got 0.025L～0.05L mixed solution, by the clad nano Fe taking₃O₄Hollow glassMicroballon adds in the mixed solution measuring, under 40 DEG C～60 DEG C conditions, with 200r/min～The speed of 500r/min stirs 5min～10min, then dropwise adds the positive silicon in step 4.2Acetoacetic ester alcohol mixed solution, by every gram of clad nano Fe₃O₄Hollow glass micropearl get 0.02L～0.04L ethyl orthosilicate alcohol mixed solution, continues to stir 6h～12h, will after reaction finishesHollow glass micropearl with react after remaining fluid separation applications, by the hollow glass micropearl of separatingFirst use washed with de-ionized water 1 time～3 times, then use absolute ethanol washing 1 time～3 times, thenIn 75 DEG C～85 DEG C vacuum drying 1h～3h, finally in 140 DEG C～160 DEG C bake 5min～10min, obtains coated flower ball-shaped SiO₂Magnetic hollow glass microballoon;

Step 5, by the coated flower ball-shaped SiO obtaining through step 4₂Magnetic hollow glass microballoonBe coated rare-earth europium dopen Nano TiO₂Process, obtain rare-earth europium dopen Nano TiO₂MagneticPhotocatalysis hollow glass micropearl, specifically implement according to following steps:

Step 5.1, be 1:0.2～20:0.0004～0.006:0.0005～0.01 in molar ratioGet respectively titanium sulfate, urea, polyvinylpyrrolidone and europium nitrate, titanium sulfate is dissolved inIn the deionized water of 55 DEG C～65 DEG C, through sonic oscillation 5min～10min, then add successivelyUrea, polyvinylpyrrolidone and europium nitrate, fully stir it fully dissolved, and obtains modificationSolution A;

Step 5.2, will obtain coated flower ball-shaped SiO through step 4₂Magnetic hollow glass microballoonAdd in the modified solution A obtaining through step 5.1, by every gram of coated flower ball-shaped SiO₂'sMagnetic hollow glass microballoon adds the modified solution A of 0.025L～0.05L, will be coated bouquetShape SiO₂Magnetic hollow glass microballoon be transferred to liner polytetrafluoro together with modified solution AIn the stainless steel cauldron of ethene, sealing stainless steel cauldron;

Step 5.3, by sealing after stainless steel cauldron be placed in homogeneous reactor, with 1 DEG C/ min～2 DEG C/min speed is warming up to 110 DEG C～160 DEG C, and isothermal reaction 2h～5h, treats stainlessAfter steel reactor is naturally cooling, utilize the floatation characteristic of hollow glass micropearl by reacted hollowGlass microballoon separates with remaining solution after reaction, and the hollow glass micropearl of separating is first usedDeionized water rinsing 1 time～3 times, then absolute ethanol washing 1 time～3 times, finally dry,Obtain rare-earth europium dopen Nano TiO₂Magnetic photocatalytic hollow glass micropearl.

2. rare-earth europium dopen Nano TiO according to claim 1₂The system of hollow glass micropearlPreparation Method, is characterized in that, described step 1 is specifically implemented according to following steps:

Step 1.1, get hollow glass micropearl and running water respectively, first by the temperature liter of running waterTemperature, to 35 DEG C～45 DEG C, is then added hollow glass micropearl in running water to, by every liter certainlyIn water, add the hollow glass micropearl of 10g～20g, with the speed of 100rpm～200rpmStir the hollow glass micropearl 5min～10min in running water, then the temperature of running water is risen to70 DEG C～90 DEG C, constant temperature soaks hollow glass micropearl 50min～70min, leaves standstill until natureBe cooled to room temperature, after hollow glass micropearl layering by the hollow glass swimming on running water liquid levelGlass microballon is fished for out, separately gets clean running water and rinses the hollow glass micropearl 1 of fishing for outInferior～3 time, drain deionized water, complete flotation and cleaning to hollow glass micropearl, obtainClean hollow glass micropearl;

Step 1.2, take respectively for 1:0.8～1.2 obtain through step 1.1 clean in mass ratioClean hollow glass micropearl, NaOH, add the NaOH taking in deionized water to,Be mixed with 10g/L～20g/L sodium hydroxide solution;

Step 1.3, first sodium hydroxide solution that step 1.2 is made be warming up to 40 DEG C～80 DEG C, then pour the clean hollow glass micropearl taking through step 1.2 into sodium hydroxide solutionMiddle immersion, stirs 10min～30min with the speed of 100rpm～200rpm, then by hydrogen-oxygenChange the hollow glass micropearl soaking in sodium solution and fish for out, with deionized water washing, until washTill the pH value of the deionized water after washing is neutrality, complete the pretreatment to hollow glass micropearl;

Step 1.4, will be through the pretreated hollow glass micropearl of step 1.3 in 110 DEG C～150 DEG CDrying 2h～4h under condition.

3. rare-earth europium dopen Nano TiO according to claim 1₂The system of hollow glass micropearlPreparation Method, is characterized in that, in described step 5.3 by the hollow glass micropearl of separating inVacuum drying under 60 DEG C～80 DEG C conditions.