CN103801283B - A kind of lanthanum and the preparation method of gadolinium codope titanium dioxide mesoporous microsphere - Google Patents
A kind of lanthanum and the preparation method of gadolinium codope titanium dioxide mesoporous microsphere Download PDFInfo
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Abstract
The present invention proposes a kind of lanthanum and the preparation method of gadolinium codope titanium dioxide mesoporous microsphere, and with P123 as template, butyl titanate is raw material, and dehydrated alcohol is solvent, and adds acetylacetone,2,4-pentanedione, hydrochloric acid and distilled water, stirring in whipping process；With molar fraction, the doping of lanthanum is 0.2 ~ 4.0%, and the doping of gadolinium is 0.2% ~ 2.0%, after stirring, is transferred to hydro-thermal reaction in politef, after washing, and drying to lanthanum and the mesoporous titanium dioxide microspheres of gadolinium codope.Multiple rare earth ion can be successfully supported on surface and the inside of titanium dioxide microballoon sphere by this preparation method, and rare earth ion dispersibility 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 surface area is big, is expected to be applied to photocatalysis field.
Description
Technical field
The present invention relates to the preparation method of a kind of mesoporous microsphere, particularly relate to a kind of lanthanum and the preparation method of gadolinium codope titanium dioxide mesoporous microsphere, belong to mesoporous material and field of photocatalytic material.
Background technology
Along with developing rapidly of World Economics, excessively using of mankind's fossil energy to depending on for existence result in a series of serious problem of environmental pollutions such as greenhouse effect, atmospheric pollution, soil pollution, water pollution, thus destroy the ecological environment of the earth greatly.Environmental pollution is in addition to causing to ecosystem and directly destroying and affect, and the accumulation of pollutant and migration, conversion also can cause various derivative environmental effect, cause the most serious harm to ecosystem and human society.Therefore, solve environmental problem thus realize the sustainable development of the mankind and become 21st century extremely challenging problem.Photocatalytic oxidation is the high-grade water treatment technology occurred in recent years, can be generally CO by Organic substance permineralization within certain response time2And H2The simple inorganic matter such as O, it is to avoid secondary pollution, simple, efficiently, it is the high-level oxidation technology that a kind of application is the strongest.Semiconductor light-catalyst TiO2The extensive concern of people is caused due to photoelectric properties nontoxic, inexpensive, that stability is high and excellent.But, traditional TiO2Photocatalyst limits its large-scale environmental applications because photogenerated charge recombination rate is high.Therefore, TiO is improved the most further2The photocatalysis efficiency of photocatalyst becomes the problem that letter is to be solved.
In order to solve the problems referred to above, raising crystallization degree, the increase method such as specific surface area and element doping can be taked to expand the spectral response range to sunlight and suppress the compound of electron-hole pair.Owing to mesoporous material has the aperture of 2nm to 50nm, specific surface area is big, therefore, and mesoporous anatase phase TiO of high-crystallinity2Will be provided with good photocatalysis performance and potential application prospect.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 TiO2Semiconductor property, rare earth ion can replace TiO2In Ti so that TiO2Under not reducing ultraviolet light, while activity, expand its spectral response range to sunlight, improve its utilization rate to visible ray.In recent years, about rare earth element, titanium dioxide being doped modified research and also achieve key progress, but still suffer from the biggest research space, the research that especially double rare-earth elements is modified is little.
Summary of the invention
It is an object of the invention to solve the technical problems such as existing titanium dioxide optical catalyst specific surface area little, photocatalytic activity is low, inefficient, using P123 block copolymer is the double rear-earth-doped TiO that template preparation has high-specific surface area, high-crystallinity2Mesoporous microsphere.
The present invention provides a kind of lanthanum and the preparation method of gadolinium codope titanium dioxide mesoporous microsphere, it is characterised in that comprise the steps:
(1) P123 template being dissolved in dehydrated alcohol, stirring makes template be completely dissolved；
(2) add titanate esters, acid, acetylacetone,2,4-pentanedione and deionized water, be stirred vigorously and be allowed to mix homogeneously；
(3) adding lanthanum salt, gadolinium salt in above-mentioned solution, stirring is allowed to form homogeneous solution；
(4) suspension of mix homogeneously is put in the stainless steel autoclave of teflon lined, hydro-thermal reaction 12～72 hours at 120 DEG C～180 DEG C.
(5) by precipitated product distilled water, absolute ethanol washing after reaction terminates, then it is dried 6～24 hours at 60 DEG C～80 DEG C, i.e. obtains lanthanum and the mesoporous titanium dioxide microspheres of gadolinium codope.
P123 template described in step (1) is 1:10～1:20 with the ratio of dehydrated alcohol.
Step (2) described titanate esters is butyl titanate, or isopropyl titanate, and addition is 1:6～1:8 with the ratio of dehydrated alcohol.
Step (2) described acid can be concentrated hydrochloric acid or nitric acid, or acetic acid, is 1:5～1:10 with the volume of titanate esters；Deionized water is 0.25:1～0.5:1 with the volume ratio of titanate esters, is 1:1～1:3 with the volume ratio of acetylacetone,2,4-pentanedione；Deionized water is 0.25:1～0.5:1 with the volume ratio of titanate esters.
The addition of the rare earth Lanthanum (III) nitrate described in step (3) is measured by the molar percentage of gadolinium ion with titanium dioxide, and addition is 0.2%～4.0%.
The addition of the rare earth Gadolinium trinitrate described in step (3) is measured by the molar percentage of gadolinium ion with titanium dioxide, and addition is 0.2%～2.0%.
Drying means described in step (5) is constant pressure and dry, or vacuum drying, and described drying time is 6～24 hours.
In the present invention, used butyl titanate, isopropyl titanate, Lanthanum (III) nitrate, Gadolinium trinitrate, hydrochloric acid, nitric acid, acetylacetone,2,4-pentanedione are analytical pure.
The structure of the inventive method products therefrom, pattern, composition characterize, and select X-ray powder diffraction (XRD), scanning electron microscope (SEM), N respectively2The means such as adsorption specific surface area tester (BET) characterize.
Multiple rare earth ion can be successfully supported on surface and the inside of titanium dioxide microballoon sphere by this preparation method, and rare earth ion dispersibility 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 surface area is big, is expected to be applied to photocatalysis field.
The mesoporous titanium dioxide microspheres of double rare earth codopes prepared by the present invention is anatase crystal, has bigger specific surface area, and has the highest degree of crystallinity.Titanium dioxide optical catalyst prepared by the inventive method has abundant loose structure, and this is conducive to reactant and the diffusion of product and absorbs light.Porous nano titanium dioxide optical catalyst prepared by the inventive method has the highest photocatalytic activity, under ultraviolet light irradiates, and can the organic pollution in catalytic degradation air and water effectively.With methyl orange for target degradation product, the photocatalysis performance of product is characterized.Result shows, in the dye solution containing the product of 0.1g (dye volume is 100ml, and concentration is 20mg L), under the irradiation of high voltage mercury lamp (300W), methyl orange can be degradable in 20min.
Accompanying drawing explanation
Scanning electron microscope (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 mutually for anatase phase.
The nitrogen adsorption desorption isotherm of Fig. 3: embodiment 1 products therefrom.
Specific surface area is 91.4m2·g-1
Fig. 4: be embodiment 1 products therefrom and methyl orange mixed solution under the conditions of UV Light, dye strength and its initial concentration ratio (C/Co) graph of a relation over time.
Detailed description of the invention
Below by embodiment, the present invention is further elaborated, and its purpose is only that and is best understood from present disclosure.Therefore, the cited case is not limiting as protection scope of the present invention.
Embodiment 1;
(1) the P123 template weighing 1.5g is dissolved in 15ml dehydrated alcohol, and stirring makes template be completely dissolved；
(2) add 7ml butyl titanate, 1.5ml nitric acid, 1.5ml acetylacetone,2,4-pentanedione and 0.5ml deionized water, be stirred vigorously and be allowed to mix homogeneously；
(3) in above-mentioned solution, 2.0% lanthanum salt, 0.5% gadolinium salt are added (with TiO2Mol ratio), stirring be allowed to form homogeneous solution；
(4) suspension of mix homogeneously is put in the stainless steel autoclave of teflon lined, hydro-thermal reaction 24 hours at 120 DEG C.
(5) by precipitated product distilled water, absolute ethanol washing after reaction terminates, then it is dried 12 hours at 80 DEG C, i.e. obtains that there is high specific surface area (> 90m2·g-1), the mesoporous anatase phase of highly crystalline, lanthanum and the mesoporous titanium dioxide microspheres of gadolinium codope.
Being characterized its structure and crystal formation with SEM, XRD, BET respectively by products therefrom in step (5), Fig. 1,2,3,4 are the pattern of the mesoporous titanium dioxide microspheres of this reaction condition gained, crystal form and nitrogen adsorption-desorption curve.It can be seen that the product of preparation is microsphere, microsphere is made up of nano-particle, the uniform particle sizes of nano-particle, about 20nm；It is anatase crystal form from the crystal formation of products obtained therefrom seen from X-ray powder diffraction pattern, and the diffraction maximum of XRD does not has other impurity peaks, show that the degree of crystallinity of products therefrom is fine, sample does not occur the diffraction maximum of rare earth lanthanum oxide and Gadolinia., this doping being likely due to rare earth element is less, and caused by the lattice of rare earth ion entrance titanium dioxide, also indicate that doped chemical high degree of dispersion simultaneously, there is not serious reunion, cause the XRD characteristic peak that can't detect doping phase crystal structure in composite nano particle.The specific surface area of product is 91.4m2/ g, this is TiO2The application in terms of photocatalysis of mesoporous microsphere is laid a good foundation.
Embodiment 2；
(1) the P123 template weighing 1.5g is dissolved in 15ml dehydrated alcohol, and stirring makes template be completely dissolved；
(2) add 7ml isopropyl titanate, 2ml nitric acid, 1.5ml acetylacetone,2,4-pentanedione and 0.5ml deionized water, be stirred vigorously and be allowed to mix homogeneously；
(3) in above-mentioned solution, 1.0% lanthanum salt, 1.0% gadolinium salt are added (with TiO2Mol ratio), stirring be allowed to form homogeneous solution；
(4) suspension of mix homogeneously is put in the stainless steel autoclave of teflon lined, hydro-thermal reaction 24 hours at 150 DEG C.
(5) by precipitated product distilled water, absolute ethanol washing after reaction terminates, then it is dried 12 hours at 80 DEG C.
Embodiment 3:
(1) the P123 template weighing 1.5g is dissolved in 20ml dehydrated alcohol, and stirring makes template be completely dissolved；
(2) add 8ml butyl titanate, 2ml hydrochloric acid, 1.5ml acetylacetone,2,4-pentanedione and 0.5ml deionized water, be stirred vigorously and be allowed to mix homogeneously；
(3) in above-mentioned solution, 0.5% lanthanum salt, 1.5% gadolinium salt are added (with TiO2Mol ratio), stirring be allowed to form homogeneous solution；
(4) suspension of mix homogeneously is put in the stainless steel autoclave of teflon lined, hydro-thermal reaction 12 hours at 180 DEG C.
(5) by precipitated product distilled water, absolute ethanol washing after reaction terminates, then it is dried 12 hours at 80 DEG C.
Embodiment 4:
(1) the P123 template weighing 1.5g is dissolved in 25ml dehydrated alcohol, and stirring makes template be completely dissolved；
(2) add 7ml isopropyl titanate, 2ml nitric acid, 1.5ml acetylacetone,2,4-pentanedione and 0.2ml deionized water, be stirred vigorously and be allowed to mix homogeneously；
(3) in above-mentioned solution, 2.0% lanthanum salt, 2.0% gadolinium salt are added (with TiO2Mol ratio), stirring be allowed to form homogeneous solution；
(4) suspension of mix homogeneously is put in the stainless steel autoclave of teflon lined, hydro-thermal reaction 24 hours at 180 DEG C.
(5) by precipitated product distilled water, absolute ethanol washing after reaction terminates, then it is dried 12 hours at 80 DEG C.
Embodiment 5:
(1) the P123 template weighing 1.5g is dissolved in 15ml dehydrated alcohol, and stirring makes template be completely dissolved；
(2) add 8ml butyl titanate, 2ml hydrochloric acid, 1.5ml acetylacetone,2,4-pentanedione and 0.5ml deionized water, be stirred vigorously and be allowed to mix homogeneously；
(3) in above-mentioned solution, 4.0% lanthanum salt, 2.0% gadolinium salt are added (with TiO2Mol ratio), stirring be allowed to form homogeneous solution；
(4) suspension of mix homogeneously is put in the stainless steel autoclave of teflon lined, hydro-thermal reaction 24 hours at 180 DEG C.
(5) by precipitated product distilled water, absolute ethanol washing after reaction terminates, then it is dried 24 hours at 60 DEG C.
Claims (2)
1. a lanthanum and the preparation method of gadolinium codope titanium dioxide mesoporous microsphere, it is characterised in that comprise the steps:
(1) P123 template being dissolved in dehydrated alcohol, stirring makes template be completely dissolved；
Described P123 template is 1:10～1:20 with the ratio of dehydrated alcohol；
(2) add titanate esters, acid, acetylacetone,2,4-pentanedione and deionized water, be stirred vigorously and be allowed to mix homogeneously；
Described titanate esters is butyl titanate, or isopropyl titanate, and addition with the ratio of dehydrated alcohol is1:6～1:8；
Described acid can be concentrated hydrochloric acid or nitric acid, or acetic acid, with the volume ratio of titanate esters is1:5～1:10；Deionized water with the volume ratio of titanate esters is0.25:1～0.5:1, it is 1:1～1:3 with the volume ratio of acetylacetone,2,4-pentanedione；
(3) adding lanthanum salt, gadolinium salt in above-mentioned solution, stirring is allowed to form homogeneous solution；
The addition of described rare earth Lanthanum (III) nitrate is measured by the molar percentage of lanthanum ion with titanium dioxide, and addition is 0.2%～4.0%；
The addition of described rare earth Gadolinium trinitrate is measured by the molar percentage of gadolinium ion with titanium dioxide, and addition is 0.2%～2.0%；
(4) suspension of mix homogeneously is put in the stainless steel autoclave of teflon lined, hydro-thermal reaction 12～72 hours at 120 DEG C～180 DEG C；
(5) by precipitated product distilled water, absolute ethanol washing after reaction terminates, then it is dried 6～24 hours at 60 DEG C～80 DEG C, i.e. obtains lanthanum and the mesoporous titanium dioxide microspheres of gadolinium codope.
A kind of lanthanum the most according to claim 1 and the preparation method of gadolinium codope titanium dioxide mesoporous microsphere, it is characterised in that: the drying means described in step (5) is constant pressure and dry, or vacuum drying, and described drying time is 6～24 hours.
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| 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 |
| 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 |
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