CN103641148A - Method for preparing mesoporous cerium oxide powder by using sol-gel method - Google Patents
Method for preparing mesoporous cerium oxide powder by using sol-gel method Download PDFInfo
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- CN103641148A CN103641148A CN201310671603.XA CN201310671603A CN103641148A CN 103641148 A CN103641148 A CN 103641148A CN 201310671603 A CN201310671603 A CN 201310671603A CN 103641148 A CN103641148 A CN 103641148A
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- cerium oxide
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Abstract
The invention belongs to the technical field of crystal powder materials, and in particular relates to a method for preparing mesoporous cerium oxide powder by using a sol-gel method. According to the method provided by the invention, a mixture liquid consisting of ethanol, acetic acid, butanediol and citric acid is adopted as a template agent, and a novel synthesis route is provided for synthesis of the mesoporous cerium oxide powder. The template agent is a chemical reagent which is easy to obtain and low in cost; 2.30 Yuan is spent in preparing 1g of the mesoporous cerium oxide powder. The method provided by the invention has the following advantages: the preparation period is short, and the shortest reaction period is 6 hours; the process is controllable, i.e., only a calcining step needs to be accomplished under a high temperature condition, and the highest required temperature is 450 DEG C; the efficiency is high, i.e., 0.40g of the mesoporous cerium oxide powder can be produced from 1g of Ce(NO3)3.6H2O. The prepared mesoporous cerium oxide powder is small in grain, the average particle size is 5.00 mu m, the pore passage is small and uniform, 90% of the apertures are within 3.0-5.0nm.
Description
Technical field
The invention belongs to crystal powder technical field of material, be specifically related to a kind of method that sol-gel method is prepared mesoporous cerium oxide powder.
Background technology
Rare earth element is owing to having unique 4f electronics, and its compound has special optical, electrical, magnetic property.Wherein, the cerium oxide of fluorite type structure and sosoloid thereof, have the performances such as stronger storage oxygen and oxygen release ability and high temperature ionic conductivity, at catalysis, the energy, electronics, magnetics, superconduction, optics energy numerous areas, has huge development potentiality.Especially micro-nano cerium oxide powder, has Ce
4+/ Ce
3+two kinds of oxidation state (Ce
3+ce
4++ e).Under oxygen deprivation or reductive condition, a part of Ce on cerium oxide surface
4+be reduced into Ce
3+, and produce oxygen room, form a series of CeO with oxygen defect structure
2-xcompound, provides CO and HC to be oxidized needed oxygen.Under oxygen enrichment or oxidizing condition, Ce
3+can be oxidized to Ce
4+thereby, CeO
2-Xbe converted into CeO
2, realize the NO storing in oxygen, reduction vehicle exhaust
xobject.Mesoporous cerium oxide powder as high-specific surface area, the also well-regulated pore passage structure of tool, good chemical stability and to unique performances such as high loaded metal dispersity, show extremely strong oxygen function and the quick oxygen of the high temperature room diffusibility stored, at aspects such as fuel cell electrode, vehicle tail gas triple effect catalyzer and catalytic hydrogenation reactions, highlight wide application prospect.
The preparation research of nano-cerium oxide can trace back to the end of the eighties in last century, and the method for employing mainly comprises mechanochemical reaction, the precipitator method, electrochemical process, solvent-thermal method, hydrothermal method etc.Since 20 century 70s, template progressively grows up, and the method is relatively simple, controllability is strong, has become the main synthetic method of synthetizing micro-nano porous material at present.According to liquid crystal templated mechanism, synthesising mesoporous cerium oxide need add template as structure directing agent, by the synergy of template or the interaction between molecular self-assembling and inorganic precursor and template molecule, form stable molecule aggregates, utilize subsequently the methods such as calcining or solvent extraction that collaborative template agent is removed, finally form meso-hole structure.Zhang etc. utilize cerous nitrate as cerium source, and selected palmityl trimethyl ammonium chloride is template.The synthetic mesoporous cerium oxide of the method is homogeneous fluorite structure, and duct is even.But its building-up process need be in pH value crystallization 5 days under 11 environment, and the reaction times is longer, has affected further propagation and employment (J.H. Zhang, Y.Q. Yang, J.M. Shen, the J.A. Wang. Mesostrcutured CeO of the method
2and Pd/CeO
2nanophases:Templated synthesis, crystalline structure and catalysis properties. Journal of Molecular Catalysis A:Chemical, 2005,237 (1-2): 182-190).In employing polyethylene glycol-propylene glycol-polyoxyethylene glycol triblock polymers such as Qiang Qiang, do template, the tetraethoxy of take has the SBA-15 molecular sieve of meso-hole structure as silicon source Hydrothermal Synthesis, then take its as hard template, sucrose be the synthetic CMK-3 carbon material with order mesoporous structure of carbon source.Finally CMK-3 be impregnated in cerium nitrate solution, through super-dry, roasting, the synthetic cerium oxide powder with meso-hole structure.The preparation of SBA-15 molecular sieve need be at 550 ℃ roasting 5h, and CMK-3 carbon material need to complete carbonization process (Yu Qiangqiang by constant temperature 4h at 650 ℃, Liu Yuliang, He Tao, rope palm bosom. the synthetic and sign of meso-porous titanium dioxide cerium material. Journal of Yantai University, 2010,23 (3): 172-175).Yang Ru is used cerous sulfate as cerium source, and selected triethylamine and polyoxyethylene glycol are made template, synthetic mesoporous cerium oxide powder aperture be about 5nm left and right (Yang Ru, Liu Jianhong, Li Min. nonsurfactant synthesizes CeO
2mesoporous material. China rare earth journal, 2004,22 (6): 739-745).It is raw material that Tan Ninghui etc. be take ceric sulfate, diethylenetriamine, ammoniacal liquor is done precipitation agent, temperature of reaction is 80 ℃, digestion time reaches 12h, synthesising mesoporous cerium oxide (Tan Ninghui, Liu Yingliang, Xu Li. the precipitator method are prepared mesoporous ceria. Ji'nan University's journal, 2010,31 (1): 67-70).How further simplifying synthesis path, and realize the control in aperture, the specific surface area of increase powder, and then promote its catalytic performance, is the subject matter that needs solution.
Summary of the invention
The object of the present invention is to provide the preparation method of low, the simple to operate and mesoporous cerium oxide powder that is easy to control of a kind of cost.
For achieving the above object, the technical solution used in the present invention is:
Sol-gel method is prepared a method for mesoporous cerium oxide powder,
Use the mixed solution and the Ce (NO that by ethanol, acetic acid, butyleneglycol and citric acid, are formed
3)
36H
2o effect, forms gel; By gel calcining, obtain light yellow mesoporous cerium oxide powder.
Method of the present invention, adopts the mixed solution of ethanol, acetic acid, butyleneglycol and citric acid composition as template; For mesoporous cerium oxide powder synthetic provides new synthetic route.Ethanol, acetic acid, butyleneglycol and citric acid solution are the chemical reagent easily obtaining, and with low cost.
In above-mentioned preparation method, raw materials used wherein a kind of presentation mode is:
By Ce (NO
3)
36H
2o is mixed with the Ce (NO that concentration is 0.30～0.65mol/l
3)
36H
2o deionized water solution;
Citric acid is mixed with to the citric acid deionization solution that concentration is 0.17～0.26mol/l.
The mol ratio of described ethanol, acetic acid, butyleneglycol is 35～50:2～5:1;
The total amount of ethanol, acetic acid and butyleneglycol and the mass ratio between citric acid are about 17～28:1;
The total amount of ethanol, acetic acid and butyleneglycol and Ce (NO
3)
36H
2mass ratio between O is about 4.0～4.6:1.
Described gel, the wherein a kind of condition that forms gel is: mixed solution and Ce (NO
3)
36H
2o stirs 2～4h at 60～80 ℃, then at 50～70 ℃, is incubated 2.5～5h.
Described calcining, wherein a kind of calcination condition is: temperature is 180-450 ℃.
Above-mentioned preparation method, wherein a kind of concrete operations mode is:
By ethanol, acetic acid, butyleneglycol and Ce (NO
3)
36H
2o mixes, and then adds citric acid, at 60～80 ℃ of stirred in water bath 2～4h, then is placed in 50～70 ℃ of drying ovens and is incubated 2.5～5h, obtains gel;
Gel is placed in to retort furnace, is first heated to 180～210 ℃, insulation 15～30min, then the heat-up rate with 10 ℃/min is heated to 400～450 ℃, insulation 0.5～1.5h; Cool to room temperature with the furnace, obtain light yellow mesoporous cerium oxide powder.
Beneficial effect
Further expanded the preparation method of mesoporous cerium oxide powder;
Present method cost is low, preparation 1g mesoporous cerium oxide powder, and raw materials used cost is 2.30 yuan, heating is 1.50 yuan by energy cost,
Preparation cycle is short, and the short reaction cycle is 6h;
Technique is controlled, and only calcining step need to complete under hot conditions, and required top temperature is 450 ℃;
Efficiency is high, every 1gCe (NO
3)
36H
2o can output 0.40g mesoporous cerium oxide powder;
And simple process easily control be suitable for industrialization, significant to the preparation of cerium oxide;
Mesoporous cerium oxide powder, particle is little, and median size is 5.00 μ m, and duct is little and even, and 90% aperture size distribution range is at 3.0～5.0nm.
Accompanying drawing explanation
Fig. 1 is the XRD diffractogram of the cerium oxide powder of embodiment 1 preparation;
Fig. 2 is the scanning electron microscope picture of the mesoporous cerium oxide powder of embodiment 1 preparation.
Embodiment
Embodiment 1
Step 1: prepare raw material
By the analytically pure Ce (NO of 3.91g
3)
36H
2o is dissolved in deionized water to obtain the concentration Ce (NO that is 0.30mol/l
3)
3solution; 0.98g analytical pure citric acid is dissolved in deionized water to obtain to the concentration citric acid solution that is 0.17mol/l; Ethanol, acetic acid, butyleneglycol are mixed with to 17.14g mixed solution by 35:2.5:1 mol ratio;
Step 2: preparation
By mixed solution and Ce (NO
3)
3solution mixing and stirring, then adds citric acid solution, in 65 ℃ of water-baths, utilizes magnetic agitation 4h to mix, and is then placed in 55 ℃ of drying ovens and is incubated 4.5h, obtains gel; Gained gel is placed in to retort furnace, is first heated to 180 ℃ of insulation 30min, then the heat-up rate with 10 ℃/min is heated to 400 ℃ of insulation 1.5h, cools to room temperature with the furnace; Obtain the light yellow mesoporous cerium oxide powder of 1.50g.
The whole preparation process used time is about 11 hours, has greatly shortened preparation cycle, has improved production efficiency.In reaction process, 100 ℃ of above operating times are 145min, greatly reduce energy consumption; Saved production cost.
The mesoporous cerium oxide powder of gained is measured with the German Brooker production D8 ADVANCE of company type X-ray diffractometer, and result as shown in Figure 1.Obtain the good homogeneous fluorite structure cerium oxide powder of crystallinity.The hot field emission scanning electron microscope of FEI QUANTA FEG 250 model that the microscopic appearance of this sample adopts U.S. FEI Co. to produce is analyzed, and result is as Fig. 2.As can be seen from the figure on prepared cerium oxide powder, contain the mesoporous of a large amount of apertures homogeneous.
Embodiment 2
Step 1: prepare raw material
By the analytically pure Ce (NO of 7.45g
3)
36H
2o is dissolved in deionized water to obtain the concentration Ce (NO that is 0.429mol/l
3)
3solution; 1.70g analytical pure citric acid is dissolved in deionized water to obtain to the concentration citric acid solution that is 0.221mol/l; Ethanol, acetic acid, butyleneglycol are mixed with to 32.48g mixed solution by 42:3:1 mol ratio;
Step 2: preparation
By mixed solution and Ce (NO
3)
3solution mixing and stirring, then adds citric acid solution, in 70 ℃ of water-baths, utilizes magnetic agitation 3h to mix, and is then placed in 60 ℃ of drying ovens and is incubated 4h, obtains gel; Gained gel is placed in to retort furnace, is first heated to 200 ℃ of insulation 20min, then the heat-up rate with 10 ℃/min is heated to 415 ℃ of insulation 1h, cools to room temperature with the furnace; Obtain the light yellow mesoporous cerium oxide powder of 2.90g.
The whole preparation process used time is about 9 hours, has greatly shortened preparation cycle, has improved production efficiency.In reaction process, 100 ℃ of above operating times are 100min, greatly reduce energy consumption; Saved production cost.
Embodiment 3
Step 1: prepare raw material
By the analytically pure Ce (NO of 15.62g
3)
36H
2o is dissolved in deionized water to obtain the concentration Ce (NO that is 0.60mol/l
3)
3solution; 2.58g analytical pure citric acid is dissolved in deionized water to obtain to the concentration citric acid solution that is 0.25mol/l; Ethanol, acetic acid, butyleneglycol are mixed with to 69.68g mixed solution by 50:5:1 mol ratio;
Step 2: preparation
By mixed solution and Ce (NO
3)
3solution mixing and stirring, then adds citric acid solution, in 80 ℃ of water-baths, utilizes magnetic agitation 2h to mix, and is then placed in 70 ℃ of drying ovens and is incubated 2.5h, obtains gel; Gained gel is placed in to retort furnace, is first heated to 210 ℃ of insulation 15min, then the heat-up rate with 10 ℃/min is heated to 450 ℃ of insulation 0.5h, cools to room temperature with the furnace; Obtain the light yellow mesoporous cerium oxide powder of 6.15g.The whole preparation process used time is about 6 hours, has greatly shortened preparation cycle, has improved production efficiency.In reaction process, 100 ℃ of above operating times are 75min, greatly reduce energy consumption; Saved production cost.
Claims (6)
1. sol-gel method is prepared a method for mesoporous cerium oxide powder, it is characterized in that,
Use the mixed solution and the Ce (NO that by ethanol, acetic acid, butyleneglycol and citric acid, are formed
3)
36H
2o effect, forms gel; By gel calcining, obtain light yellow mesoporous cerium oxide powder.
2. method according to claim 1, is characterized in that,
By Ce (NO
3)
36H
2o is mixed with the Ce (NO that concentration is 0.30～0.65mol/l
3)
36H
2o deionized water solution;
Citric acid is mixed with to the citric acid deionization solution that concentration is 0.17～0.26mol/l.
3. method according to claim 1, is characterized in that,
The mol ratio of described ethanol, acetic acid, butyleneglycol is 35～50:2～5:1;
The total amount of ethanol, acetic acid and butyleneglycol and the mass ratio between citric acid are about 17～28:1;
The total amount of ethanol, acetic acid and butyleneglycol and Ce (NO
3)
36H
2mass ratio between O is about 4.0～4.6:1.
4. method according to claim 1, is characterized in that,
The formation condition of described gel is: mixed solution and Ce (NO
3)
36H
2o stirs 2～4h at 60～80 ℃, then at 50～70 ℃, is incubated 2.5～5h.
5. method according to claim 1, is characterized in that,
Described calcination condition is: temperature is 180-450 ℃.
6. according to the method described in claim 1,2,3 or 5, it is characterized in that, concrete operations mode is:
By ethanol, acetic acid, butyleneglycol and Ce (NO
3)
36H
2o mixes, and then adds citric acid, at 60～80 ℃ of stirred in water bath 2～4h, then is placed in 50～70 ℃ of drying ovens and is incubated 2.5～5h, obtains gel;
Gel is placed in to retort furnace, is first heated to 180～210 ℃, insulation 15～30min, then the heat-up rate with 10 ℃/min is heated to 400～450 ℃, insulation 0.5～1.5h; Cool to room temperature with the furnace, obtain light yellow mesoporous cerium oxide powder.
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|---|---|---|---|---|
| CN109437326A (en) * | 2018-12-19 | 2019-03-08 | 渤海大学 | The preparation method of the adjustable mesoporous metal composite oxide nano-material in aperture |
| CN111620362A (en) * | 2020-04-24 | 2020-09-04 | 广西科学院 | Microwave preparation method of mesoporous holmium oxide powder |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102942205A (en) * | 2012-11-20 | 2013-02-27 | 陕西科技大学 | Morphology controllable nanometer CeO2 preparation method |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109437326A (en) * | 2018-12-19 | 2019-03-08 | 渤海大学 | The preparation method of the adjustable mesoporous metal composite oxide nano-material in aperture |
| CN111620362A (en) * | 2020-04-24 | 2020-09-04 | 广西科学院 | Microwave preparation method of mesoporous holmium oxide powder |
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