CN114671452B - Method for preparing massive cerium oxide aerogel by taking epoxy compound as gel accelerator - Google Patents
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- 239000004964 aerogel Substances 0.000 title claims abstract description 43
- 229910000420 cerium oxide Inorganic materials 0.000 title claims abstract description 33
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 title claims abstract description 33
- 239000004593 Epoxy Substances 0.000 title claims abstract description 23
- 150000001875 compounds Chemical class 0.000 title claims abstract description 23
- 238000000034 method Methods 0.000 title claims abstract description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 44
- 239000011240 wet gel Substances 0.000 claims abstract description 34
- 150000000703 Cerium Chemical class 0.000 claims abstract description 28
- 238000000352 supercritical drying Methods 0.000 claims abstract description 25
- 239000000499 gel Substances 0.000 claims abstract description 19
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 claims abstract description 18
- 230000032683 aging Effects 0.000 claims abstract description 17
- 229910052751 metal Inorganic materials 0.000 claims abstract description 17
- 239000002184 metal Substances 0.000 claims abstract description 17
- 229920002125 Sokalan® Polymers 0.000 claims abstract description 13
- 239000000654 additive Substances 0.000 claims abstract description 13
- 229910052684 Cerium Inorganic materials 0.000 claims abstract description 11
- 238000007789 sealing Methods 0.000 claims abstract description 11
- 239000004584 polyacrylic acid Substances 0.000 claims abstract description 10
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 6
- 230000000996 additive effect Effects 0.000 claims abstract description 5
- 239000004372 Polyvinyl alcohol Substances 0.000 claims abstract description 3
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 3
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 3
- 229920002451 polyvinyl alcohol Polymers 0.000 claims abstract description 3
- 238000003756 stirring Methods 0.000 claims abstract description 3
- 238000006243 chemical reaction Methods 0.000 claims description 38
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 claims description 23
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims description 23
- 239000002243 precursor Substances 0.000 claims description 23
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 18
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 13
- 238000001035 drying Methods 0.000 claims description 12
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims description 9
- 238000004321 preservation Methods 0.000 claims description 9
- 238000007599 discharging Methods 0.000 claims description 7
- 239000007788 liquid Substances 0.000 claims description 7
- 238000002360 preparation method Methods 0.000 claims description 7
- 235000019441 ethanol Nutrition 0.000 claims description 6
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 claims description 3
- 239000004967 Metal oxide aerogel Substances 0.000 claims description 3
- 229910002492 Ce(NO3)3·6H2O Inorganic materials 0.000 claims description 2
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 2
- 238000002210 supercritical carbon dioxide drying Methods 0.000 claims description 2
- -1 cerium salt Chemical class 0.000 abstract description 4
- 238000003980 solgel method Methods 0.000 abstract description 4
- 239000012530 fluid Substances 0.000 abstract 1
- 239000001301 oxygen Substances 0.000 description 23
- 229910052760 oxygen Inorganic materials 0.000 description 23
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 22
- 239000003755 preservative agent Substances 0.000 description 16
- 230000002335 preservative effect Effects 0.000 description 16
- 239000000463 material Substances 0.000 description 15
- 238000007254 oxidation reaction Methods 0.000 description 14
- 230000003647 oxidation Effects 0.000 description 11
- 230000003197 catalytic effect Effects 0.000 description 10
- 239000013078 crystal Substances 0.000 description 8
- 239000011521 glass Substances 0.000 description 8
- 239000007789 gas Substances 0.000 description 7
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 6
- 239000002202 Polyethylene glycol Substances 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 229920001223 polyethylene glycol Polymers 0.000 description 5
- 230000007547 defect Effects 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000002086 nanomaterial Substances 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- 238000003860 storage Methods 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- 239000004005 microsphere Substances 0.000 description 3
- 239000002105 nanoparticle Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 239000001294 propane Substances 0.000 description 3
- 238000005086 pumping Methods 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000002073 nanorod Substances 0.000 description 2
- 230000001699 photocatalysis Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- RBACIKXCRWGCBB-UHFFFAOYSA-N 1,2-Epoxybutane Chemical compound CCC1CO1 RBACIKXCRWGCBB-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910052765 Lutetium Inorganic materials 0.000 description 1
- 230000010718 Oxidation Activity Effects 0.000 description 1
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000001588 bifunctional effect Effects 0.000 description 1
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical group [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000010436 fluorite Substances 0.000 description 1
- 230000002431 foraging effect Effects 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002159 nanocrystal Substances 0.000 description 1
- 239000002121 nanofiber Substances 0.000 description 1
- 239000007783 nanoporous material Substances 0.000 description 1
- 239000002135 nanosheet Substances 0.000 description 1
- 239000002077 nanosphere Substances 0.000 description 1
- 239000002071 nanotube Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000013307 optical fiber Substances 0.000 description 1
- 238000006362 organocatalysis Methods 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000009877 rendering Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000004449 solid propellant Substances 0.000 description 1
- 239000004071 soot Substances 0.000 description 1
- 230000007847 structural defect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
Classifications
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- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
- B01J13/0091—Preparation of aerogels, e.g. xerogels
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/10—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of rare earths
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/20—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state
- B01J35/23—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state in a colloidal state
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- 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
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- 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
- C01P2006/10—Solid density
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- 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
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- 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
- C01P2006/90—Other properties not specified above
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Analytical Chemistry (AREA)
- Dispersion Chemistry (AREA)
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
Abstract
The invention discloses a method for preparing massive cerium oxide aerogel by using an epoxy compound as a gel accelerator through a sol-gel method, which comprises the following specific steps: 1) Inorganic metal cerium salt is taken as a metal source and is dissolved in absolute ethyl alcohol; epoxy compound is used as a gel accelerator, and formamide, polyvinyl alcohol PEG-X with different molecular weights and polyacrylic acid with different molecular weights are used as additives; 2) Rapidly adding the epoxy compound solution into the inorganic metal cerium salt/absolute ethyl alcohol solution containing the additive, rapidly stirring, sealing, and then putting into an oven to obtain wet gel; 3) Aging the wet gel; 4) And (3) taking absolute ethyl alcohol and carbon dioxide as supercritical fluid media, and performing supercritical drying treatment on the aged wet gel to finally obtain the massive cerium oxide aerogel. By adjusting the ratio of the metal cerium salt and the epoxy compound, the bulk cerium oxide aerogel with low density, high specific surface area and high porosity can be successfully prepared.
Description
Technical Field
The invention relates to the technical field of aerogel preparation, in particular to a method for preparing massive cerium oxide aerogel by taking an epoxy compound as a gel accelerator.
Background
Research shows that the catalytic CO oxidation reaction of cerium oxide follows the Mars-van Krevelen mechanism, namely that the lattice oxygen on the surface of cerium oxide oxidizes CO to form holes after being consumed, and oxygen in the atmosphere or bulk lattice oxygen continues to oxidize CO after the oxygen vacancies are activated.
In recent years, the realization of oxidation of CO at lower temperatures has been of interest. Whereas CeO 2 The base material is well suited for CO oxidation reactions. Cerium oxide (CeO) 2 ) Is a yellow-white rare earth oxide, and the crystal structure is fluorite. Under different redox conditions, cerium ions are easy to realize conversion between trivalent and tetravalent, so that the cerium oxide has high oxygen storage capacity. Ce in cerium oxide crystals 3+ The more oxygen defects are formed, the more oxygen vacancies are formed, and the less oxygen the ceria can lose part of the lattice oxygen, thereby forming a plurality of oxygen vacancies. When the oxygen content is high, the ceria can store a large amount of oxygen, so that the ceria has a strong redox ability. Wherein CeO is 2 Has an important influence on the oxidation of CO, as well as structural defects and oxygen vacancies. For example, zhang et al compared two different CeO 2 The CO oxidation performance of the one-dimensional nano material to obtain CeO 2 The single-wall/multi-wall hollow microsphere can make the conversion rate of CO reach 100% at 230 ℃, and the bulk CeO 2 The same conversion was achieved at 500℃because the hollow microsphere structure provided more available oxygen for CO oxidation and oxygen defects [ Zhang Y, cheng T, hu Q, fang Z, han K, study of the Preparation and Properties of CeO ] 2 Single/Multiwall Hollow Microspheres,Journal of Materials Research,2011,22,1472-1478]. Furthermore, ceO 2 One of the best soot combustion catalysts is considered to significantly reduce the reaction temperature.
CeO 2 Has the advantages of good oxygen storage capacity, good ionic conductivity and the like. CeO (CeO) 2 The most important characteristic is its oxygen storage capacity. Obviously, this characteristic is associated with CeO 2 The oxygen migration capability of the lattice at the surface of the material is related to the gradual decrease of the concentration of oxygen vacancies from the surface to the bulk, the gradient causes the lattice oxygen to diffuse from the outside to the surface, and the oxygen ions will Ce 4+ Reduction to Ce 3+ Resulting in the creation of surface oxygen vacancies, thereby rendering such materials suitable for most electrochemical and photochemical applications. In addition, in the case of the optical fiber,it is well known that the catalytic activity of nanoparticles depends largely on the size and morphology of the material, thus regulating CeO 2 The size and morphology of nanoporous materials is a hotspot for research.
By utilizing advanced synthesis technology, researchers can reasonably design and synthesize the high-efficiency cerium oxide catalyst with specific morphology, size, structure, component and crystal face. To study CeO 2 The relationship between morphology and catalytic performance has been synthesized by researchers into CeO with novel structure and various morphologies 2 Nanomaterial, including rod-like [ Li, j.; zhang, z.; tian, z.; zhou, x; zheng, z.; ma, y; qu, Y., low pressure induced porous nanorods of ceria with high reducibility and large oxygen storage capacity: synthesis and catalytic applications. Journal of Materials Chemistry A2014,2 (39), 16459-16466]Spherical [ Yang, f.; wei, J.; liu, w; guo, j.; yang, Y., copper doped ceria nanospheres: surface defects promoted catalytic activity and a versatile app. Journal of Materials Chemistry A2014,2 (16), 5662-5667]Cube [ Wu, q.; zhang, f; xiao, p.; tao, h.; wang, x.; hu, z; lu, Y., great influence of anions for controllable synthesis of CeO 2 nanostructures:from nanorods to nanocubes.The Journal of Physical Chemistry C 2008,112(44),17076-17080]Flake-like [ Huang, y.c.; long, b.; tang, m.n.; rui, Z.B.; balogun, m. -s; tong, y.x.; ji, H.B., bifunctional catalytic material: an ultrastable and high-performance surface defect CeO 2 nanosheets for formaldehyde thermal oxidation and photocatalytic oxidation.Applied Catalysis B:Environmental 2016,181,779-787]Tubular [ Wan, c.; cheng, d.g.; chen, f.q.; zhan, x.l., fabrication of CeO 2 nanotube supported Pt catalyst encapsulated with silica for high and stable performance.Chemical Communications 2015,51(48),9785-9788]And fibrous [ Lu, p.; qiao, b.; lu, n.; hyun, d.c.; wang, j.; kim, m.j.; liu, j.; xia, y., photochemical deposition of highly dispersed Pt nanoparticles on porous CeO 2 nanofibers for the water-gas shift reaction.Advanced Functional Materials 2015,25(26),4153-4162]。CeO 2 The difference in morphology and size often causes differences in crystal surface atomic arrangement, energy level structure, interface properties and the like, and further influences the physicochemical properties of the material. For example, guo et al [ Hu, z.; liu, x; meng, d.; guo, y.; guo, y.; lu, G., effect of ceria crystal plane on the physicochemical and catalytic properties of Pd/ceria for CO and propane oxidation. ACS Catalysis 2016,6 (4), 2265-2279]Study of Pd-supported CeO 2 The catalyst has different crystal planes and catalytic oxidation performance to CO and propane. It was found that a rod-like cerium oxide CeO surrounded by (110) and (100) crystal planes 2-R Has the highest CO catalytic oxidation activity, and on the contrary, the octahedral cerium oxide CeO with exposed (111) crystal face 2 Has the highest activity on the catalytic oxidation of propane. To further improve CeO 2 Generally two strategies are employed: 1. optimizing the structure and morphology of cerium oxide; 2. other metal ions, such as noble metals or transition metal oxides, are incorporated into the cerium oxide lattice. Various CeO with specific morphology and size 2 And CeO-based 2 Has been reported and is widely used in CO oxidation, CO selective oxidation, three-way catalysts, low temperature steam shift reactions, biomedical applications, water treatment, solid fuel cells, photocatalytic and organocatalytic reactions, and the like.
Sol-gel methods have a wide range of applications in wet chemical synthesis. In a typical sol-gel synthesis method, precursor metal salt is hydrolyzed, dehydrated and condensed to gradually form sol, gel is formed along with further progress of condensation reaction, and then drying and roasting are carried out to obtain the required nano material. The sol-gel reaction is generally performed to obtain cerium oxide nanocrystals having a porous structure. However, the conventional sol-gel method generally yields CeO in powder form 2 And the specific surface area is generally small.
Disclosure of Invention
The invention aims to solve the technical problems that: a method for preparing bulk metal cerium dioxide aerogel material by taking inorganic or organic metal cerium salt as a precursor raw material and epoxy compounds as gel accelerators has the characteristics of low cost and simple reaction.
In order to solve the technical problems, the invention provides the following technical scheme:
a method for preparing bulk cerium oxide aerogel by using an epoxy compound as a gel accelerator comprises the following specific preparation steps:
1) Dissolving inorganic or organic metal cerium salt in absolute ethyl alcohol to prepare a metal cerium salt precursor solution, wherein the concentration of the metal salt is 0.01-10.0mol/L;
2) Respectively adding additives with different contents and different types into the metal cerium salt precursor solution; the additive is one or more of formamide, polyvinyl alcohol with different molecular weights and polyacrylic acid with different molecular weights;
3) Adding an epoxy compound solution into the solution obtained in the step 2), rapidly stirring, sealing, and then placing into an environment of 25-70 ℃ for treatment for a certain time to obtain wet gel; the volume ratio of the epoxy compound solution to the solution obtained in the step 2) is 1/100-1/1;
4) Immersing the wet gel in aging liquid at 25-70deg.C, aging for 2-7d; the aging liquid is one or more of isopropanol, absolute ethyl alcohol or absolute methyl alcohol;
5) Placing the wet gel after aging treatment into a high-pressure reaction kettle of a supercritical drying device, and performing supercritical drying by adopting ethanol or carbon dioxide as a supercritical medium, wherein the temperature of the ethanol supercritical drying is 260-300 ℃, the heat preservation time is 10-120min, and the pressure is 7-12MPa; the supercritical carbon dioxide drying temperature is 45-75deg.C, the heat preservation time is 90-150min, and the pressure is 10-15MPa; and after the drying is finished, discharging gas in the high-pressure reaction kettle to obtain the massive metal oxide aerogel.
Preferably, the inorganic or organometallic cerium salt used is Ce 2 (SO 4 ) 3 ,Ce 2 (SO 4 ) 3 ·8H 2 O,Ce(COOCH 3 ) 3 ,Ce(Ac) 3 ·nH 2 O,Ce(NO 3 ) 3 ,Ce(NO 3 ) 3 ·6H 2 O,CeCl 3 ,CeCl 3 ·7H 2 O,Ce 2 (CO 3 ) 3 ,Ce 2 (CO 3 ) 3 ·xH 2 O,Ce 2 (C 2 O 4 ) 3 ,Ce 2 (C 2 O 4 ) 3 ·xH 2 O, and one or more of the following.
Preferably, the epoxy compound includes, but is not limited to, one or more of ethylene oxide, propylene oxide, epichlorohydrin, butylene oxide, and the concentration of the epoxy compound is 0-30mol/L.
Preferably, isopropanol, absolute ethanol and absolute methanol or mixtures thereof in different proportions are used in the aging liquid.
Preferably, the final concentration of the additive in step 2) is 0-30mol/L.
The beneficial effects obtained by the invention are as follows:
according to the preparation method, the preparation process of the cerium oxide bulk aerogel material and the aerogel material with low cost and stable structure are further searched as research targets, and from the perspective of regulating and controlling the sol-gel process and gel structure of the inorganic cerium salt raw material and the characteristics of the cerium oxide aerogel material, formamide, polyethylene glycol with different molecular weights and polyacrylic acid with different molecular weights are introduced into the preparation process of the cerium oxide aerogel, so that the formation of powder in the gel and drying processes is avoided, and the bulk cerium oxide aerogel is obtained. The prepared cerium oxide aerogel material has the characteristics of large specific surface area and high porosity, and can be used as a catalyst carrier in CO oxidation reaction.
The metal oxide aerogel prepared by taking the cerium-containing metal salt as a precursor and the epoxy compound as a gel accelerator has low density (0.05-0.3 g/cm) 3 ) High porosity (95-99%), high specific surface area (100-1000 m) 2 And/g), and the application prospect is wide.
Drawings
FIG. 1 is a scanning electron micrograph of the ceria aerogel material prepared in example 1.
Detailed Description
The following description of the embodiments of the present invention is provided to facilitate a more complete, accurate and thorough understanding of the present invention's inventive concepts and technical solutions by those skilled in the art.
Example 1
(1) Preparing cerium salt precursor solution: 0.261g Ce (NO) 3 ) 3 ·6H 2 O is added into 60mL of absolute ethanol, wherein [ Ce 3+ ]=0.01 mol/L, sealed with a preservative film, and put on a magnetic stirrer to be stirred until completely dissolved.
(2) The addition of 5mL of formamide was continued and the solution was stirred until it was clear.
(3) 10mL of propylene oxide was added to the cerium salt-containing precursor solution of (2), and stirred for 1min to homogeneity to form a sol.
(4) Pouring the sol into a culture dish, sealing with a preservative film, and putting into a baking oven at 60 ℃ to form wet gel.
(5) The wet gel is put into a glass dish containing absolute ethyl alcohol, sealed and then put into a baking oven at 40 ℃ for aging for 5 days.
(6) Placing the wet gel obtained after aging into a high-pressure reaction kettle of a supercritical drying device, and performing supercritical drying by adopting supercritical ethanol, wherein the supercritical drying temperature is 260 ℃, the heat preservation time is 60min, the pressure is 7MPa, and discharging gas in the high-pressure reaction kettle after drying is finished, so that the massive cerium oxide aerogel is obtained.
(7) The density of the obtained bulk ceria aerogel was 0.325g/cm 3 Specific surface area of 320m 2 The porosity per gram was 93.5%.
Example 2
(1) Preparing cerium salt precursor solution: 11.17g CeCl 3 ·7H 2 O is added into 60mL of absolute ethanol, wherein [ Ce 3+ ]=0.5 mol/L, sealed with a preservative film, and put on a magnetic stirrer to be stirred until completely dissolved.
(2) The addition of 6mL of polyacrylic acid PAA (M) V =4000000), and stirred until the solution is clear.
(3) 5mL of epichlorohydrin is added into the precursor solution containing cerium salt in the step (2), and the mixture is stirred for 1min to be uniform, so as to form sol.
(4) Pouring the sol into a culture dish, sealing with a preservative film, and forming wet gel at room temperature of 25 ℃.
(5) The wet gel was placed in a glass dish of absolute ethanol and aged in an oven at 40 ℃ for 5d.
(6) And (3) placing the wet gel obtained after ageing into a high-pressure reaction kettle of a supercritical drying device, and performing supercritical drying under the absolute ethyl alcohol atmosphere, wherein the supercritical drying temperature is 260 ℃, the heat preservation time is 80min, the pressure is 8MPa, and discharging gas in the high-pressure reaction kettle after the drying is finished, so as to obtain the cerium oxide aerogel.
(7) The density of the obtained bulk ceria aerogel was 0.163g/cm 3 Specific surface area of 260m 2 The porosity per gram was 96.4%.
Example 3
(1) Preparing cerium salt precursor solution: 22.86g Ce 2 (C 2 O 4 ) 3 ·xH 2 O is added into 60mL of absolute ethanol, wherein [ Ce 3+ ]=0.7 mol/L, sealed with a preservative film, and put on a magnetic stirrer to be stirred until completely dissolved.
(2) Continue to add 5mL polyethylene glycol (M) n =10000), and stirred until the solution is clear.
(3) 8ml of 1, 2-butylene oxide was added to the cerium salt-containing precursor solution of (2), and stirred for 1min to uniformity to form a sol.
(4) Pouring the sol into a culture dish, sealing with a preservative film, and putting into a baking oven at 60 ℃ to form wet gel.
(5) The wet gel was placed in a glass dish containing absolute ethanol/tetraethyl orthosilicate (V/v=7:3) and aged in an oven at 25 ℃ for 7d.
(6) And (3) placing the wet gel obtained after aging into a high-pressure reaction kettle of a supercritical drying device, and performing supercritical drying by using supercritical ethanol, wherein the supercritical drying temperature is 270 ℃, the heat preservation time is 90min, the pressure is 9MPa, and discharging gas in the high-pressure reaction kettle after the drying is finished, so as to obtain the cerium oxide aerogel.
(7) The obtainedThe bulk ceria aerogel has a density of 0.213g/cm 3 A specific surface area of 360m 2 The porosity per gram was 97.1%.
Example 4
(1) Preparing cerium salt precursor solution: 5.22g Ce (NO) 3 ) 3 ·6H 2 O is added into 60mL of absolute ethanol, wherein [ Ce 3+ ]=0.2 mol/L, sealed with a preservative film, and put on a magnetic stirrer to be stirred until completely dissolved.
(2) Continue adding 3mL polyethylene glycol (M) n =4000), and stirred until the solution is clear.
(3) 15mL of propylene oxide is added into the precursor solution containing cerium salt in (2), and the mixture is stirred for 1min to be uniform, so as to form sol.
(4) Pouring the sol into a culture dish, sealing with a preservative film, and putting into a baking oven at 60 ℃ to form wet gel.
(5) The wet gel was placed in a glass dish containing absolute ethanol and aged in an oven at 70 ℃ for 2d.
(6) And (3) placing the wet gel obtained after ageing into a high-pressure reaction kettle of a supercritical drying device, and performing supercritical drying under the absolute ethyl alcohol atmosphere, wherein the supercritical drying temperature is 280 ℃, the heat preservation time is 100min, the pressure is 10MPa, and discharging gas in the high-pressure reaction kettle after the drying is finished, so that the massive cerium oxide aerogel is obtained.
(7) The density of the obtained massive cerium oxide composite aerogel is 0.235g/cm 3 Specific surface area of 386m 2 The porosity per gram was 98.1%.
Example 5
(1) Preparing cerium salt precursor solution: 27.62g Ce 2 (CO 3 ) 3 ·xH 2 O is added into 60mL of absolute ethanol, wherein [ Ce 3+ ]=1.0 mol/L, sealed with a preservative film, and put on a magnetic stirrer to be stirred until completely dissolved.
(2) 3mL of polyacrylic acid PAA (M) was added n 130000), and stirred until the solution is clear.
(3) 12mL of propylene oxide was added to the cerium salt-containing precursor solution of (2), and stirred for 1min to homogeneity to form a sol.
(4) Pouring the sol into a culture dish, sealing with a preservative film, and forming wet gel at room temperature.
(5) The wet gel was placed in a glass dish containing absolute ethanol/absolute methanol (V/v=3:1) and aged in an oven at 40 ℃ for 5d.
(6) And (3) placing the wet gel obtained after ageing into a high-pressure reaction kettle of a supercritical drying device, and performing supercritical drying under the absolute ethyl alcohol atmosphere, wherein the supercritical drying temperature is 300 ℃, the heat preservation time is 120min, the pressure is 12MPa, and after the drying is finished, discharging gas in the high-pressure reaction kettle to obtain the massive cerium oxide aerogel.
(7) The density of the obtained bulk ceria aerogel was 0.129g/cm 3 Specific surface area of 5000m 2 The porosity per gram was 98.2%.
Example 6
(1) Preparing cerium salt precursor solution: 43.83g Ce 2 (SO 4 ) 3 ·8H 2 O is added into 60mL of absolute ethanol, wherein [ Ce 3+ ]=10mol/L, sealed with preservative film, and put on a magnetic stirrer to be stirred until completely dissolved.
(2) A further addition of 0.6mL of polyacrylic acid PAA (M n =3000), and stirred until the solution is clear.
(3) 8mL of propylene oxide is added into the precursor solution containing cerium salt in (2), and the mixture is stirred for 1min to be uniform, so as to form sol.
(4) Pouring the sol into a culture dish, sealing with a preservative film, and forming wet gel at room temperature.
(5) The wet gel was placed in a glass dish containing absolute ethanol/isopropanol (V/v=3:1) and aged in an oven at 40 ℃ for 5d.
(6) Placing the aged wet gel into a high-pressure reaction kettle of a supercritical drying device, and adding CO when the temperature of the high-pressure reaction kettle reaches 45 DEG C 2 Pumping into a high-pressure reaction kettle, and when the pressure of the high-pressure reaction kettle reaches 10MPa, enabling the system to reach a supercritical state; maintaining for 90min; after the drying is finished, CO in the high-pressure reaction kettle is discharged 2 Obtaining the bulk cerium oxide aerogel.
(7) The density of the obtained bulk ceria aerogel was 0.145g/cm 3 A specific surface area of 450m 2 The porosity per gram was 96.3%.
Example 7
(1) Preparing cerium salt precursor solution: 5.71g Ce (Ac) 3 ·nH 2 O is added into 60mL of absolute ethanol, wherein [ Ce 3+ ]=0.3 mol/L, sealed with a preservative film, and put on a magnetic stirrer to be stirred until completely dissolved.
(2) The addition of 5mL of formamide was continued and the solution was stirred until it was clear.
(3) 3mL of propylene oxide was added to the cerium salt-containing precursor solution of (2), and stirred for 1min to homogeneity to form a sol.
(4) Pouring the sol into a culture dish, sealing with a preservative film, and forming wet gel at room temperature.
(5) The wet gel was placed in a glass dish containing anhydrous methanol and aged in an oven at 40 ℃ for 5d.
(6) Placing the aged wet gel into a high-pressure reaction kettle of a supercritical drying device, and adding CO when the temperature of the high-pressure reaction kettle reaches 60 DEG C 2 Pumping into a high-pressure reaction kettle, and when the pressure of the high-pressure reaction kettle reaches 12MPa, enabling the system to reach a supercritical state; maintaining for 120min; after the drying is finished, CO in the high-pressure reaction kettle is discharged 2 Obtaining the bulk cerium oxide aerogel.
(7) The density of the obtained bulk ceria aerogel was 0.185g/cm 3 A specific surface area of 445m 2 The porosity per gram was 96.7%.
Example 8
(1) Preparing cerium salt precursor solution: 52.2g Ce (NO) 3 ) 3 ·6H 2 O is added into 60mL of absolute ethanol, wherein [ Ce 3+ ]=2.0 mol/L, sealed with preservative film, and put on a magnetic stirrer to be stirred until completely dissolved.
(2) The addition of 5mL of formamide was continued and the solution was stirred until it was clear.
(3) 30mL of propylene oxide was added to the cerium salt-containing precursor solution of (2), and stirred for 1min to homogeneity to form a sol.
(4) Pouring the sol into a culture dish, sealing with a preservative film, and putting into a baking oven at 70 ℃ to form wet gel.
(5) The wet gel was placed in a glass dish containing isopropyl alcohol and placed in an oven at 40 ℃ for 5d aging.
(6) Placing the aged wet gel into a high-pressure reaction kettle of a supercritical drying device, and adding CO when the temperature of the high-pressure reaction kettle reaches 75 DEG C 2 Pumping into a high-pressure reaction kettle, and when the pressure of the high-pressure reaction kettle reaches 15MPa, enabling the system to reach a supercritical state; maintaining for 150min; after the drying is finished, CO in the high-pressure reaction kettle is discharged 2 Obtaining the bulk cerium oxide aerogel.
(7) The density of the obtained bulk ceria aerogel was 0.321g/cm 3 Specific surface area of 313m 2 The porosity per gram was 94.2%.
Comparative examples: the other components were the same as in example 1 except that additives such as formamide, polyethylene glycol and polyacrylic acid were not added. Since additives such as formamide, polyethylene glycol and polyacrylic acid are not added, no gel can be obtained, and only precipitation can be obtained. Its density is 0.67g/cm 3 Specific surface area of 10m 2 /g。
As is apparent from comparison of the ceria aerogels prepared in the comparative examples and examples 1 to 8, the addition of additives such as polyacrylic acid can form the wet gel into a three-dimensional network structure so that the ceria aerogel is eventually in a bulk rather than a powder form. The formation of the bulk aerogel can effectively increase the specific surface area and the porosity of the ceria and reduce the density of the aerogel. The improvement of the key performances mainly results from the addition of additives, the addition of the additives into the system can form hydrogen bond and coordination bond actions, and then the propylene oxide gel accelerator is added to form a three-dimensional network structure.
In addition, fig. 1 shows the microscopic morphology of the aerogel sample obtained in embodiment 1, and it can be seen that the structure obtained by stacking the nano particles is consistent with the microscopic morphology of the aerogel prepared in the conventional sense.
The above embodiments are only for illustrating the technical idea of the present invention, and the protection scope of the present invention is not limited by the above embodiments, and any modification made on the basis of the technical scheme according to the technical idea of the present invention falls within the protection scope of the present invention; the technology not related to the invention can be realized by the prior art.
Claims (5)
1. A method for preparing massive cerium oxide aerogel by taking an epoxy compound as a gel accelerator is characterized by comprising the following specific preparation steps:
1) Dissolving inorganic or organic metal cerium salt in absolute ethyl alcohol to prepare a metal cerium salt precursor solution, wherein the concentration of the metal cerium salt is 0.01-10.0mol/L;
2) Respectively adding additives with different contents and different types into the metal cerium salt precursor solution; the additive is one or more of formamide, polyvinyl alcohol with different molecular weights and polyacrylic acid with different molecular weights;
3) Adding an epoxy compound solution into the solution obtained in the step 2), rapidly stirring, sealing, and then placing into an environment of 25-70 ℃ for treatment for a certain time to obtain wet gel; the volume ratio of the epoxy compound solution to the solution obtained in the step 2) is 1/100-1/1;
4) Immersing the wet gel in aging liquid at 25-70deg.C, aging for 2-7d; the aging liquid is one or more of isopropanol, absolute ethyl alcohol or absolute methyl alcohol;
5) Placing the wet gel after aging treatment into a high-pressure reaction kettle of a supercritical drying device, and performing supercritical drying by adopting ethanol or carbon dioxide as a supercritical medium, wherein the temperature of the ethanol supercritical drying is 260-300 ℃, the heat preservation time is 10-120min, and the pressure is 7-12MPa; the supercritical carbon dioxide drying temperature is 45-75deg.C, the heat preservation time is 90-150min, and the pressure is 10-15MPa; and after the drying is finished, discharging gas in the high-pressure reaction kettle to obtain the massive metal oxide aerogel.
2. The method for preparing the bulk ceria aerogel according to claim 1, wherein the gel accelerator is an epoxy compound, comprising the steps of:the inorganic or organic metal cerium salt is Ce 2 (SO 4 ) 3 ,Ce 2 (SO 4 ) 3 ·8H 2 O,Ce(COOCH 3 ) 3 ,Ce(Ac) 3 ·nH 2 O,Ce(NO 3 ) 3 ,Ce(NO 3 ) 3 ·6H 2 O,CeCl 3 ,CeCl 3 ·7H 2 O,Ce 2 (CO 3 ) 3 ,Ce 2 (CO 3 ) 3 ·xH 2 O,Ce 2 (C 2 O 4 ) 3 ,Ce 2 (C 2 O 4 ) 3 ·xH 2 O, and one or more of the following.
3. The method for preparing the bulk ceria aerogel according to claim 1, wherein the gel accelerator is an epoxy compound, comprising the steps of: the epoxy compound includes, but is not limited to, one or more of ethylene oxide, propylene oxide, epichlorohydrin and butylene oxide, and the concentration of the epoxy compound is 0-30mol/L.
4. The method for preparing the bulk ceria aerogel according to claim 1, wherein the gel accelerator is an epoxy compound, comprising the steps of: the adopted ageing liquid is isopropanol, absolute ethyl alcohol and absolute methyl alcohol or mixed liquid with different proportions.
5. The method for preparing the bulk ceria aerogel according to claim 1, wherein the gel accelerator is an epoxy compound, comprising the steps of: the final concentration of the additive in the step 2) is 0-30mol/L.
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Citations (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2000010705A1 (en) * | 1998-08-20 | 2000-03-02 | Conoco Inc. | Fischer-tropsch processes using xerogel and aerogel catalysts |
| JP2005087946A (en) * | 2003-09-19 | 2005-04-07 | Casio Comput Co Ltd | Catalyst and production method therefor |
| CN101219360A (en) * | 2008-01-24 | 2008-07-16 | 同济大学 | Process for producing transition metal base silica aerogel, transition metal oxide silica aerogel, composite transition metal oxide silica aerogel |
| CN101948127A (en) * | 2010-09-20 | 2011-01-19 | 烟台大学 | Industrial preparation method of non-oxidative cerium oxide nanoparticles |
| CN104607116A (en) * | 2015-01-12 | 2015-05-13 | 朱秀榕 | Universal preparation method of high-specific surface area rare earth element-doped carbon gas gel |
| CN104772084A (en) * | 2015-03-31 | 2015-07-15 | 浙江大学 | Method for preparing metal oxide aerogel by taking inorganic salt as raw material |
| CN104941538A (en) * | 2015-06-03 | 2015-09-30 | 金承黎 | In-situ composite silicon-based multibasic oxide oxide aerogel material and preparation method thereof |
| CN105051118A (en) * | 2013-02-05 | 2015-11-11 | 巴斯夫欧洲公司 | Method for producing porous or fine-particle solid inorganic materials |
| JP2017048064A (en) * | 2015-08-31 | 2017-03-09 | 日立化成株式会社 | Aerogel composite |
| CN107162050A (en) * | 2017-06-06 | 2017-09-15 | 浙江大学 | A kind of method that block zirconia aerogels are prepared by gel accelerator of acidic amino acid |
| CN108355639A (en) * | 2018-02-10 | 2018-08-03 | 浙江大学 | A method of preparing porous oxidation cerium catalysis material |
| CN112058314A (en) * | 2020-08-31 | 2020-12-11 | 安徽壹石通材料科技股份有限公司 | Normal-pressure preparation method of rare earth oxide blended cerium oxide aerogel |
| CN112915979A (en) * | 2021-01-25 | 2021-06-08 | 伯克利南京医学研究有限责任公司 | Aerogel sponge material and preparation method and application thereof |
| CN113181845A (en) * | 2021-06-08 | 2021-07-30 | 浙江大学 | Cerium oxide aerogel loaded with alloy nanoparticles and preparation method thereof |
| CN113842922A (en) * | 2021-09-08 | 2021-12-28 | 南京工业大学 | Composite aerogel and preparation method and application thereof |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| ITPD20060465A1 (en) * | 2006-12-22 | 2008-06-23 | Univ Degli Studi Trieste | AEROGEL MATERIALS BASED ON METALLIC OXIDES AND COMPOSITES OF THE SAME |
| US10336937B2 (en) * | 2016-03-17 | 2019-07-02 | Lawrence Livermore National Security, Llc | Monolithic rare earth oxide aerogels |
-
2022
- 2022-03-03 CN CN202210201933.1A patent/CN114671452B/en active Active
Patent Citations (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2000010705A1 (en) * | 1998-08-20 | 2000-03-02 | Conoco Inc. | Fischer-tropsch processes using xerogel and aerogel catalysts |
| JP2005087946A (en) * | 2003-09-19 | 2005-04-07 | Casio Comput Co Ltd | Catalyst and production method therefor |
| CN101219360A (en) * | 2008-01-24 | 2008-07-16 | 同济大学 | Process for producing transition metal base silica aerogel, transition metal oxide silica aerogel, composite transition metal oxide silica aerogel |
| CN101948127A (en) * | 2010-09-20 | 2011-01-19 | 烟台大学 | Industrial preparation method of non-oxidative cerium oxide nanoparticles |
| CN105051118A (en) * | 2013-02-05 | 2015-11-11 | 巴斯夫欧洲公司 | Method for producing porous or fine-particle solid inorganic materials |
| CN104607116A (en) * | 2015-01-12 | 2015-05-13 | 朱秀榕 | Universal preparation method of high-specific surface area rare earth element-doped carbon gas gel |
| CN104772084A (en) * | 2015-03-31 | 2015-07-15 | 浙江大学 | Method for preparing metal oxide aerogel by taking inorganic salt as raw material |
| CN104941538A (en) * | 2015-06-03 | 2015-09-30 | 金承黎 | In-situ composite silicon-based multibasic oxide oxide aerogel material and preparation method thereof |
| JP2017048064A (en) * | 2015-08-31 | 2017-03-09 | 日立化成株式会社 | Aerogel composite |
| CN107162050A (en) * | 2017-06-06 | 2017-09-15 | 浙江大学 | A kind of method that block zirconia aerogels are prepared by gel accelerator of acidic amino acid |
| CN108355639A (en) * | 2018-02-10 | 2018-08-03 | 浙江大学 | A method of preparing porous oxidation cerium catalysis material |
| CN112058314A (en) * | 2020-08-31 | 2020-12-11 | 安徽壹石通材料科技股份有限公司 | Normal-pressure preparation method of rare earth oxide blended cerium oxide aerogel |
| CN112915979A (en) * | 2021-01-25 | 2021-06-08 | 伯克利南京医学研究有限责任公司 | Aerogel sponge material and preparation method and application thereof |
| CN113181845A (en) * | 2021-06-08 | 2021-07-30 | 浙江大学 | Cerium oxide aerogel loaded with alloy nanoparticles and preparation method thereof |
| CN113842922A (en) * | 2021-09-08 | 2021-12-28 | 南京工业大学 | Composite aerogel and preparation method and application thereof |
Non-Patent Citations (1)
| Title |
|---|
| A sol–gel methodology for the preparation of lanthanide-oxide aerogels: preparation and characterization;Brady J. Clapsaddle et al.;《J Sol-Gel Sci Technol》;第64卷;第2.1-2.2节 * |
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