CN115385387A - Defect-rich mesoporous metal oxide with high specific surface area and preparation method and application thereof - Google Patents

Defect-rich mesoporous metal oxide with high specific surface area and preparation method and application thereof Download PDF

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CN115385387A
CN115385387A CN202210930242.5A CN202210930242A CN115385387A CN 115385387 A CN115385387 A CN 115385387A CN 202210930242 A CN202210930242 A CN 202210930242A CN 115385387 A CN115385387 A CN 115385387A
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mesoporous
metal oxide
surface area
specific surface
silica
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顾栋
宋述华
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Wuhan University WHU
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G51/00—Compounds of cobalt
    • C01G51/04—Oxides; Hydroxides
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
    • C01F17/00—Compounds of rare earth metals
    • C01F17/10—Preparation or treatment, e.g. separation or purification
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
    • C01F17/00—Compounds of rare earth metals
    • C01F17/20—Compounds containing only rare earth metals as the metal element
    • C01F17/206—Compounds containing only rare earth metals as the metal element oxide or hydroxide being the only anion
    • C01F17/224—Oxides or hydroxides of lanthanides
    • C01F17/235—Cerium oxides or hydroxides
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G49/00—Compounds of iron
    • C01G49/02—Oxides; Hydroxides
    • C01G49/06—Ferric oxide (Fe2O3)
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G53/00—Compounds of nickel
    • C01G53/04—Oxides; Hydroxides
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/12—Surface area
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/14—Pore volume

Abstract

The invention discloses a defect-rich mesoporous metal oxide with a high specific surface area, and a preparation method and application thereof. The invention adopts a designed double-hard template method, takes mesoporous silica as a first hard template and silica nanoparticles generated in situ as a second hard template, simultaneously fills inorganic metal salt and silica nanoparticle precursors into pores of the mesoporous silica template, directly converts the inorganic metal salt into corresponding metal oxide and simultaneously converts the silica precursors into silica nanoparticles by roasting in the air, and then uses sodium hydroxideThe solution removes the two silicon dioxide templates simultaneously to finally obtain the mesoporous metal oxide nano material rich in defects. The preparation method is simple and universal, and the prepared mesoporous metal oxide has high specific surface area (150-370 m) 2 g ‑1 ) Rich structural defects, interpenetrated mesoporous channels and the like, and has great application potential in the fields of catalysis, energy sources and the like.

Description

Defect-rich mesoporous metal oxide with high specific surface area and preparation method and application thereof
Technical Field
The invention relates to the technical field of porous materials, in particular to a preparation method and application of a defect-rich mesoporous metal oxide with a high specific surface area.
Background
The metal oxide has good oxidation-reduction performance and stability, abundant reserves and low price, and has wide application in the fields of catalytic energy sources and the like. In the field of catalysis, the catalytic performance of metal oxides is closely related to composition, morphology and crystal structure. Introducing a mesoporous structure to fully expose more active sites and accelerate mass transfer is an effective strategy for improving the catalytic performance; in addition, increasing the defect concentration on the surface of the material is also one of the effective methods for improving the catalytic activity.
The mesoporous metal oxide integrates the unique properties of high specific surface area, rich pore channels, variable valence state and the like of the mesoporous material, and has wide application prospect in the fields of catalysis, adsorption, energy storage, conversion and the like. At present, methods for preparing mesoporous metal oxides mainly include a soft template method and a hard template method. The soft template method is to use a surfactant or an organic polymer as a structure directing agent to obtain mesoporous metal oxide through the processes of self-assembly with a metal precursor and the like. The method relates to a complex metal salt hydrolysis process, is easily influenced by conditions such as pH, temperature and the like, has harsh synthesis conditions, and has the defects that a mesostructure is easy to collapse in the process of removing the surfactant, and the like, thereby limiting the wide application of the method. The hard template method takes rigid materials such as mesoporous silica or mesoporous carbon as templates, the method is relatively simple and controllable, but the specific surface area and the pore volume of the prepared material are often low due to the fact that metal oxide nanoparticles are easy to sinter in the calcining process, and the practical application of mesoporous metal oxides is limited to a certain extent.
Disclosure of Invention
In view of the above technical problems, the present invention aims to provide a preparation method and application of a defect-rich mesoporous metal oxide with a high specific surface area.
The invention provides a preparation method of a defect-rich mesoporous metal oxide with high specific surface area, which comprises the following steps:
1) Preparing a mesoporous silica template by a hydrothermal method;
2) Preparing a precursor solution: adding inorganic metal salt and silicon oxide precursor into an acid solution or an alkali solution, and fully and uniformly stirring to obtain a mixed solution A;
3) Adding mesoporous silica into the mixed solution A, fully stirring and drying to obtain a metal salt-silica composite;
4) Roasting the metal salt-silicon dioxide compound, and removing a silicon dioxide template by using an alkali solution to obtain a defect-rich mesoporous metal oxide with a high specific surface area;
further, in the step 1), the mesoporous silica template material having abundant silicon hydroxyl groups includes SBA series (e.g., SBA-15), KIT series (e.g., KIT-6), FSM series, FDU series (e.g., FDU-12), MCM series (e.g., MCM-41), MCF, silica gel, and the like.
Further, in step 2), the inorganic metal salt includes any one or more of ferric nitrate, cobalt nitrate, nickel nitrate, cerium nitrate, manganese nitrate, and chromium nitrate, and the silicon oxide precursor includes: methyl orthosilicate, ethyl orthosilicate, propyl orthosilicate, isopropyl orthosilicate, butyl orthosilicate, sodium silicate and water glass. The nitrates have good solubility in solution, can be mixed with silicon oxide precursor, and can be hydrolyzed gradually in appropriate acid (alkali) solution to form monosilicic acid Si (OH) 4 This hydroxyl-rich silicic acid is capable of interacting with metal cations. In addition, each nitrate has poor thermal stability, and can be completely decomposed into the corresponding metal oxide by appropriate heating in air.
Further, in the step 2), the use ratio of the inorganic metal salt, the silica precursor and the acid solution (alkali solution) is 1g to 5 g.
Further, in the step 2), the defect concentration of the mesoporous metal oxide nano material is regulated and controlled by changing the adding amount of the silicon oxide precursor.
Furthermore, in the range of the usage ratio of the inorganic metal salt, the silicon oxide precursor and the acid solution (alkali solution) being 1g.
Further, in the step 3), the dosage ratio of the mesoporous silica template to the mixed solution a is 1g:10-30mL, preferably in a 1g:20mL.
Further, in the step 3), the stirring temperature is 10-90 ℃, the stirring time is 0.5-48h, and the drying temperature is 40-100 ℃.
Further, in the step 4), the calcination temperature is 200-1000 ℃, the alkali solution is NaOH, KOH solution or ammonia water, diethylamine and the like, the concentration is 0.1-12M, and the reaction temperature is 10-90 ℃.
The invention provides a double-hard template method, and provides a universal method for synthesizing mesoporous metal oxide with high specific surface area. The method takes two kinds of silicon dioxide (one is directly synthesized mesoporous silicon dioxide such as SBA-15/MCF and the like, and the other is silicon dioxide nano particles formed by in-situ hydrolysis of silicon sources such as silicon oxide precursors such as tetraethyl orthosilicate and the like) with different sources as a hard template, inorganic metal salts and silicon oxide nano particle precursors (tetraethyl orthosilicate and the like) are simultaneously filled into pore channels of the mesoporous silicon dioxide template, the inorganic metal salts are directly converted into corresponding metal oxides by roasting in the air, meanwhile, the silicon oxide precursors are converted into silicon oxide nano particles, and a large number of pore defects can be formed inside a framework structure of the mesoporous metal oxides after alkali etching, so that the prepared mesoporous metal oxides have high specific surface area and can provide rich active sites for catalytic reaction. Wherein, the defect-rich mesoporous Co with high specific surface area 3 O 4 The catalyst shows excellent CO low-temperature catalytic oxidation activity.
The silicon oxide precursor, i.e. the inorganic silicon source, is hydrolyzed under suitable acidic or alkaline conditions to form the corresponding monosilicic acid Si (OH) 4 The monosilicic acid rich in hydroxyl and metal cations interact and are filled into the mesoporous pore canal together, and the both are uniformly dispersed in the mesoporous pore canal. After roasting, the generated silicon oxide nano particles are embedded into a metal oxide framework,forming a structure similar to a cement-brick structure. At this time, the amorphous silica nanoparticles act as a "glue" to bind the crystallized metal oxide nanoparticles in the mesoporous framework while inhibiting them from sintering seriously at high temperature calcination. In the subsequent alkali etching, both the original silica template and the in-situ generated silica nanoparticles can be removed, thereby forming a large number of structural defects. In addition, the content of monosilicic acid after hydrolysis can be regulated and controlled by changing the adding amount of the inorganic silicon source, and after calcination, the content of the silicon oxide nano particles embedded into the metal oxide skeleton is changed, so that the structural defects formed after alkali etching are correspondingly changed.
The second aspect of the present invention provides a defect-rich mesoporous metal oxide prepared using the method of the first aspect.
In a third aspect, the invention provides the use of the defect-rich mesoporous metal oxide of the second aspect in catalyzing the low-temperature oxidation of CO.
The invention has the following beneficial effects:
1) According to the method, the mesoporous silicon dioxide and the silicon dioxide formed by hydrolyzing the inorganic silicon source are used as templates, the two silicon dioxide templates can be synchronously etched through the alkali solution, and multi-step operation is avoided;
2) Silicon dioxide generated by in-situ hydrolysis of an inorganic silicon source is embedded into a metal oxide mesoporous framework, so that sintering of metal oxide nanoparticles can be effectively inhibited in the high-temperature calcination process; in addition, after the silicon dioxide is etched by alkali, a large number of hole defects can be formed inside the metal oxide skeleton;
3) The defect concentration of the mesoporous metal oxide nano material can be regulated and controlled by changing the addition of the inorganic silicon source;
4) The prepared mesoporous metal oxide nano material has rich defects, high specific surface area and mutually communicated pore channel structures, and can fully expose a large number of active sites;
4) The synthesis method is simple and controllable, and the mesoporous metal oxide prepared by the method is expected to play an important role in the fields of catalysis, energy, sensing and the like.
Drawings
FIG. 1 is a defect-rich high specific surface area mesoporous Co prepared in example 1 3 O 4 N of (a) 2 Adsorption-desorption isotherms and (b) TEM images;
FIG. 2 is a diagram of defect-rich mesoporous Fe with high specific surface area prepared in example 2 2 O 3 N of (a) 2 Adsorption-desorption isotherms and (b) TEM images;
FIG. 3 shows the (a) N of the defect-rich mesoporous NiO with high specific surface area prepared in example 3 2 Adsorption-desorption isotherms and (b) TEM images;
FIG. 4 is a high specific surface area mesoporous CeO enriched with defects prepared in example 4 2 N of (a) 2 Adsorption-desorption isotherms and (b) TEM images;
FIG. 5 shows (a) N of mesoporous CuO prepared in comparative example 1 2 Adsorption-desorption isotherms and (b) TEM images;
FIG. 6 shows defect-rich mesoporous Co with high specific surface area prepared in example 1 3 O 4 CO oxidation activity of (3).
Detailed Description
In order to more clearly illustrate the problems to be solved by the present invention, the following further describes the specific implementation steps of the present invention with reference to the attached drawings, and the content of the present invention is not limited thereto at all.
Example 1
1) Preparing a mesoporous silica SBA-15 template: taking 20.0g of block copolymer P123, adding 650mL of deionized water and 100mL of concentrated hydrochloric acid (37 wt%), stirring in a water bath at 38 ℃ for 2h, adding 41.6g of tetraethyl orthosilicate, stirring at 38 ℃ for 24h, transferring to a hydrothermal kettle after stirring, carrying out hydrothermal treatment at 110 ℃ for 24h, cooling, carrying out suction filtration, and drying at 50 ℃ to obtain white powder. 8.0g of white powder was dispersed in 120mL of concentrated HNO 3 (65 wt%) and 40mL of hydrogen peroxide (35 wt%) solution, heating to 80 ℃ and refluxing for 3h, and finally filtering, washing and drying to obtain the mesoporous silica substrate material rich in silicon hydroxyl.
2) Mesoporous Co rich in defects 3 O 4 Preparing a nano material: balance with scaleAfter 1g of cobalt nitrate hexahydrate and 2g of tetraethyl orthosilicate were added to 20mL of HCl solution (pH = 2) and sufficiently dissolved, 1g of SBA-15 template was added, and the mixture was hermetically stirred at 50 ℃ for 2 hours, followed by drying the solvent at 70 ℃. The dried sample was then transferred to a muffle furnace for calcination at 300 ℃ for 5h. Finally, soaking the calcined sample in 2M NaOH solution, heating to 70 ℃ to remove the silicon dioxide template, and washing and drying to obtain the defect-rich mesoporous Co with high specific surface area 3 O 4 And (3) nano materials.
Mesoporous Co prepared in example 1 3 O 4 The specific surface area and pore volume of the nanomaterial were 169m, respectively 2 g -1 And 0.40cm 3 g -1 . As can be seen from the TEM image shown in FIG. 1, the material shows a porous structure, and the nanorods have abundant cracked pores, forming an open pore channel structure.
Example 2
Defect-rich mesoporous Fe with high specific surface area 2 O 3 Preparing a nano material: the preparation method is the same as that of example 1, except that the inorganic metal salt is ferric nitrate, and the dosage ratio of ferric nitrate, tetraethyl orthosilicate and hydrochloric acid solution is 1g.
Mesoporous Fe prepared in example 2 2 O 3 The specific surface area and the pore volume of the nano material are 368m respectively 2 g -1 And 1.00cm 3 g -1 . As can be seen from the TEM image shown in fig. 2, the material exhibits porous characteristics and an open channel structure.
Example 3
Preparing a defect-rich mesoporous NiO nano material with high specific surface area: the preparation method is the same as example 1, except that the added inorganic metal salt is nickel nitrate, and the dosage ratio of the nickel nitrate, tetraethyl orthosilicate and hydrochloric acid solution is 1g.
The specific surface area and the pore volume of the mesoporous NiO nano material prepared in the example 3 are 210m respectively 2 g -1 And 0.58cm 3 g -1 . As can be seen from the TEM image shown in fig. 3, the material has abundant pore defects and an open pore structure.
Example 4
Defect-rich high specific surface area mesoporous CeO 2 Preparing a nano material: the preparation method is the same as example 1, except that the inorganic metal salt is cerium nitrate, and the dosage ratio of the cerium nitrate, tetraethyl orthosilicate and hydrochloric acid solution is 1g.
Mesoporous CeO prepared in example 4 2 The specific surface area and the pore volume of the nano material are respectively 290m 2 g -1 And 0.66cm 3 g -1 . As can be seen from the TEM image shown in fig. 4, the material exhibited a porous structure characteristic.
Comparative example 1
Preparation of mesoporous CuO nano material: the preparation method is the same as that of example 1, except that the added inorganic metal salt is copper nitrate, and the dosage ratio of the copper nitrate, tetraethyl orthosilicate and hydrochloric acid solution is 1g.
The specific surface area and the pore volume of the mesoporous CuO nanomaterial prepared in comparative example 1 were 116m 2 g -1 And 0.38cm 3 g -1 . The TEM image is shown in fig. 5, and formation of a defective void structure is not observed.
In the mesoporous copper oxide material prepared by using the copper salt in the comparative example 1, since the copper oxide is an amphoteric metal oxide, the copper oxide and the silicon dioxide both react with the alkali in the process of alkali etching, and in order to ensure that the copper oxide is not completely etched, the etching duration and the alkali concentration need to be strictly controlled, the silicon dioxide in the framework is difficult to be completely etched, and the structural defect is difficult to form. The difference is that the designed metal oxide has good strong alkali resistance, the metal oxide does not participate in reaction in the alkali etching process, silicon dioxide in the framework can be fully etched, structural defects can be formed and fully exposed, and good structural stability can be maintained.
Application example 1
The high specific surface area Co rich in defects prepared in example 1 3 O 4 The application of the nano material in CO oxidation reaction comprises the following specific implementation processes: taking 50mg of mesoporous Co 3 O 4 The nanomaterials were placed in a fixed bed reactor at 1vol.% CO/20vol.% O 2 Per 79vol.% atmosphere at 300 ℃ for 30min. After the pretreatment was completed, the reactor was cooled to the target temperature, and then the reaction gas was introduced into the reactor in an amount of 1vol.% CO/20vol.% O 2 79vol.% He, with a total gas flow rate of 67mL/min, heated to 300 ℃ at a ramp rate of 2 ℃/min, and the change in CO concentration at different temperatures recorded. The CO conversion was calculated according to the following formula:
Figure BDA0003780705400000061
wherein Xco represents the CO conversion, [ CO ]] in And [ CO ]] out Representing the concentration of inlet and outlet CO gas, respectively.
As can be seen from FIG. 5, the prepared mesoporous Co 3 O 4 Shows very excellent CO low-temperature activity, and has the reaction temperature of-43 ℃ and the high space velocity of 80 000mL g cat -1 h -1 Under the condition, CO can be completely converted.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any modification, equivalent replacement, and improvement made by those skilled in the art within the technical scope of the present invention should be included in the scope of the present invention.

Claims (10)

1. A preparation method of a defect-rich mesoporous metal oxide with high specific surface area is characterized by comprising the following steps:
1) Synthesizing a mesoporous silica template by a hydrothermal synthesis method;
2) Adding inorganic metal salt and a silicon oxide precursor into an acid solution or an alkali solution for dissolving, and fully and uniformly stirring to obtain a mixed solution A;
3) Adding the mesoporous silica template into the mixed solution A, uniformly stirring and drying to obtain a metal salt-silica composite;
4) And (3) roasting the metal salt-silicon dioxide compound, and then reacting with an alkali solution to remove the silicon dioxide component to obtain the defect-rich mesoporous metal oxide with the high specific surface area.
2. The production method according to claim 1, characterized in that: in the step 1), the silica template includes any one of SBA series, KIT series, FSM series, FDU series, MCM series, MCF, and silica gel.
3. The method of claim 1, wherein: in the step 2), the inorganic metal salt comprises any one or a mixture of more of ferric nitrate, cobalt nitrate, nickel nitrate, cerium nitrate, manganese nitrate and chromium nitrate; the silicon oxide precursor includes: the defect concentration of the mesoporous metal oxide nano material is regulated and controlled by changing the adding amount of the silicon oxide precursor through mixing any one or more of methyl orthosilicate, ethyl orthosilicate, propyl orthosilicate, isopropyl orthosilicate, butyl orthosilicate, sodium silicate and water glass.
4. The method of claim 1, wherein: in the step 2), the acid solution comprises one or a mixture of hydrochloric acid, nitric acid, acetic acid and carbonic acid; the alkaline solution comprises one or more of sodium hydroxide, potassium hydroxide, ammonia water and ammonium carbonate.
5. The production method according to claim 1, characterized in that: in the step 2), the silicon oxide precursor is hydrolyzed under acidic or alkaline conditions and interacts with metal salt, and the silica nanoparticles formed after roasting can be embedded into the framework of the mesoporous metal oxide.
6. The method of claim 1, wherein: in the step 3), the dosage ratio of the mesoporous silica template to the solution A is 1g.
7. The production method according to claim 1, characterized in that: in the step 3), the temperature is 10-90 ℃ during stirring, the stirring time is 0.5-48h, and the drying temperature is 40-100 ℃.
8. The method of claim 1, wherein: in the step 4), the calcining temperature is 200-1000 ℃; the alkali solution is NaOH or KOH solution or ammonia water or diethylamine, etc., the concentration is 0.1-12M, and the reaction temperature is 10-90 ℃.
9. A mesoporous metal oxide nanometer material with high specific surface area and rich defects is characterized in that: prepared by the process of any one of claims 1 to 8.
10. Use of the mesoporous metal oxide nanomaterial of claim 9 in a low temperature oxidation reaction of CO.
CN202210930242.5A 2022-08-03 2022-08-03 Defect-rich mesoporous metal oxide with high specific surface area and preparation method and application thereof Pending CN115385387A (en)

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