WO2022160411A1 - Matériau de dioxyde de cérium poreux tridimensionnel à plusieurs étages ultra-léger et son procédé de préparation - Google Patents

Matériau de dioxyde de cérium poreux tridimensionnel à plusieurs étages ultra-léger et son procédé de préparation Download PDF

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WO2022160411A1
WO2022160411A1 PCT/CN2021/079237 CN2021079237W WO2022160411A1 WO 2022160411 A1 WO2022160411 A1 WO 2022160411A1 CN 2021079237 W CN2021079237 W CN 2021079237W WO 2022160411 A1 WO2022160411 A1 WO 2022160411A1
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preparation
ultra
light
cerium
ceria
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PCT/CN2021/079237
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Chinese (zh)
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吴张雄
吴雷
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苏州大学
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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
    • 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
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
    • 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
    • C01P2004/03—Particle morphology depicted by an image obtained by SEM
    • 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
    • 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
    • C01P2006/16—Pore diameter
    • C01P2006/17—Pore diameter distribution

Definitions

  • the invention relates to the field of rare earth metal oxide nanomaterials, in particular to an ultra-light three-dimensional hierarchical porous ceria material and a preparation method thereof.
  • Ceria is a light yellow or white powder, a very well-known cerium compound, generally calcined from cerium precursor salts or hydroxides, CeO 2 is most commonly used as a catalyst or as a catalyst non-inert carrier. It has been 44 years since ceria was first used by Ford Motor Company as an oxygen storage component in automotive converters, and ceria has become an irreplaceable component in three-way catalysts (TWCs). In addition to this recognized use, ceria is increasingly becoming a catalyst component for various catalytic applications.
  • CeO2-based materials For its application in fuel cells, CeO2-based materials have almost entered the market stage, while for some other catalytic reactions such as reforming processes, photocatalysis, water gas shift reactions, thermochemical water splitting and organic reactions, ceria as A unique material is on the rise, offering great prospects for future market breakthroughs.
  • the existing preparation methods of CeO 2 mainly include solid-phase sintering method, precipitation method, hydrothermal method, microemulsion method, sol-gel method and the like.
  • the solid-phase sintering method is a traditional powder preparation process, which is a method of preparing materials by solid-solid reaction at high temperature.
  • the solid-phase sintering method has the advantages of large output and simple preparation process.
  • most of the CeO 2 directly prepared by high temperature calcination are bulk particles with irregular morphology and dense surface, and most of them are narrow particles stacked between CeO 2 particles.
  • CeO 2 prepared by this method is prone to agglomeration and sintering, which leads to its compact surface as a catalyst, which is not conducive to the mass transfer in the catalytic process.
  • Precipitation synthesis is a simple and easy-to - operate method to prepare CeO2 nanomaterials, so this method is widely used in industrial applications.
  • the CeO2 nanomaterials obtained by this method are non-uniform in morphology and size, with small porosity and low particle dimension.
  • the product has poor dispersibility and is easy to aggregate after heat treatment.
  • the hydrothermal method provides a reaction environment that cannot be obtained under normal temperature and pressure conditions for the preparation of nano-oxides.
  • no high temperature calcination treatment is carried out, which avoids the phenomenon of oxide powder agglomeration, so that the prepared oxide has the unique advantages of high purity, good dispersibility, and good shape controllable crystal form.
  • most of the particles prepared by this method are 0-dimensional, 1-dimensional and 2-dimensional particles, and the pore structure of the particles does not contain macropores.
  • the hydrothermal method has strict requirements on equipment requirements and reaction conditions, and the equipment is expensive and the preparation time is long.
  • Microemulsion method also known as reverse micelle method, is a new liquid-phase chemical synthesis method for the synthesis of monodisperse nanomaterials in recent years.
  • the reason why the microemulsion method has aroused great research interest is that the microbubbles formed in the microemulsion act as a microreactor, and the formation of crystal nuclei and the growth process of particles are controlled in the microreactor, so that the prepared nanoparticles Narrow size distribution, controllable particle size, not easy to agglomerate between particles, good stability, etc.
  • Most of the particles prepared by this method are 0-dimensional, 1-dimensional and 2-dimensional particles, and the pore structure of the particles does not contain macropores.
  • the sol-gel method is to form a sol through the polymerization and hydrolysis of metal alkoxides or inorganic substances under low temperature conditions, and generate a gel with a certain spatial structure under certain conditions, and obtain the corresponding nano-metal after further heat treatment. Oxide solid powder.
  • This method has the advantages of low reaction temperature, small product particles, narrow particle size distribution and high purity, but the whole sol-gel process takes a long time, and most of the particles prepared by this method are 0-dimensional, 1-dimensional and 2-dimensional particles.
  • the pore structure of the particles does not contain macropores.
  • the CeO 2 prepared by the above method generally has a dense surface and the mesopores stacked between CeO 2 particles are small in size, which is not only unfavorable for the mass transfer in the catalytic process, but also easily leads to a large pressure drop in the reactor due to the dense accumulation of particles.
  • the preparation of three-dimensional hierarchical porous materials has received extensive attention in recent years.
  • the three-dimensional hierarchical porous material has a high effective specific surface area and can form a communication channel between the hierarchical pores, which is beneficial to the mass transfer of the catalytic reaction.
  • three-dimensional hierarchical porous materials often have ultra-light properties like aerogels, and devices or devices using such materials, such as automotive converters and certain fuel cells, will become lighter, especially in In some large-scale usage, its advantages will be more obvious.
  • Three-dimensional hierarchically porous materials have shown obvious advantages in the fields of catalysis, energy, environment, etc. Therefore, the development of a simple, fast, and low-waste synthetic method for the large-scale preparation of three - dimensional hierarchically porous CeO2 materials is bound to promote its Rapid development in many market applications.
  • CN200410023273 Cerium dioxide prepared by using small organic molecules as precipitating agent is a common low-dimensional solid powder material with a single pore size and mainly mesopores; CN201310228257 uses Artemia eggshell as a hard template, and the processing process is complicated; CN201510254070 uses Sodium dodecyl sulfonate was used as a template to synthesize porous CeO 2 with macropores and mesopores, which did not contain microporous structure; CN201310111043 combined hydrothermal method with cerium dioxide prepared by cysteine also did not have a three-dimensional structure. Therefore, there is still a need for a CeO 2 material that is simple to prepare and has through-through macropore-mesoporous-micropore hierarchical channels.
  • the present invention provides an ultra-light three-dimensional hierarchical porous ceria material and a preparation method thereof.
  • the ceria material of the present invention has through macropore-mesoporous-microporous crystallinity, high porosity and large specific surface area, aerogel-like ultralight properties and good thermal stability.
  • a preparation method of an ultra-light three-dimensional hierarchical porous ceria material of the present invention comprises the following steps:
  • step (2) drying the precursor solution obtained in step (1), and heat-treating the dried product at 400-1000° C. for 0.5-4.0 h to obtain an ultra-light three-dimensional hierarchical porous ceria material.
  • the cerium salt is selected from one or more of cerium nitrate hexahydrate, cerium chloride, cerium sulfate and cerium bromide.
  • the molecular foaming agent is amino acid.
  • This method adopts chemical foaming, a large amount of gas generated by the pyrolysis of the complex of Ce 3+ and amino acid, after reaching the foaming temperature, the foaming conditions are available during the synthesis of ceria, and as the temperature increases, bubbles nucleate And grow up until it bursts. Due to the different sizes of the bubbles, the bubbles burst to form pore structures of different sizes, that is, multi-level pore channels.
  • the molar ratio of cerium salt and molecular blowing agent is 30-1:1-30.
  • the molar ratio of cerium salt and molecular foaming agent specifically refers to the molar ratio of Ce 3+ ions and molecular foaming agent.
  • the solvent for dissolving the cerium salt and the molecular foaming agent is water.
  • step (1) a pore-forming agent is added in the mixing process, and the pore-forming agent can be decomposed at high temperature or can be removed by subsequent treatment of acid washing or alkali washing.
  • the pore-forming agent is selected from one or more of nonionic surfactants, cationic surfactants, polymers, soluble inorganic salts and colloidal crystals; wherein, the nonionic surfactants include F127, F108, P123, Cationic surfactants include CTAB and CTAC, polymers include polystyrene and polyethylene glycol, soluble inorganic salts include sodium chloride and potassium chloride, and the colloidal crystals include silica nanoparticles.
  • step (2) drying at 40-200° C. for 0.5-6 h.
  • the heating rate of the heat treatment is 1-20°C/min.
  • the purpose of the calcination temperature higher than 400°C is to ensure the purity of the prepared ceria.
  • the present invention also provides an ultra-light three-dimensional hierarchical porous ceria material prepared by the above preparation method.
  • the present invention has at least the following advantages:
  • cerium salt is mixed with amino acid, and after reaching the foaming temperature, cerium dioxide foams during synthesis, and bubbles nucleate, grow and burst, and fluid foam becomes solid foam through stabilization process. Differently, a hierarchical pore structure is formed after bubble collapse.
  • ( 2 ) CeO2 prepared by the present invention has through-penetrating macropore-mesoporous-microporous hierarchical channels, good crystallinity, high porosity and large specific surface area, aerogel-like ultra-light properties and good Thermal stability.
  • the present invention can adjust the pore structure and crystal grain state of ceria by adjusting the amount of Ce 3+ and amino acid, and the calcination temperature.
  • the solvent used in the present invention is water, which can be recycled and reused by condensation in the subsequent drying process, and no waste liquid is produced.
  • the whole preparation process of the present invention is simple, fast, low-waste and easy to operate, and is suitable for industrialized mass preparation without special expensive equipment.
  • Figure 1 shows Example 1 (Ce-His-1-1-400), Example 2 (Ce-His-1-1-500), Example 3 (Ce-His-1-1-600) and Wide-angle XRD pattern of ceria prepared in Example 4 (Ce-His-1-1-800);
  • Fig. 2 is the embodiment 1 (Ce-His-1-1-400) of the present invention, embodiment 5 (Ce-His-2-1-400), embodiment 6 (Ce-His-1-2-400) and Wide-angle XRD pattern of ceria prepared in Example 7 (Ce-His-1-4-400);
  • Figure 3 is prepared by Example 1 (a, b and c), Example 2 (d, e and f), Example 3 (g, h and i) and Example 4 (j, k and l) of the present invention SEM pattern of ceria;
  • Figure 4 is prepared by Example 1 (a, b and c), Example 5 (d, e and f), Example 6 (g, h and i) and Example 7 (j, k and l) of the present invention SEM pattern of ceria;
  • Fig. 5 is the nitrogen adsorption and desorption curves of ceria prepared in Example 1 (Ce-His-1-1-400) and Example 8 (Ce-His-1-1-400-0.62F127) of the present invention;
  • Fig. 6 is the micropore pore size distribution diagram of the ceria prepared in Example 1 (Ce-His-1-1-400) and Example 8 (Ce-His-1-1-400-0.62F127) of the present invention;
  • Fig. 7 is the pore size distribution diagram of the ceria prepared in Example 1 (Ce-His-1-1-400) and Example 4 (Ce-His-1-1-800) of the present invention, measured by a mercury porosimeter.
  • This example is a preparation process without adding a pore-forming agent.
  • 1.735g of Ce(NO 3 ) 3 ⁇ 6H 2 O was weighed and dissolved in 10ml of water, which was recorded as solution A; in addition, 0.62g of histidine was weighed and dissolved in 30ml of water.
  • the water is recorded as solution B; the solution A and solution B are mixed and stirred to obtain a precursor solution (the molar ratio of Ce 3+ ions and histidine is 1:1).
  • the prepared precursor solution was transferred to an oven at 100 °C for drying. After drying, the dried product was placed in a muffle furnace, and the temperature was raised to 400 °C for 3 hours at a heating rate of 5 °C/min.
  • Example 1 The calcination temperature in the muffle furnace in Example 1 was changed to 500° C., and other operations were the same as those in Example 1.
  • Example 1 The calcination temperature in the muffle furnace in Example 1 was changed to 600° C., and other operations were the same as those in Example 1.
  • Example 1 The calcination temperature in the muffle furnace in Example 1 was changed to 800° C., and other operations were the same as those in Example 1.
  • Example 1 The dosage of Ce(NO 3 ) 3 ⁇ 6H 2 O in Example 1 was changed to 3.47 g (the molar ratio of Ce 3+ ion and histidine was 2:1), and other operations were the same as those in Example 1.
  • Example 1 The dosage of histidine in Example 1 was changed to 1.24 g (the molar ratio of Ce 3+ ions and histidine was 1:2), and other operations were the same as those in Example 1.
  • Example 1 The dosage of histidine in Example 1 was changed to 2.48 g (the molar ratio of Ce 3+ ions and histidine was 1:4), and other operations were the same as those in Example 1.
  • F127 is polyoxyethylene-polyoxypropylene-polyoxyethylene, add 0.62g F127, other operations are the same as Example 1.
  • Figure 1 shows the wide-angle XRD patterns of ceria prepared in Examples 1, 2, 3 and 4. It can be seen that with the increase of calcination temperature, the half-peak width of characteristic peaks gradually narrows, indicating that adjusting the calcination temperature can adjust the particle size CeO2 grain size and degree of crystallization.
  • Figure 2 is the wide-angle XRD patterns of ceria prepared in Examples 1, 5, 6 and 7. Under the condition of a certain temperature, with the increase of the addition ratio of histidine, the half-peak width of the characteristic peak gradually becomes wider, indicating that The grain size of CeO2 in the particles can be adjusted by adjusting the addition ratio of histidine.
  • Figure 3 is the SEM spectra of the ceria prepared in Examples 1, 2, 3 and 4.
  • the prepared ceria has a three-dimensional structure and well-developed pores, and can maintain the porous morphology at different temperatures. At 800 °C high temperature, the porous morphology can still be maintained, indicating that ceria has good thermal stability.
  • Figure 4 shows the SEM images of the ceria prepared in Examples 1, 5, 6 and 7. The porous morphology of CeO 2 synthesized by adjusting the ratio of different Ce 3+ ions and histidine can still be maintained.
  • Fig. 5 is the nitrogen adsorption and desorption curves of the ceria prepared in Examples 1 and 8
  • Fig. 6 is the pore size distribution diagram of the ceria prepared in Examples 1 and 8.
  • FIG. 7 is the pore size distribution diagram of the ceria prepared in Examples 1 and 4 measured by a mercury porosimeter.
  • the prepared CeO 2 contains abundant macropores and some mesopores.
  • the measured accumulation of ceria in Example 1 The density is 0.0887 g ⁇ cm -3 and the total porosity is 76.86%.
  • the CeO2 material prepared by this method has through-penetrating macropore-mesoporous-microporous hierarchical channels, good crystallinity, high porosity and large specific surface area, aerogel-like ultralight properties and good thermal stability. sex.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Geology (AREA)
  • Inorganic Chemistry (AREA)
  • Analytical Chemistry (AREA)
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  • Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)

Abstract

La présente invention concerne un matériau de dioxyde de cérium poreux tridimensionnel à plusieurs étages ultra-léger et son procédé de préparation, comprenant les étapes suivantes : respectivement dissoudre et mélanger un sel de cérium et un agent moussant moléculaire pour obtenir une solution précurseur ; sécher la solution précurseur et traiter thermiquement le produit séché à une température de 400 à 1 000 °C pendant 0,5 à 4,0 h pour obtenir le matériau de dioxyde de cérium poreux tridimensionnel à plusieurs étages ultra-léger. Le dioxyde de cérium poreux tridimensionnel multi-étage ultra-léger selon la présente invention présente des canaux de pores multi-étages macroporeux-mésoporeux-microporeux connectés, une bonne cristallinité, une porosité élevée et une grande surface spécifique, des propriétés ultra-légères de type aérogel et une bonne stabilité thermique, et le procédé de préparation est simple, rapide, facile à utiliser, approprié pour une préparation à grande échelle, économique et respectueux de l'environnement.
PCT/CN2021/079237 2021-01-27 2021-03-05 Matériau de dioxyde de cérium poreux tridimensionnel à plusieurs étages ultra-léger et son procédé de préparation WO2022160411A1 (fr)

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Citations (4)

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GB1004352A (en) * 1960-12-14 1965-09-15 Gen Electric Improvements in porous material and method of making such material
CN1500735A (zh) * 2002-10-04 2004-06-02 ס�ѻ�ѧ��ҵ��ʽ���� 一种制造二氧化钛的方法
CN107275098A (zh) * 2017-06-30 2017-10-20 湖南大学 一种具有多尺度孔结构的三维中空碳泡沫电极材料及其制备方法与应用
CN108355639A (zh) * 2018-02-10 2018-08-03 浙江大学 一种制备多孔氧化铈催化材料的方法

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US20030186805A1 (en) * 2002-03-28 2003-10-02 Vanderspurt Thomas Henry Ceria-based mixed-metal oxide structure, including method of making and use
CN103395818B (zh) * 2013-07-16 2015-06-10 上海应用技术学院 一种介孔氧化铈纳米材料及其制备方法
CN104150525B (zh) * 2014-08-21 2016-05-18 安徽理工大学 氧化物多孔材料及其普适性制备方法
CN106946282B (zh) * 2017-02-27 2018-12-28 广东省稀有金属研究所 一种多孔铈基复合氧化物的制备方法
CN107381615A (zh) * 2017-09-08 2017-11-24 济南大学 一种有效调控二氧化铈介孔球粒径的方法及其应用

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1004352A (en) * 1960-12-14 1965-09-15 Gen Electric Improvements in porous material and method of making such material
CN1500735A (zh) * 2002-10-04 2004-06-02 ס�ѻ�ѧ��ҵ��ʽ���� 一种制造二氧化钛的方法
CN107275098A (zh) * 2017-06-30 2017-10-20 湖南大学 一种具有多尺度孔结构的三维中空碳泡沫电极材料及其制备方法与应用
CN108355639A (zh) * 2018-02-10 2018-08-03 浙江大学 一种制备多孔氧化铈催化材料的方法

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