CN101391753B - Method for preparing mesoporous metallic oxide material - Google Patents
Method for preparing mesoporous metallic oxide material Download PDFInfo
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- CN101391753B CN101391753B CN2008102022832A CN200810202283A CN101391753B CN 101391753 B CN101391753 B CN 101391753B CN 2008102022832 A CN2008102022832 A CN 2008102022832A CN 200810202283 A CN200810202283 A CN 200810202283A CN 101391753 B CN101391753 B CN 101391753B
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Abstract
The invention provides a mesoporous metal oxide preparation method belonging to the inorganic nano material synthesis field. The invention adds a precursor solution into a mesoporous template powder so as to lead the precursor solution to penetrate into mesoporous channels through capillary force. After the following drying and heating, the mesoporous template is removed to obtain the corresponding mesoporous oxide. The preparation condition is simple; the cost is low; the productivity is high; the operation is easy and the environment protection can be guaranteed; and the prepared metal oxide is better, the mesopore structure is ordered and the wall is crystallized.
Description
Technical field
The invention provides a kind of mesoporous metal oxide preparation method, belong to the synthetic field of inorganic nano material.
Background technology
Mesopore metal oxide is owing to its unique catalysis, optics and electrology characteristic, so wide application prospect is being arranged aspect heterogeneous catalysis, transmitter and the electrode materials.Therefore the synthetic research focus that becomes scientists in recent years of mesopore metal oxide has proposed a lot of synthetic methods." soft template method " and " hard template method " arranged substantially.The mesopore metal oxide of soft template method preparation, though meso-hole structure is preferably arranged, mesoporous body of wall is amorphous state or half hitch crystalline state, this has limited the application of prepared mesopore metal oxide greatly; Received a lot of concerns so hard template method prepares mesoporous metallic oxide material, developed many compound methods, wherein had: solvent pairs method, Microwave Digestion, organically-modified method and multiple maceration.But the solvent (as: normal hexane, ethanol) that the needs that these methods have are a large amount of; The suitable surface-treated of the needs that have.Therefore, these building-up processes generally need long generated time, and need a large amount of solvent or silane coupling agent, and these all are unfavorable for reducing cost, and enhance productivity and environment protection." the accurately progressively dampening under the control " that we propose can be strong overcome these shortcomings.The concrete report that does not also have this method at present both at home and abroad.
Summary of the invention
The purpose of this invention is to provide a kind of pervasive and economic preparation mesopore metal oxide method.
The preparation technology of mesopore metal oxide is described below:
(1) prepares the mesopore silicon oxide powder according to the bibliographical information mode, comprise KIT-6, SBA-15, MCM-41, MCM-48 etc.Here selecting KIT-6 and SBA-15 is template.
(2) inorganic precursors comprises Xiao Suangu, iron nitrate, cupric nitrate, nickelous nitrate, cerous nitrate, phospho-wolframic acid, phospho-molybdic acid, manganous nitrate.According to the physical properties of precursor, be configured to unsaturation solution, as: the ethanolic soln concentration range of Xiao Suangu is 2.0-4.0mol/L, and the ethanolic soln concentration range of nickelous nitrate is 2.0-4.2mol/L; According to the 1g KIT-6 of preparation or the mesoporous pore volume of SBA-15, the solution of getting proper volume drips.Here the volume number of selecting solution is 1.1-1.3 with the ratio of mesopore silicon oxide pore volume number.
(3) with inorganic precursor solution with being added drop-wise in the mesopore silicon oxide powder, the control rate of addition is at 0.5-1.0mL/min.
(4) powder after will dripping is put into baking oven and is dried.
(5) powder calcination after the oven dry makes inorganic precursors be decomposed into corresponding metal oxide.The calcination temperature range of Xiao Suangu is 300-550 ℃, and the calcination temperature range of nickelous nitrate is 300-550 ℃, and the calcination temperature range of manganous nitrate is 300-650 ℃.
(6) use hot sodium hydroxide solution or hydrofluoric acid solution to remove the silicon oxide template, select sodium hydroxide solution to remove template here.
(7) filter and, just obtained corresponding mesopore metal oxide powder with drying after the washed with de-ionized water.
Adopt the preparation technology progressively drip precursor solution, make precursor solution to get into mesopore orbit by capillary force, and the discharge of also can taking advantage of a situation of the gas in the duct.
Owing to be to drip precursor solution comparatively slowly, so solvent has a certain amount of volatilization, separate out plugging hole road junction, back in order not make solute, the precursor solution of configuration is a unsaturation solution here.
Characteristics of the present invention are:
(1) adopted " the accurately progressively dampening under the control " to prepare mesopore metal oxide.Simple to operate, cost is low, output big be beneficial to environment protection.
(2) this is a kind of pervasive method, can be used for preparing multiple mesopore metal oxide.
(3) with the mesopore metal oxide of this method preparation, mesoporous order degree is high, and specific surface area is big, narrow and the mesoporous body of wall with crystallization of pore size distribution.
(4) synthetic mesopore metal oxide, in catalysis, transmitter preparation and electrode materials field have broad application prospects.
Description of drawings
Fig. 1 KIT-6, Co
3O
4-1, Co
3O
4-2 and Co
3O
4-3 little angle XRD.Can find out that from little angle XRD the quality of the mesoporous order of prepared powder blue is followed successively by Co
3O
4-2, Co
3O
4-1, Co
3O
4-3.
Fig. 2 Co
3O
4-1, Co
3O
4-2 and Co
3O
4-3 wide-angle XRD.Can find out that from wide-angle XRD prepared powder blue is a crystal form.
Fig. 3 Co
3O
4-1 TEM image.The powder blue that can intuitively see preparation from transmission electron microscope observing has orderly meso-hole structure.
Fig. 4 Co
3O
4-2 TEM image.
The little angle XRD of Fig. 5 NiO.
The wide-angle XRD of Fig. 6 NiO.
The TEM image of Fig. 7 NiO.
Fig. 8 Mn
2O
3Little angle XRD.
Fig. 9 Mn
2O
3Wide-angle XRD.
Figure 10 Mn
2O
3The TEM image.
Figure 11 Co
3O
4Little angle XRD.
Figure 12 Co
3O
4Wide-angle XRD.
Figure 13 Co
3O
4The TEM image.
Figure 14 Co
3O
4-3 TEM image.
Can intuitively find prepared Co from transmission electron microscope
3O
4-3 mesoporous order is than Co
3O
4-1 and Co
3O
4-2 is poor.
Specific embodiment
Further specify the present invention through embodiment below, but be not limited to following embodiment.
According to bibliographical information, (pore volume is 1.2cm to have prepared KIT-6 mesopore silicon oxide template
3/ g).The cobalt nitrate hexahydrate of 1.8g is dissolved in the absolute ethyl alcohol of 1.5mL, and in the inhalation syringe.Get the KIT-6 template of 1g, then cobalt nitrate solution is added with the mode that drips.The baking oven of the powder that obtains being put into 70 ℃ is dried, and the powder after the oven dry is put into resistance furnace with the heat-up rate to 500 of 2 ℃/min ℃ and under this temperature, keep 2h.The gained powder is removed silicon oxide template twice with 80 ℃ 2M sodium hydroxide solution, filters and with drying behind the deionized water wash, finally obtains mesoporous powder blue (Co
3O
4-1).The specific surface area of this sample is 97.7m
2/ g, the most probable aperture is 3.3nm.
Mesoporous powder blue (the Co of gained
3O
4-1) structural characterization is seen accompanying drawing 1,2 and 3.
According to technical process said (with embodiment 1), but the powder that has infiltrated presoma is put into resistance furnace with the heat-up rate to 300 of 2 ℃/min ℃ and under this temperature, keep 2h.Repeat embodiment 1 (precursor solution of dropping is that the cobalt nitrate hexahydrate of 1.6g is dissolved in the ethanol of 1.3mL) then, resulting mesoporous powder blue is Co
3O
4-2.The specific surface area of this sample is 79.2m
2/ g, the most probable aperture is 2.8nm.
Mesoporous powder blue (the Co of gained
3O
4-2) structural characterization is seen accompanying drawing 1,2 and 4.
According to technical process said (with embodiment 1), the six water nickelous nitrates of 1.93g are dissolved in the absolute ethyl alcohol of 1.5mL, and in the inhalation syringe.Other have obtained mesoporous nickel oxide (NiO) with embodiment 1.The specific surface area of this sample is 73.6m
2/ g, the most probable aperture is 2.8nm.
The structural characterization of the mesoporous nickel oxide (NiO) of gained is seen accompanying drawing 5,6 and 7.
Said according to technical process; Here precursor solution is the manganese nitrate aqueous solution (50wt%) of 1.3mL; Be added drop-wise in the 1g KIT-6 template powder, put into 70 ℃ of baking ovens and dry, then in resistance furnace with the heat-up rate to 200 of 2 ℃/min ℃ and under this temperature, keep 2h.Repeat said process then, but precursor solution is got the manganese nitrate aqueous solution of 1.1mL, after the oven dry; During thermal treatment with the heat-up rate to 600 of 2 ℃/min ℃ and under this temperature, keep 2h.Remove the silicon oxide template at last, and, obtained mesoporous manganic oxide (Mn with the deionized water wash oven dry
2O
3).The specific surface area of this sample is 65.3m
2/ g, the most probable aperture is 2.9nm.
The structural characterization of the mesoporous manganic oxide of gained is seen accompanying drawing 8,9 and 10.
In order to explain that said technical process also is adapted to the mesoporous silicon oxide template of other structures, also is applied to said flow process among the SBA-15.
According to bibliographical information, (pore volume is 1.0cm to have prepared SBA-15 mesopore silicon oxide template
3/ g).The cobalt nitrate hexahydrate of 1.5g is dissolved in the absolute ethyl alcohol of 1.3mL, and in the inhalation syringe.Get the SBA-15 template of 1g, then cobalt nitrate solution is added with the mode that drips.The baking oven of the powder that obtains being put into 70 ℃ is dried, and the powder after the oven dry is put into resistance furnace with the heat-up rate to 500 of 2 ℃/min ℃ and under this temperature, keep 2h.The gained powder is removed silicon oxide template twice with 80 ℃ 2M sodium hydroxide solution, filters and with drying behind the deionized water wash, finally obtains mesoporous powder blue (Co
3O
4).The specific surface area of this sample is 71m
2/ g, the most probable aperture is 3.7nm.
Mesoporous powder blue (the Co of gained
3O
4) structural characterization see accompanying drawing 11,12 and 13.
Comparative Examples 1
According to technical process said (with embodiment 1), (pore volume is 2.16cm but adopt 1.8g KIT-6
3) as template, the cobalt nitrate hexahydrate of getting 1.8g simultaneously is dissolved in the absolute ethyl alcohol of 1.5mL as precursor solution (the precursor solution volume is less than the template pore volume), other are with embodiment 1, and the specific surface area of the mesoporous powder blue of gained is 85.7m
2/ g, the most probable aperture is 2.6nm.
The result shows the mesoporous powder blue (Co of gained
3O
4-3) meso-hole structure does not have good among embodiment 1 and the embodiment 2, and it is synthetic that this has explained that also accurate control precursor solution amount is of value to the high mesopore metal oxide of the degree of order.Relevant structural characterization is seen accompanying drawing 1,2 and 14.
Claims (7)
1. the preparation method of a mesoporous metallic oxide material comprises the steps:
(1) be template with the mesopore silicon oxide powder;
(2) configuration inorganic precursors unsaturation solution; Described inorganic precursors comprises Xiao Suangu, iron nitrate, cupric nitrate, nickelous nitrate, cerous nitrate, phospho-wolframic acid, phospho-molybdic acid or manganous nitrate; The volume number of selection solution is 1.1-1.3 with the ratio of mesopore silicon oxide pore volume number;
(3) with inorganic precursor solution with being added drop-wise in the mesopore silicon oxide powder, the control rate of addition adds hot sodium hydroxide solution or hydrofluoric acid solution again and removes the silicon oxide template at 0.5-1.0mL/min;
(4) powder after will dripping is put into baking oven oven dry, calcining.
2. by the preparation method of the described a kind of mesoporous metallic oxide material of claim 1, it is characterized in that preferred sodium hydroxide solution removal template.
3. by the preparation method of claim 1 or 2 described a kind of mesoporous metallic oxide materials, it is characterized in that described mesopore silicon oxide powder is MCM-41, SBA-15, KIT-6 or MCM-48.
4. by the preparation method of the described a kind of mesoporous metallic oxide material of claim 3, it is characterized in that described mesopore silicon oxide powder is KIT-6 or SBA-15.
5. by the preparation method of claim 1 or 2 described a kind of mesoporous metallic oxide materials, it is characterized in that described Xiao Suangu calcining temperature is 300-550 ℃.
6. by the preparation method of claim 1 or 2 described a kind of mesoporous metallic oxide materials, it is characterized in that described nickelous nitrate calcining temperature is 300-550 ℃.
7. by the preparation method of claim 1 or 2 described a kind of mesoporous metallic oxide materials, it is characterized in that described manganous nitrate calcining temperature is 300-650 ℃.
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| CN106082346A (en) * | 2016-06-21 | 2016-11-09 | 苏州帝瀚环保科技股份有限公司 | The preparation method of meso-porous titanium dioxide manganese |
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| CN110586151B (en) * | 2019-08-14 | 2022-12-06 | 中国科学院宁波材料技术与工程研究所 | Preparation method of ordered mesoporous transition metal nitride |
| CN110801858B (en) * | 2019-10-29 | 2021-12-07 | 中国科学院山西煤炭化学研究所 | Catalyst for preparing carbonyl compound by catalyzing benzyl compound oxidation, preparation method and application thereof |
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| CN113620334B (en) * | 2021-08-20 | 2022-08-09 | 武汉大学 | Dendritic ordered mesoporous copper oxide nano material and preparation method and application thereof |
| CN116120168B (en) * | 2022-09-20 | 2024-05-14 | 湖北泰盛化工有限公司 | Preparation process for catalytic synthesis of 2, 4-D |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1431144A (en) * | 2003-01-09 | 2003-07-23 | 复旦大学 | Method for preparing nano line of oxide of transition metals and nano crystals with multi-holes in 3D |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1431144A (en) * | 2003-01-09 | 2003-07-23 | 复旦大学 | Method for preparing nano line of oxide of transition metals and nano crystals with multi-holes in 3D |
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