CN103801283A - Preparation method for lanthanum and gadolinium-codoped titanium dioxide mesoporous microsphere - Google Patents
Preparation method for lanthanum and gadolinium-codoped titanium dioxide mesoporous microsphere Download PDFInfo
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- CN103801283A CN103801283A CN201210455870.9A CN201210455870A CN103801283A CN 103801283 A CN103801283 A CN 103801283A CN 201210455870 A CN201210455870 A CN 201210455870A CN 103801283 A CN103801283 A CN 103801283A
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- lanthanum
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Abstract
The invention provides a preparation method for a lanthanum and gadolinium-codoped titanium dioxide mesoporous microsphere. The preparation method comprises the steps of: by taking P123 as a template agent, butyl titanate as active ingredients and anhydrate ethanol as a solvent, adding acetylacetone, hydrochloric acid and distilled water in the mixing process, and mixing; doping 0.2-4.0% in mole fraction of lanthanum and 0.2-2.0% in mole fraction of gadolinium, mixing to be uniform, transferring into polytetrafluoroethylene for performing hydrothermal reaction, washing, and drying to obtain the lanthanum and gadolinium-codoped titanium dioxide mesoporous microsphere. By using the preparation method, various rare earth ions can be successfully loaded on the surface and interior of the titanium dioxide microsphere, the dispersity of the rare earth ions in the titanium dioxide microsphere is high, and the properties of the product are stable; the product is in an anatase crystal form, and the degree of crystallinity is high; the preparation method of the product is simple, low in cost, and large in specific area, and is hopefully applied into the field of photocatalysis.
Description
Technical field
The present invention relates to a kind of preparation method of mesoporous microsphere, particularly relate to the preparation method of a kind of lanthanum and gadolinium codope titanium dioxide mesoporous microsphere, belong to mesoporous material and field of photocatalytic material.
Background technology
Along with the develop rapidly of World Economics, the mankind have caused a series of serious problem of environmental pollutions such as greenhouse effects, atmosphere pollution, soil pollution, water pollution to the excessive use of the fossil energy of depending on for existence, thereby have destroyed greatly the ecological environment of the earth.Environmental pollution is except causing to the ecosystem direct destruction and impact, and the accumulation of pollutant and migration, conversion also can cause various derivative environmental effects, causes indirectly more serious harm to the ecosystem and human society.Therefore, thus solving sustainable development that environmental problem realizes the mankind becomes 21st century and has challenging problem.Photocatalytic oxidation is the high-grade water treatment technology occurring in recent years, within certain reaction time, can be CO by organic matter permineralization conventionally
2and H
2the simple inorganic matter such as O, has avoided secondary pollution, simple, efficient, is the high-level oxidation technology that a kind of application is very strong.Semiconductor light-catalyst TiO
2because the photoelectric properties nontoxic, inexpensive, stability is high and excellent have caused people's extensive concern.But, traditional TiO
2photochemical catalyst has limited its large-scale environmental applications because photogenerated charge recombination rate is high.Therefore, how further to improve TiO
2the photocatalysis efficiency of photochemical catalyst becomes letter problem to be solved.
In order addressing the above problem, can to take to improve the methods such as crystallization degree, increase specific area and element doping and expand the spectral response range to sunshine and suppress the compound of electron-hole pair.Because mesoporous material has the aperture of 2nm to 50nm, specific area is large, therefore, and the mesoporous anatase phase TiO of high-crystallinity
2good photocatalysis performance and potential application prospect will be possessed.In addition research shows, rare earth element has special 4f electronic structure, and rare earth oxide has polymorphic, strong adsorptivity, stability, and the doping of appropriate rare earth ion can effectively improve TiO
2semiconductor property, rare earth ion can replace TiO
2in Ti, thereby make TiO
2expand its spectral response range to sunshine not reducing under ultraviolet light in active, improve its utilization rate to visible ray.In recent years, the research of titanium dioxide being carried out to doping vario-property about rare earth element has also obtained key progress, but still has very large research space, and especially the research of double rare-earth elements modification is little.
Summary of the invention
The object of the invention is to solve the technical problems such as existing titanium dioxide optical catalyst specific area is little, photocatalytic activity is low, efficiency is poor, adopting P123 leading portion copolymer is the two rear-earth-doped TiO that template preparation has high-specific surface area, high-crystallinity
2mesoporous microsphere.
The preparation method who the invention provides a kind of lanthanum and gadolinium codope titanium dioxide mesoporous microsphere, is characterized in that, comprises the steps:
(1) P123 template is dissolved in absolute ethyl alcohol, stirs template is dissolved completely;
(2) add titanate esters, acid, acetylacetone,2,4-pentanedione and deionized water, vigorous stirring makes it to mix;
(3) in above-mentioned solution, add lanthanum salt, gadolinium salt, stir and make it to form homogeneous solution;
(4) suspension mixing is put into the stainless steel autoclave of teflon lined, hydro-thermal reaction 12～72 hours at 120 ℃～180 ℃.
(5) reaction finish after by distilled water, absolute ethanol washing precipitated product for, then at 60 ℃～80 ℃, be dried 6～24 hours, obtain the mesoporous titanium dioxide microspheres of lanthanum and gadolinium codope.
The P123 template that step (1) is described and the ratio of absolute ethyl alcohol are 1:10～1:20.
The described titanate esters of step (2) is butyl titanate, or isopropyl titanate, and the ratio of addition and absolute ethyl alcohol is 1:6～1:8.
The described acid of step (2) can be concentrated hydrochloric acid or nitric acid, or acetic acid, with the volume of titanate esters be 1:5～1:10; The volume ratio of deionized water and titanate esters is 0.25:1～0.5:1, with the volume ratio of acetylacetone,2,4-pentanedione be 1:1～1:3; The volume ratio of deionized water and titanate esters is 0.25:1～0.5:1.
The addition of the rare earth lanthanum nitrate described in step (3) is measured by the molar percentage of gadolinium ion and titanium dioxide, and addition is 0.2%～4.0%.
The addition of the rare earth gadolinium nitrate described in step (3) is measured by the molar percentage of gadolinium ion and titanium dioxide, and addition is 0.2%～2.0%.
The described drying means of step (5) is constant pressure and dry, or vacuum drying, and be 6～24 hours described drying time.
In the present invention, it is pure that the butyl titanate that adopts, isopropyl titanate, lanthanum nitrate, gadolinium nitrate, hydrochloric acid, nitric acid, acetylacetone,2,4-pentanedione are analysis.
The structure of the inventive method products therefrom, pattern, composition characterize, and select respectively X-ray powder diffraction (XRD), SEM (SEM), N
2the means such as adsorption specific surface area tester (BET) characterize.
This preparation method can successfully load on multiple rare earth ion the surperficial and inner of titanium dioxide microballoon sphere, and the dispersiveness of rare earth ion in titanium dioxide microballoon sphere is high, and product characteristics is stable; Product is anatase crystal, and degree of crystallinity is high; The preparation method of this product is simple, with low cost, and specific area is large, is expected to be applied to photocatalysis field.
The mesoporous titanium dioxide microspheres of two rare earth codopes prepared by the present invention is anatase crystal, has larger specific area, and has very high degree of crystallinity.Titanium dioxide optical catalyst prepared by the inventive method has abundant loose structure, and this is conducive to the diffusion of reactant and product and absorbing light.Porous nano titanium dioxide optical catalyst prepared by the inventive method has very high photocatalytic activity, under UV-irradiation, and the organic pollution in the empty G&W of catalytic degradation effectively.Take methyl orange as target degradation product, the photocatalysis performance of product is characterized.Result shows, in the dye solution of the product that contains 0.1g (dye volume is 100ml, and concentration is 20mgL), under the irradiation of high-pressure sodium lamp (300W), methyl orange can be degradable in 20 min.
Accompanying drawing explanation
ESEM (SEM) figure of Fig. 1: embodiment 1 products therefrom.
X-ray diffraction (XRD) figure of Fig. 2: embodiment 1 products therefrom.
Show that thing is anatase phase mutually.
The nitrogen adsorption desorption isotherm of Fig. 3: embodiment 1 products therefrom.
Specific area is 91.4m
2g
-1
Fig. 4: be embodiment 1 products therefrom and methyl orange mixed solution under UV Light condition, dye strength and its initial concentration ratio (C/Co) graph of a relation over time.
The specific embodiment
Below by embodiment, the present invention is further elaborated, and its object is only better to understand content of the present invention.Therefore, the cited case does not limit the scope of the invention.
Embodiment 1;
(1) the P123 template that takes 1.5g is dissolved in 15ml absolute ethyl alcohol, stirs template is dissolved completely;
(2) add 7ml butyl titanate, 1.5ml nitric acid, 1.5ml acetylacetone,2,4-pentanedione and 0.5ml deionized water, vigorous stirring makes it to mix;
(3) in above-mentioned solution, add 2.0% lanthanum salt, 0.5% gadolinium salt (with TiO
2mol ratio), stir and make it to form homogeneous solution;
(4) suspension mixing is put into the stainless steel autoclave of teflon lined, hydro-thermal reaction 24 hours at 120 ℃.
(5) reaction finish after by distilled water, absolute ethanol washing precipitated product for, then at 80 ℃ be dried 12 hours, obtain thering is high specific surface area (>90m
2g
-1), the mesoporous titanium dioxide microspheres of mesoporous anatase phase, lanthanum and the gadolinium codope of highly crystalline.
Products therefrom in step (5) is characterized its structure and crystal formation with SEM, XRD, BET respectively, and Fig. 1,2,3,4 is pattern, crystalline form and nitrogen adsorption-desorption curve of the mesoporous titanium dioxide microspheres of reaction condition gained for this reason.As can be seen from the figure, the product of preparation is microballoon, and microballoon is made up of nano particle, and the particle diameter of nano particle is even, is about 20nm; Anatase crystalline form from the crystal formation of the visible products obtained therefrom of X-ray powder diffraction collection of illustrative plates, and in the diffraction maximum of XRD, there is no other impurity peaks, the degree of crystallinity that shows products therefrom is fine, in sample, there is not the diffraction maximum of rare earth lanthanum oxide and gadolinium oxide, this may be because the doping of rare earth element is less, and it is caused that rare earth ion enters the lattice of titanium dioxide, also show doped chemical high degree of dispersion simultaneously, there is not serious reunion, cause can't detect in composite nano particle the XRD characteristic peak of doping phase crystal structure.The specific area of product is 91.4 m
2/ g, this is TiO
2the application aspect photocatalysis of mesoporous microsphere is laid a good foundation.
Embodiment 2;
(1) the P123 template that takes 1.5g is dissolved in 15ml absolute ethyl alcohol, stirs template is dissolved completely;
(2) add 7ml isopropyl titanate, 2ml nitric acid, 1.5ml acetylacetone,2,4-pentanedione and 0.5ml deionized water, vigorous stirring makes it to mix;
(3) in above-mentioned solution, add 1.0% lanthanum salt, 1.0% gadolinium salt (with TiO
2mol ratio), stir and make it to form homogeneous solution;
(4) suspension mixing is put into the stainless steel autoclave of teflon lined, hydro-thermal reaction 24 hours at 150 ℃.
(5) reaction finish after by distilled water, absolute ethanol washing precipitated product for, then at 80 ℃ be dried 12 hours.
Embodiment 3:
(1) the P123 template that takes 1.5g is dissolved in 20ml absolute ethyl alcohol, stirs template is dissolved completely;
(2) add 8ml butyl titanate, 2ml hydrochloric acid, 1.5ml acetylacetone,2,4-pentanedione and 0.5ml deionized water, vigorous stirring makes it to mix;
(3) in above-mentioned solution, add 0.5% lanthanum salt, 1.5% gadolinium salt (with TiO
2mol ratio), stir and make it to form homogeneous solution;
(4) suspension mixing is put into the stainless steel autoclave of teflon lined, hydro-thermal reaction 12 hours at 180 ℃.
(5) reaction finish after by distilled water, absolute ethanol washing precipitated product for, then at 80 ℃ be dried 12 hours.
Embodiment 4:
(1) the P123 template that takes 1.5g is dissolved in 25ml absolute ethyl alcohol, stirs template is dissolved completely;
(2) add 7ml isopropyl titanate, 2ml nitric acid, 1.5ml acetylacetone,2,4-pentanedione and 0.2ml deionized water, vigorous stirring makes it to mix;
(3) in above-mentioned solution, add 2.0% lanthanum salt, 2.0% gadolinium salt (with TiO
2mol ratio), stir and make it to form homogeneous solution;
(4) suspension mixing is put into the stainless steel autoclave of teflon lined, hydro-thermal reaction 24 hours at 180 ℃.
(5) reaction finish after by distilled water, absolute ethanol washing precipitated product for, then at 80 ℃ be dried 12 hours.
Embodiment 5:
(1) the P123 template that takes 1.5g is dissolved in 15ml absolute ethyl alcohol, stirs template is dissolved completely;
(2) add 8ml butyl titanate, 2ml hydrochloric acid, 1.5ml acetylacetone,2,4-pentanedione and 0.5ml deionized water, vigorous stirring makes it to mix;
(3) in above-mentioned solution, add 4.0% lanthanum salt, 2.0% gadolinium salt (with TiO
2mol ratio), stir and make it to form homogeneous solution;
(4) suspension mixing is put into the stainless steel autoclave of teflon lined, hydro-thermal reaction 24 hours at 180 ℃.
(5) reaction finish after by distilled water, absolute ethanol washing precipitated product for, then at 60 ℃ be dried 24 hours.
Claims (7)
1. a preparation method for lanthanum and gadolinium codope titanium dioxide mesoporous microsphere, is characterized in that, comprises the steps:
(1) P123 template is dissolved in absolute ethyl alcohol, stirs template is dissolved completely;
(2) add titanate esters, acid, acetylacetone,2,4-pentanedione and deionized water, vigorous stirring makes it to mix;
(3) in above-mentioned solution, add lanthanum salt, gadolinium salt, stir and make it to form homogeneous solution;
(4) suspension mixing is put into the stainless steel autoclave of teflon lined, hydro-thermal reaction 12～72 hours at 120 ℃～180 ℃;
(5) reaction finish after by distilled water, absolute ethanol washing precipitated product for, then at 60 ℃～80 ℃, be dried 6～24 hours, obtain the mesoporous titanium dioxide microspheres of lanthanum and gadolinium codope.
2. the preparation method of a kind of lanthanum according to claim 1 and gadolinium codope titanium dioxide mesoporous microsphere, is characterized in that: the P123 template that step (1) is described and the ratio of absolute ethyl alcohol are 1:10～1:20.
3. the preparation method of a kind of lanthanum according to claim 1 and gadolinium codope titanium dioxide mesoporous microsphere, is characterized in that: the described titanate esters of step (2) is butyl titanate, or isopropyl titanate, and the ratio of addition and absolute ethyl alcohol is 1:6～1:8.
4. the preparation method of a kind of lanthanum according to claim 1 and gadolinium codope titanium dioxide mesoporous microsphere, is characterized in that: the described acid of step (2) can be concentrated hydrochloric acid or nitric acid, or acetic acid, with the volume of titanate esters be 1:5～1:10; The volume ratio of deionized water and titanate esters is 0.25:1～0.5:1, with the volume ratio of acetylacetone,2,4-pentanedione be 1:1～1:3; The volume ratio of deionized water and titanate esters is 0.25:1～0.5:1.
5. the preparation method of a kind of lanthanum according to claim 1 and gadolinium codope titanium dioxide mesoporous microsphere, it is characterized in that: the addition of the rare earth lanthanum nitrate described in step (3) is measured by the molar percentage of gadolinium ion and titanium dioxide, and addition is 0.2%～4.0%.
6. the preparation method of a kind of lanthanum according to claim 1 and gadolinium codope titanium dioxide mesoporous microsphere, it is characterized in that: the addition of the rare earth gadolinium nitrate described in step (3) is measured by the molar percentage of gadolinium ion and titanium dioxide, and addition is 0.2%～2.0%.
7. according to the preparation method of a kind of lanthanum described in claim 1 any one and gadolinium codope titanium dioxide mesoporous microsphere, it is characterized in that: the described drying means of step (5) is constant pressure and dry, or vacuum drying, and be 6～24 hours described drying time.
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Cited By (7)
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| CN105399052A (en) * | 2015-11-09 | 2016-03-16 | 上海纳米技术及应用国家工程研究中心有限公司 | Dual-rare earth-co-doped titanium dioxide gas sensitive sensing material preparation |
| CN105435828A (en) * | 2015-12-31 | 2016-03-30 | 北京化工大学 | Fe and N co-doped mesoporous TiO2 microsphere array visible light photocatalyst and preparation method |
| CN107445201A (en) * | 2017-09-11 | 2017-12-08 | 广东工业大学 | A kind of preparation method of rear-earth-doped anatase titanium dioxide micro-nano-sphere |
| CN108017936A (en) * | 2017-12-05 | 2018-05-11 | 华北水利水电大学 | A kind of preparation method of spherical compound ultra-fine yellow ceramic paint |
| CN109865511A (en) * | 2017-12-04 | 2019-06-11 | 天津发洋环保科技有限公司 | A kind of preparation method of doped nano photo-catalytic emulsion |
| CN113576982A (en) * | 2021-09-02 | 2021-11-02 | 和也健康科技有限公司 | Preparation method of multifunctional nano stone needle fiber mask capable of diminishing inflammation and whitening skin |
| CN113698827A (en) * | 2021-09-02 | 2021-11-26 | 和也健康科技有限公司 | Preparation method of multifunctional health-care coating |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105399052A (en) * | 2015-11-09 | 2016-03-16 | 上海纳米技术及应用国家工程研究中心有限公司 | Dual-rare earth-co-doped titanium dioxide gas sensitive sensing material preparation |
| CN105435828A (en) * | 2015-12-31 | 2016-03-30 | 北京化工大学 | Fe and N co-doped mesoporous TiO2 microsphere array visible light photocatalyst and preparation method |
| CN107445201A (en) * | 2017-09-11 | 2017-12-08 | 广东工业大学 | A kind of preparation method of rear-earth-doped anatase titanium dioxide micro-nano-sphere |
| CN107445201B (en) * | 2017-09-11 | 2019-01-08 | 广东工业大学 | A kind of preparation method of rear-earth-doped anatase titanium dioxide micro-nano-sphere |
| CN109865511A (en) * | 2017-12-04 | 2019-06-11 | 天津发洋环保科技有限公司 | A kind of preparation method of doped nano photo-catalytic emulsion |
| CN108017936A (en) * | 2017-12-05 | 2018-05-11 | 华北水利水电大学 | A kind of preparation method of spherical compound ultra-fine yellow ceramic paint |
| CN113576982A (en) * | 2021-09-02 | 2021-11-02 | 和也健康科技有限公司 | Preparation method of multifunctional nano stone needle fiber mask capable of diminishing inflammation and whitening skin |
| CN113698827A (en) * | 2021-09-02 | 2021-11-26 | 和也健康科技有限公司 | Preparation method of multifunctional health-care coating |
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