CN102992397B - Preparation method for rare earth element-doped titanium dioxide nano material - Google Patents
Preparation method for rare earth element-doped titanium dioxide nano material Download PDFInfo
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Abstract
The invention relates to a preparation method for a rare earth element-doped titanium dioxide nano material. The method comprises the steps of dissolving urea and rare earth element nitrate in absolute ethyl alcohol; adding liquid titanium source into the above solution to form a homogeneous solution; adding deionized water with stirring to form a transparent gel; performing hydro-thermal treatment on the above gel; washing, filtering and drying to obtain the rare earth element-doped titanium dioxide nano material. An object of doping titanium dioxide by using the rare earth element is realized through automatic regulation and control of pH value of a reaction system by slow decomposition of urea in the hydrothermal process. The preparation method is simple in process and flow, has wide parameter adjustable range, strong repeatability and low cost, and can be used for preparing different rare earth element-doped titanium dioxide nano materials or a plurality of the rare earth elements co-doped titanium dioxide nano material.
Description
Technical field
The present invention relates to a kind of preparation method of titanium dioxide nano material, particularly relate to a kind of preparation method of rare earth doped titanium dioxide nano material, belong to technical field of inorganic nano-material preparation.
Background technology
Spectrochemical property is stable, catalytic efficiency is high, oxidation capacity is strong owing to having for titanium dioxide, nontoxic, cheap, the advantage such as technical process simple, operational condition easily controls, non-secondary pollution in actual applications, and it receives the increasingly extensive concern of people as photocatalyst.The developed countries such as America and Europe have all injected capital into and have carried out the research and development of optically catalytic TiO 2 technology with research effort, and new high-tech industry based on this is also formed.
Titanium dioxide is as a kind of semiconductor functional material, and its photocatalytic activity determines primarily of the crystalline structure of self, but also very responsive to a small amount of impurity.Spectral response range and the catalytic efficiency of photocatalyst can be improved by doping vario-property.Research comparative maturity at present to single doping vario-property of titanium dioxide, by the doping of some metallic elements and non-metallic element, the photocatalysis performance of titanium dioxide significantly improves.Adulterate a small amount of metal ion in titanium dioxide, the shallow gesture that can become photo-generate electron-hole right catches trap, extend the recombination time in electronics and hole, improve the photocatalysis performance of titanium dioxide, and, some doping can also reduce the energy gap of titanium dioxide, expand its light abstraction width, improve the utilization ratio to sunlight.
Rare earth is one of grand strategy resource of China, and its reserves, output and export volume be row the first in the world all.Rare earth element has complicated level structure and spectral response curve, carries out doping vario-property, can effectively improve its photocatalysis efficiency to nano titanium oxide, is that most wishes one of technology solving visible ray utilization ratio., some preparation method's rare earth elements doping utilization ratio is in the past not high, and the rare earth atom ratio that successfully can replace the lattice sites in titanium dioxide is lower, and therefore photocatalytic activity improves not obvious.Further, adopt the preparation method of two kinds of rare earth element co-doped titanium dioxide, report is less at present; The preparation method of more than three kinds rare earth element co-doped titanium dioxide is adopted to there is no report.
Summary of the invention
In order to overcome the deficiencies in the prior art, the invention provides a kind of preparation method of rare earth doped titanium dioxide nano material.
A preparation method for rare earth doped titanium dioxide nano material, is characterized in that, comprises the steps:
(1) in dehydrated alcohol, add urea, rare earth element nitrate, after stirring and dissolving, add liquid phase titanium source, stir and form homogeneous phase solution; Then in above-mentioned system, deionized water is dripped while stirring, until form clear gel;
(2) above-mentioned gel is put into the stainless steel autoclave of teflon lined, hydro-thermal reaction 12 ~ 48 hours at 120 ~ 200 DEG C; By precipitated product deionized water wash after reaction terminates, until the pH of washings is in neutral, then carries out drying treatment, obtain rare earth doped titanium dioxide nano material.
The urea quality added described in step (1) and reaction soln cumulative volume ratio are 0.1 gram/100 milliliters ~ 3 grams/100 milliliters.
Rare earth element nitrate described in step (1) is one in the cerous nitrate of hydration or non-hydrated, lanthanum nitrate, neodymium nitrate, Yttrium trinitrate, Gadolinium trinitrate, europium nitrate, Terbium trinitrate, samaric nitrate, thulium nitrate, Erbium trinitrate, ytterbium nitrate or its combination.
The rare earth element nitrate quality added described in step (1) is 0.001 gram/10 milliliters ~ 0.5 gram/10 milliliters with adding liquid phase titanium volume source ratio.
Liquid phase titanium source described in step (1) is one in positive four butyl esters of metatitanic acid, isopropyl titanate, tetraethyl titanate or its combination.
Liquid phase titanium source described in step (1) adds volume with reaction soln cumulative volume than being 5:100 ~ 30:100.
The deionized water volume added described in step (1) and reaction soln cumulative volume are than being 2:100 ~ 20:100.
In the present invention, liquid phase titanium source is slowly hydrolyzed and forms aqua oxidation titanium gel, and rare earth ion is evenly dispersed in aqua oxidation titanium gel; By the slow decomposition of urea in water-heat process, the acid-basicity of system moves to weakly alkaline direction gradually, achieves in-situ doped in titanium oxide lattice of thulium.This preparation method's technique and simple flow, Parameter adjustable wide ranges, repeatable strong, cost is low, can prepare different rare earth doped and multiple rare earth element codoping titanium dioxide nano material.By the rare earth doped titanium dioxide nano material that above-mentioned preparation method obtains, be the nanocrystal of polymolecularity, grain size is within 10 nanometers, and size uniformity, has higher photocatalysis Decomposition organic contamination physical performance.
Accompanying drawing explanation
Fig. 1: the X-ray powder diffraction pattern of the rare earth doping titanium dioxide nano material obtained by embodiment 2.
Fig. 2: the high-resolution-ration transmission electric-lens photo of the rare earth doping titanium dioxide nano material obtained by embodiment 2.
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 gram of urea, 0.5 gram of lanthanum nitrate hexahydrate is added successively in 80 milliliters of dehydrated alcohols.Add 12 milliliters of isopropyl titanates after stirring and dissolving, stir.Then in above-mentioned system, 7 ml deionized water are dripped while stirring, until form clear gel.Above-mentioned gel is put into the stainless steel autoclave of teflon lined, 170 degrees Celsius of lower hydro-thermal reactions 48 hours.By precipitated product deionized water wash after reaction terminates, until the pH of washings is in neutral, then carries out drying treatment, obtain the rare earth doped titanium dioxide nano material of target compound.
Gained rare earth doping titanium dioxide nano material is the nanocrystal of polymolecularity, and particle diameter is approximately 8 ~ 10 nanometers, size uniformity.0.1 gram of above-mentioned product reaches more than 99% to the degradation rate of 20 mg/litre methyl orange solutions in 40 minutes under the UV-light of 300 watts.
Embodiment 2:
0.5 gram of urea, 0.3 gram of lanthanum nitrate hexahydrate, 0.02 gram of six nitric hydrate cerium is added successively in 50 milliliters of dehydrated alcohols.Add 8 milliliters of positive four butyl esters of metatitanic acid after stirring and dissolving, stir.Then in above-mentioned system, 4 ml deionized water are dripped while stirring, until form clear gel.Above-mentioned gel is put into the stainless steel autoclave of teflon lined, 150 degrees Celsius of lower hydro-thermal reactions 24 hours.By precipitated product deionized water wash after reaction terminates, until the pH of washings is in neutral, then carries out drying treatment, obtain the rare earth doped titanium dioxide nano material of target compound.
Gained rare earth doping titanium dioxide nano material is the nanocrystal of polymolecularity, and particle diameter is approximately 5 ~ 7 nanometers, size uniformity.0.1 gram of above-mentioned product reaches more than 99% to the degradation rate of 20 mg/litre methyl orange solutions in 30 minutes under the UV-light of 300 watts.
Embodiment 3:
1.2 grams of urea, 0.1 gram of gadolinium nitrate hexahydrate, 0.05 gram of six nitric hydrate neodymium is added successively in 100 milliliters of dehydrated alcohols.Add 15 milliliters of tetraethyl titanates after stirring and dissolving, stir.Then in above-mentioned system, 8 ml deionized water are dripped while stirring, until form clear gel.Above-mentioned gel is put into the stainless steel autoclave of teflon lined, at 200 degrees celsius hydro-thermal reaction 16 hours.By precipitated product deionized water wash after reaction terminates, until the pH of washings is in neutral, then carries out drying treatment, obtain the rare earth doped titanium dioxide nano material of target compound.
Gained rare earth doping titanium dioxide nano material is the nanocrystal of polymolecularity, and particle diameter is approximately 7 ~ 9 nanometers, size uniformity.0.1 gram of above-mentioned product reaches more than 99% to the degradation rate of 20 mg/litre methyl orange solutions in 50 minutes under the UV-light of 300 watts.
Embodiment 4:
0.3 gram of urea, 0.08 gram of six nitric hydrate yttrium, 0.06 gram of six nitric hydrate samarium is added successively in 30 milliliters of dehydrated alcohols.Add 5 milliliters of positive four butyl esters of metatitanic acid after stirring and dissolving, stir.Then in above-mentioned system, 2 ml deionized water are dripped while stirring, until form clear gel.Above-mentioned gel is put into the stainless steel autoclave of teflon lined, 160 degrees Celsius of lower hydro-thermal reactions 36 hours.By precipitated product deionized water wash after reaction terminates, until the pH of washings is in neutral, then carries out drying treatment, obtain the rare earth doped titanium dioxide nano material of target compound.
Gained rare earth doping titanium dioxide nano material is the nanocrystal of polymolecularity, and particle diameter is approximately 6 ~ 9 nanometers, size uniformity.0.1 gram of above-mentioned product reaches more than 99% to the degradation rate of 20 mg/litre methyl orange solutions in 40 minutes under the UV-light of 300 watts.
Embodiment 5:
0.8 gram of urea, 0.15 gram of six nitric hydrate europium, 0.09 gram of six nitric hydrate erbium is added successively in 60 milliliters of dehydrated alcohols.Add 9 milliliters of isopropyl titanates after stirring and dissolving, stir.Then in above-mentioned system, 6 ml deionized water are dripped while stirring, until form clear gel.Above-mentioned gel is put into the stainless steel autoclave of teflon lined, at one hundred and twenty degrees centigrade hydro-thermal reaction 40 hours.By precipitated product deionized water wash after reaction terminates, until the pH of washings is in neutral, then carries out drying treatment, obtain the rare earth doped titanium dioxide nano material of target compound.
Gained rare earth doping titanium dioxide nano material is the nanocrystal of polymolecularity, and particle diameter is approximately 4 ~ 6 nanometers, size uniformity.0.1 gram of above-mentioned product reaches more than 99% to the degradation rate of 20 mg/litre methyl orange solutions in 50 minutes under the UV-light of 300 watts.
Embodiment 6:
1.5 grams of urea, 0.06 gram of six nitric hydrate terbium, 0.05 gram of ytterbium nitrate, 0.02 gram of six nitric hydrate thulium is added successively in 70 milliliters of dehydrated alcohols.Add 10 milliliters of positive four butyl esters of metatitanic acid after stirring and dissolving, stir.Then in above-mentioned system, 7 ml deionized water are dripped while stirring, until form clear gel.Above-mentioned gel is put into the stainless steel autoclave of teflon lined, 150 degrees Celsius of lower hydro-thermal reactions 30 hours.By precipitated product deionized water wash after reaction terminates, until the pH of washings is in neutral, then carries out drying treatment, obtain the rare earth doped titanium dioxide nano material of target compound.
Gained rare earth doping titanium dioxide nano material is the nanocrystal of polymolecularity, and particle diameter is approximately 5 ~ 8 nanometers, size uniformity.0.1 gram of above-mentioned product reaches more than 99% to the degradation rate of 20 mg/litre methyl orange solutions in 30 minutes under the UV-light of 300 watts.
Claims (1)
1. a preparation method for rare earth doped titanium dioxide nano material, is characterized in that, comprises the steps:
(1) in dehydrated alcohol, add urea, rare earth element nitrate, after stirring and dissolving, add liquid phase titanium source, stir and form homogeneous phase solution; Then in above-mentioned system, deionized water is dripped while stirring, until form clear gel;
(2) above-mentioned gel is put into the stainless steel autoclave of teflon lined, hydro-thermal reaction 12 ~ 48 hours at 120 ~ 200 DEG C; By precipitated product deionized water wash after reaction terminates, until the pH of washings is in neutral, then carries out drying treatment, obtain rare earth doped titanium dioxide nano material;
The urea quality added described in step (1) and reaction soln cumulative volume ratio are 0.1 gram/100 milliliters ~ 3 grams/100 milliliters;
Rare earth element nitrate described in step (1) is one in the cerous nitrate of hydration or non-hydrated, lanthanum nitrate, neodymium nitrate, Yttrium trinitrate, Gadolinium trinitrate, europium nitrate, Terbium trinitrate, samaric nitrate, thulium nitrate, Erbium trinitrate, ytterbium nitrate or its combination;
The rare earth element nitrate quality added described in step (1) is 0.001 gram/10 milliliters ~ 0.5 gram/10 milliliters with adding liquid phase titanium volume source ratio;
Liquid phase titanium source described in step (1) is one in positive four butyl esters of metatitanic acid, isopropyl titanate, tetraethyl titanate or its combination;
Liquid phase titanium source described in step (1) adds volume with reaction soln cumulative volume than being 5:100 ~ 30:100;
The deionized water volume added described in step (1) and reaction soln cumulative volume are than being 2:100 ~ 20:100.
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