CN106622206A - Mesoporous cerium dioxide hollow spheres or mesoporous cerium dioxide/carbon composite material hollow spheres and preparation method thereof - Google Patents
Mesoporous cerium dioxide hollow spheres or mesoporous cerium dioxide/carbon composite material hollow spheres and preparation method thereof Download PDFInfo
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- CN106622206A CN106622206A CN201611262763.9A CN201611262763A CN106622206A CN 106622206 A CN106622206 A CN 106622206A CN 201611262763 A CN201611262763 A CN 201611262763A CN 106622206 A CN106622206 A CN 106622206A
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- hollow ball
- ceria
- hollow
- mesoporous
- carbon composite
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- 229910000422 cerium(IV) oxide Inorganic materials 0.000 title claims abstract description 96
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 title claims abstract description 91
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 51
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 49
- 239000002131 composite material Substances 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 239000000843 powder Substances 0.000 claims abstract description 67
- 238000010438 heat treatment Methods 0.000 claims abstract description 34
- 238000006243 chemical reaction Methods 0.000 claims abstract description 32
- 238000005406 washing Methods 0.000 claims abstract description 32
- 239000012298 atmosphere Substances 0.000 claims abstract description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 24
- 238000001035 drying Methods 0.000 claims abstract description 16
- 150000000703 Cerium Chemical class 0.000 claims abstract description 10
- 150000007524 organic acids Chemical class 0.000 claims abstract description 10
- 239000011259 mixed solution Substances 0.000 claims abstract description 8
- 239000012153 distilled water Substances 0.000 claims abstract description 4
- 239000000463 material Substances 0.000 claims description 32
- 239000012693 ceria precursor Substances 0.000 claims description 19
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 12
- LTUDISCZKZHRMJ-UHFFFAOYSA-N potassium;hydrate Chemical compound O.[K] LTUDISCZKZHRMJ-UHFFFAOYSA-N 0.000 claims description 9
- 229910052684 Cerium Inorganic materials 0.000 claims description 6
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims description 6
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 5
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 claims description 4
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 claims description 4
- VYLVYHXQOHJDJL-UHFFFAOYSA-K cerium trichloride Chemical compound Cl[Ce](Cl)Cl VYLVYHXQOHJDJL-UHFFFAOYSA-K 0.000 claims description 4
- 239000001630 malic acid Substances 0.000 claims description 4
- 235000011090 malic acid Nutrition 0.000 claims description 4
- 235000006408 oxalic acid Nutrition 0.000 claims description 4
- 230000031709 bromination Effects 0.000 claims description 3
- 238000005893 bromination reaction Methods 0.000 claims description 3
- OZECDDHOAMNMQI-UHFFFAOYSA-H cerium(3+);trisulfate Chemical compound [Ce+3].[Ce+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O OZECDDHOAMNMQI-UHFFFAOYSA-H 0.000 claims description 3
- 229910000333 cerium(III) sulfate Inorganic materials 0.000 claims description 3
- 239000004310 lactic acid Substances 0.000 claims description 3
- 235000014655 lactic acid Nutrition 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- 238000010792 warming Methods 0.000 claims description 2
- 239000002243 precursor Substances 0.000 abstract description 20
- 238000000034 method Methods 0.000 abstract description 15
- 239000000203 mixture Substances 0.000 abstract description 9
- 238000000967 suction filtration Methods 0.000 abstract description 3
- 239000000126 substance Substances 0.000 abstract 1
- 239000002994 raw material Substances 0.000 description 19
- 238000009413 insulation Methods 0.000 description 14
- 238000013019 agitation Methods 0.000 description 13
- 238000004821 distillation Methods 0.000 description 13
- 239000007864 aqueous solution Substances 0.000 description 12
- 239000012695 Ce precursor Substances 0.000 description 11
- 241000790917 Dioxys <bee> Species 0.000 description 11
- 238000001027 hydrothermal synthesis Methods 0.000 description 10
- 238000009833 condensation Methods 0.000 description 8
- 230000005494 condensation Effects 0.000 description 8
- 239000012071 phase Substances 0.000 description 8
- 238000004458 analytical method Methods 0.000 description 7
- 238000001069 Raman spectroscopy Methods 0.000 description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 6
- 239000011148 porous material Substances 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 5
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 description 4
- CXKWCBBOMKCUKX-UHFFFAOYSA-M methylene blue Chemical compound [Cl-].C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 CXKWCBBOMKCUKX-UHFFFAOYSA-M 0.000 description 4
- 229960000907 methylthioninium chloride Drugs 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 229910000420 cerium oxide Inorganic materials 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000010304 firing Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 239000004408 titanium dioxide Substances 0.000 description 2
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 1
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 1
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Chemical compound OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 1
- 239000005642 Oleic acid Substances 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 241000235342 Saccharomycetes Species 0.000 description 1
- 239000011358 absorbing material Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- TZIBOXWEBBRIBM-UHFFFAOYSA-N cerium(3+) oxygen(2-) titanium(4+) Chemical compound [O--].[O--].[Ti+4].[Ce+3] TZIBOXWEBBRIBM-UHFFFAOYSA-N 0.000 description 1
- VZDYWEUILIUIDF-UHFFFAOYSA-J cerium(4+);disulfate Chemical compound [Ce+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O VZDYWEUILIUIDF-UHFFFAOYSA-J 0.000 description 1
- 229910000355 cerium(IV) sulfate Inorganic materials 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 150000004676 glycans Chemical class 0.000 description 1
- 239000010416 ion conductor Substances 0.000 description 1
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000004005 microsphere Substances 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 229920001282 polysaccharide Polymers 0.000 description 1
- 239000005017 polysaccharide Substances 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 230000001603 reducing effect Effects 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000002887 superconductor Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
Classifications
-
- 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
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/51—Spheres
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
- C01P2002/82—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by IR- or Raman-data
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- 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
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/30—Particle morphology extending in three dimensions
- C01P2004/32—Spheres
- C01P2004/34—Spheres hollow
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
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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
- C01P2006/14—Pore volume
-
- 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
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
- Exhaust Gas Treatment By Means Of Catalyst (AREA)
Abstract
The invention discloses mesoporous cerium dioxide hollow spheres or mesoporous cerium dioxide/carbon composite material hollow spheres and a preparation method thereof. The preparation method comprises the following steps: 1) dissolving one cerium salt and one organic acid into distilled water according to a certain ratio of amount of the substances, so as to prepare a mixed solution; 2) putting the mixed solution in a microwave hydrothermograph for reaction for a period of time at certain temperature; after finishing the reaction, performing suction filtration and washing; drying at 80 DEG C to obtain a hollow sphere type cerium dioxide precursor; 3) carrying out heat treatment on the dried precursor in an atmosphere at certain temperature and keeping heat for a period of time to obtain mesoporous cerium dioxide hollow sphere or cerium dioxide/carbon hollow sphere powder. The mesoporous cerium dioxide (/carbon) hollow sphere powder prepared by the method has the characteristics of controllable phase composition, controllable sphere diameter and controllable wall thickness. Meanwhile, the method has the advantages of low cost, simple preparation process, high efficiency and easiness in control.
Description
【Technical field】
The invention belongs to new material technology field, and in particular to a kind of mesoporous ceria hollow ball or meso-porous titanium dioxide
Cerium/carbon composite hollow ball and preparation method thereof.
【Background technology】
CeO2It is a kind of cheap rare earth material, it has good structural stability and a catalytic performance, stronger oxidation-
Reducing property.
At present, cerium oxide hollow ball (CeO is prepared2) common method have two kinds：One kind is template.Such as open former times jade et al.
CeO has been prepared with reagents such as saccharomycete, ceric sulfate, NaOH, ethanol, acid oranges2Tiny balloon；Li Yadong etc. is by Portugal
Grape sugar makes polysaccharide microsphere, and as template, cerous nitrate is reagent, and Jing calcinings have been obtained CeO2Nano-hollow ball；Jiang Xueliang
Et al. with styrene, methyl methacrylate, polyvinylpyrrolidone, water, methyl alcohol, cerous nitrate as raw material, Jing calcining be obtained
CeO2Tiny balloon；CeO prepared by template2Tiny balloon uniformity is preferable, but the later stage need to specially remove removing template, and process is complicated.
Another kind is liquid phase method, usually hydro-thermal reaction.If horse Jingjing et al. is with hexa, citric acid, water, cerous nitrate as original
Material, has been obtained double-deck CeO2Tiny balloon；Such as high Lian et al. CeO is prepared with oleic acid, cerous nitrate, toluene, water2It is hollow to receive
Rice cube；Common hydrothermal reaction process need to add surfactant, alkaline matter or organic solvent, pollute environment, reaction
It is of long duration, complex operation.
At present, not yet at the same time without alkaline matter, surfactant-free in the presence of, be directly synthesized different size, difference
The nano Ce O of wall thickness, good dispersion2Relevant report in terms of hollow ball powder.
【The content of the invention】
For the defect for overcoming above-mentioned prior art to exist, it is an object of the invention to provide a kind of mesoporous ceria is empty
Bulbus cordis or mesoporous ceria/carbon composite hollow ball and preparation method thereof, the method has low cost, preparation process is simple
And the advantages of easily controllable and environment protection energy-saving efficient, and the phase composition of hollow ball-type powder is controllable, diameter is adjustable, wall thickness is adjustable.
The present invention is to be achieved through the following technical solutions：Comprise the following steps：
1) it is (1～1.5) according to the ratio of the amount of material by cerium salt and organic acid：During (0.1～3) is dissolved in distilled water, fill
Divide stirring that mixed solution is obtained；
2) mixed solution is reacted into 1s～10min at 150～200 DEG C, reacts and terminate rear filtering and washing and be dried to obtain
Hollow ball-type ceria presoma；
3) in atmosphere, hollow ball-type ceria presoma is incubated into 0.5～4h at 280～1000 DEG C, is then cooled down
To room temperature, mesoporous ceria hollow ball or mesoporous ceria/carbon composite hollow ball are obtained.
Further, step 1) in cerium salt be six nitric hydrate ceriums, cerium chloride, cerous sulfate or bromination cerium.
Further, step 1) in organic acid be monohydrate potassium, lactic acid, malic acid or oxalic acid.
Further, step 1) in the well-beaten time be 0.5～4h.
Further, step 1) mixed solution in cerium salt and organic acid total concentration be 0.05～2mol/L.
Further, step 2) in reaction terminate rear filtering and washing 3 times, obtain hollow ball-type two in 80 DEG C of 1～24h of drying
Cerium oxide precursor.
Further, step 3) in atmosphere be air, N2Or Ar；When atmosphere is air, ceria hollow ball is obtained；Gas
Atmosphere is N2Or during Ar, obtain mesoporous ceria/carbon composite hollow ball.
Further, step 3) in hollow ball type ceria precursor be from room temperature, with the liter of 0.5～5 DEG C/min
Warm speed, is warming up to 280～1000 DEG C.
One kind is compound using mesoporous ceria hollow ball obtained in method prepared as described above or mesoporous ceria/carbon
Material hollow ball, the mesoporous ceria hollow ball is yellow powder, and mesoporous ceria/carbon composite hollow ball is black
Powder.
Further, the mesoporous ceria hollow ball or mesoporous ceria/carbon composite hollow ball is a diameter of
0.1～1.92 μm, wall thickness is 35～90nm.
Compared with prior art, the present invention has following beneficial technique effect：
The present invention only, using microwave-hydrothermal method, need to prepare meso-porous titanium dioxide with two kinds of materials of cerium salt and organic acid as raw material
Cerium or ceria/carbon composite hollow ball.The mesoporous ceria prepared using the method and ceria/carbon hollow ball
With phase composition is controllable, diameter and the adjustable advantage of wall thickness, the problems such as can easily solve complicated raw material, complex operation, together
When, the method has that firing rate is fast, the reaction time is short, efficiency high, the features such as repeatability is high, pollution-free.It is of the invention obtained
Nano Ce O2Hollow ball has the advantages that density is little, specific surface area is big, SOFC oxygen ion conductor material,
The aspects such as glass polishing agent, UV absorbing material, cleaning catalyst for tail gases of automobiles and superconductor have important purposes, particularly originally
CeO prepared by invention2/ C hollow balls show good ultraviolet light capture-effect.
The ceria hollow ball prepared using the present invention, a diameter of 0.1～1.92 μm, wall thickness is 35～90nm, is had
Phase composition is controllable, diameter and the adjustable advantage of wall thickness, as catalyst and can prepare its doped and compounded material.
【Description of the drawings】
Fig. 1 is CeO prepared by the microwave-hydrothermal method of the specific embodiment of the invention 12The pattern of precursor hollow sphere and wall thickness
SEM photograph；Wherein (a) is the SEM photograph of pattern, is (b) SEM photograph of wall thickness；
Fig. 2 is CeO prepared by the microwave-hydrothermal method of the specific embodiment of the invention 22The pattern of precursor hollow sphere and wall thickness
SEM photograph；Wherein (a) is the SEM photograph of pattern, is (b) SEM photograph of wall thickness；
Fig. 3 is CeO prepared by the microwave-hydrothermal method of the specific embodiment of the invention 22Precursor hollow sphere heat in air atmosphere
Pattern and phase composition photo after process；Wherein, (a) be SEM photograph；B () is Raman spectrograms；C () is graph of pore diameter distribution；
Fig. 4 is CeO prepared by the microwave-hydrothermal method of the specific embodiment of the invention 32The pattern of precursor hollow sphere and wall thickness
SEM photograph；Wherein (a) is the SEM photograph of pattern, is (b) SEM photograph of wall thickness；
Fig. 5 is CeO prepared by the microwave-hydrothermal method of the specific embodiment of the invention 32Precursor hollow sphere is in an ar atmosphere at heat
Pattern and phase composition photo after reason；Wherein, (a) be SEM photograph；B () is Raman spectrograms；C () is graph of pore diameter distribution.
Fig. 6 is CeO prepared by the microwave-hydrothermal method of the specific embodiment of the invention 42The pattern of precursor hollow sphere and wall thickness
SEM photograph；Wherein (a) is the SEM photograph of pattern, is (b) SEM photograph of wall thickness；
【Specific embodiment】
The present invention is described in further details below in conjunction with the accompanying drawings.
With reference to specific embodiment, the present invention is described in further detail, it is described be explanation of the invention and
It is not to limit.
The present invention only, using microwave-hydrothermal method, need to prepare meso-porous titanium dioxide with two kinds of materials of cerium salt and organic acid as raw material
Cerium hollow ball.The ceria hollow ball prepared using the method has the adjustable advantage of controllable phase composition, diameter and wall thickness, energy
It is enough convenient the problems such as solve complicated raw material, complex operation, meanwhile, the method has that firing rate is fast, the reaction time is short, efficiency
High, repeated high, pollution-free the features such as.
Embodiment 1
1) it is 1 according to the ratio of the amount of material with six nitric hydrate ceriums and monohydrate potassium as raw material:0.1, it is made into concentration
For the aqueous solution of 0.5mol/L, at room temperature, magnetic agitation 3h is sufficiently mixed；
2) mixed liquor is put into microwave reaction bottle, 2min is reacted at 200 DEG C, reaction drops to room temperature, taken out after terminating
Filter, the sample after washing with distillation water washing 3 times, be then put into 80 DEG C of drying boxes and be dried 8h, obtains hollow ball-shape dioxy
Change cerium precursor；
3) dried hollow ball-type ceria precursor is placed in tube furnace, in air atmosphere, from room temperature,
280 DEG C are raised to the heating rate of 2 DEG C/min, 1h is incubated, insulation cools to room temperature with the furnace, obtains mesoporous ceria after terminating
Hollow ball powder.
CeO prepared by the present embodiment microwave hydrothermal2The outward appearance of presoma be pale yellow powder, the CeO after heat treatment2It is hollow
The outward appearance of ball powder is yellow powder.CeO prepared by microwave hydrothermal2Hollow ball powder carries out Morphology analysis, SEM photograph
As shown in figure 1, a diameter of 0.4-0.88 μm of the ceria hollow ball of gained is can be seen that from Fig. 1 (a), from Fig. 1 (b)
In it can be seen that wall thickness be 64nm.After heat treatment, the diameter and wall thickness of ceria hollow ball are substantially unchanged.
Embodiment 2
1) it is 1 according to the ratio of the amount of material with six nitric hydrate ceriums and monohydrate potassium as raw material:0.5, it is made into concentration
For the aqueous solution of 0.1mol/L, at room temperature, magnetic agitation 4h is sufficiently mixed；
2) mixed liquor is put into microwave reaction bottle, 2min is reacted at 170 DEG C, reaction drops to room temperature, taken out after terminating
Filter, the sample after washing with distillation water washing 3 times, be then put into 80 DEG C of drying boxes and be dried 20h, obtains hollow ball-shape dioxy
Change cerium precursor；
3) dried hollow ball-shape ceria precursor is placed in tube furnace, in air atmosphere, with 0.5 DEG C/
The heating rate of min is raised to 300 DEG C, is incubated 1h, and insulation cools to room temperature with the furnace, obtains mesoporous ceria hollow ball after terminating
Powder.
CeO prepared by the present embodiment microwave hydrothermal2The outward appearance of presoma be pale yellow powder, the CeO after heat treatment2It is hollow
The outward appearance of ball powder is yellow powder.CeO prepared by microwave hydrothermal2Hollow ball powder carries out Morphology analysis, SEM photograph
As shown in Fig. 2 a diameter of 1.17-1.92 μm of the ceria hollow ball of gained is can be seen that from Fig. 2 (a), from Fig. 2 (b)
In it can be seen that wall thickness be 55nm.After heat treatment, the diameter and wall thickness of ceria hollow ball are substantially unchanged.To heat treatment
CeO afterwards2Hollow ball powder carries out the analysis of SEM microscopic appearances, Raman constituent analyses and pore-size distribution, such as Fig. 3 (a) to Fig. 3
C shown in (), it is still hollow ball that the sample after being heat-treated under air finds out it from SEM photograph, and its group is obtained from Raman spectrograms
Become CeO2, can see from graph of pore diameter distribution, the CeO being heat-treated under air atmosphere2Pore volume is concentrated mainly on 1-2nm.
Embodiment 3
1) it is 1 according to the ratio of the amount of material with six nitric hydrate ceriums and monohydrate potassium as raw material:0.7, it is made into concentration
For the aqueous solution of 0.1mol/L, at room temperature, magnetic agitation 2h is sufficiently mixed；
2) mixed liquor is put into microwave reaction bottle, 2min is reacted at 150 DEG C, reaction drops to room temperature, taken out after terminating
Filter, the sample after washing with distillation water washing 3 times, be then put into 80 DEG C of drying boxes and be dried 12h, obtains hollow ball-shape dioxy
Change cerium precursor；
3) dried hollow ball-shape ceria precursor is placed in tube furnace, under an ar atmosphere, with 2 DEG C/min's
Heating rate is raised to 600 DEG C, is incubated 1h, and insulation cools to room temperature with the furnace, obtains mesoporous ceria/carbon composite after terminating
Hollow ball.
CeO prepared by the present embodiment microwave hydrothermal2The outward appearance of presoma be pale yellow powder, the CeO after heat treatment2/ carbon is multiple
The outward appearance of condensation material hollow ball powder is black powder.CeO prepared by microwave hydrothermal2Hollow ball powder carries out microscopic appearance point
Analysis, SEM photograph is as shown in figure 4, as can be seen that a diameter of 1.27-1.84 μ of the ceria hollow ball of gained from Fig. 4 (a)
M, it can be seen that wall thickness is 90nm from Fig. 4 (b).After heat treatment, the diameter and wall of ceria/carbon composite hollow ball
It is thick substantially unchanged.To the CeO after heat treatment2Hollow ball powder carries out SEM microscopic appearances, Raman constituent analyses and aperture point
Cloth is analyzed, and shown in such as Fig. 5 (a) to Fig. 5 (c), it is still hollow ball that the sample after being heat-treated under air finds out it from SEM photograph,
Obtain from Raman spectrograms consisting of CeO2With free state C, can see from graph of pore diameter distribution, under air atmosphere at heat
The CeO of reason2Pore volume is concentrated mainly on 1-2nm.
CeO is obtained with the present embodiment2/ C hollow balls are catalyst, and concentration is 0.5g/L, suppress the methylene blue of 0.1g/L
The aqueous solution is degraded, and after the Hg light irradiation 140min of 400W, aqueous solution of methylene blue without catalyst degraded is remaining 4% left
The right side, and with CeO2/ C hollow balls are 78% or so, CeO for the conservation rate of the aqueous solution of methylene blue Methylene Blue of catalyst2/C
Hollow ball shows good ultraviolet light screening effect.
Embodiment 4
1) it is 1.5 according to the ratio of the amount of material with six nitric hydrate ceriums and monohydrate potassium as raw material:0.1, it is made into dense
The aqueous solution for 1mol/L is spent, at room temperature, magnetic agitation 4h is sufficiently mixed；
2) mixed liquor is put into microwave reaction bottle, 10min is reacted at 180 DEG C, reaction drops to room temperature, taken out after terminating
Filter, the sample after washing with distillation water washing 3 times, be then put into 80 DEG C of drying boxes and be dried 4h, obtains hollow ball-shape dioxy
Change cerium precursor；
3) dried hollow ball-shape ceria precursor is placed in tube furnace, in N2Under atmosphere, with 2 DEG C/min's
Heating rate is raised to 800 DEG C, is incubated 1h, and insulation cools to room temperature with the furnace, obtains mesoporous ceria/carbon composite after terminating
Hollow ball powder.
CeO prepared by the present embodiment microwave hydrothermal2The outward appearance of precursor be pale yellow powder, the CeO after heat treatment2/ carbon is multiple
The outward appearance of condensation material hollow ball powder is black powder.CeO prepared by microwave hydrothermal2Hollow ball powder carries out microscopic appearance point
Analysis, SEM photograph is as shown in fig. 6, as can be seen that a diameter of 0.2-0.36 μ of the ceria hollow ball of gained from Fig. 6 (a)
M, it can be seen that wall thickness is 35nm from Fig. 6 (b).After heat treatment, the diameter and wall thickness of ceria hollow ball is substantially without change
Change.
Embodiment 5
1) it is 1 according to the ratio of the amount of material with six nitric hydrate ceriums and monohydrate potassium as raw material:2, being made into concentration is
The aqueous solution of 2mol/L, at room temperature, magnetic agitation 2h is sufficiently mixed；
2) mixed liquor is put into microwave reaction bottle, 8min is reacted at 200 DEG C, reaction drops to room temperature, taken out after terminating
Filter, the sample after washing with distillation water washing 3 times, be then put into 80 DEG C of drying boxes and be dried 12h, obtains hollow ball-shape dioxy
Change cerium precursor；
3) dried hollow ball-shape ceria precursor is placed in tube furnace, under an ar atmosphere, with 2 DEG C/min's
Heating rate is raised to 800 DEG C, is incubated 2h, and insulation cools to room temperature with the furnace, obtains mesoporous ceria/carbon composite after terminating
Hollow ball powder.
CeO prepared by the present embodiment microwave hydrothermal2The outward appearance of precursor be pale yellow powder, the CeO after heat treatment2/ carbon is multiple
The outward appearance of condensation material hollow ball powder is black powder.
Embodiment 6
1) it is 1 according to the ratio of the amount of material with six nitric hydrate ceriums and monohydrate potassium as raw material:3, being made into concentration is
The aqueous solution of 1mol/L, at room temperature, magnetic agitation 4h is sufficiently mixed；
2) mixed liquor is put into microwave reaction bottle, 1s is reacted at 200 DEG C, reaction drops to room temperature, carries out suction filtration after terminating,
With distillation water washing 3 times, then the sample after washing is put into 80 DEG C of drying boxes and is dried 1h, obtain hollow ball-shape ceria
Precursor；
3) dried hollow ball-shape ceria precursor is placed in tube furnace, in N2Under atmosphere, with 2 DEG C/min's
Heating rate is raised to 600 DEG C, is incubated 4h, and insulation cools to room temperature with the furnace, obtains ceria/carbon hollow ball powder after terminating.
CeO prepared by the present embodiment microwave hydrothermal2The outward appearance of precursor be pale yellow powder, the CeO after heat treatment2/ carbon is multiple
The outward appearance of condensation material hollow ball powder is black powder.
Embodiment 7
1) it is 1 according to the ratio of the amount of material with six nitric hydrate ceriums and monohydrate potassium as raw material:1.5, it is made into concentration
For the aqueous solution of 0.05mol/L, at room temperature, magnetic agitation 0.5h is sufficiently mixed；
2) mixed liquor is put into microwave reaction bottle, 5min is reacted at 160 DEG C, reaction drops to room temperature, taken out after terminating
Filter, the sample after washing with distillation water washing 3 times, be then put into 80 DEG C of drying boxes and be dried 5h, obtains hollow ball-shape dioxy
Change cerium precursor；
3) dried hollow ball-shape ceria precursor is placed in tube furnace, in N2Under atmosphere, with 5 DEG C/min's
Heating rate is raised to 1000 DEG C, is incubated 0.5h, and insulation cools to room temperature with the furnace, obtains ceria/carbon hollow ball powder after terminating
Body.
CeO prepared by the present embodiment microwave hydrothermal2The outward appearance of precursor be pale yellow powder, the CeO after heat treatment2/ carbon is multiple
The outward appearance of condensation material hollow ball powder is black powder.
Embodiment 8
1) it is 1 according to the ratio of the amount of material with six nitric hydrate ceriums and lactic acid as raw material:0.5, being made into concentration is
The aqueous solution of 0.1mol/L, at room temperature, magnetic agitation 2h is sufficiently mixed；
2) mixed liquor is put into microwave reaction bottle, 2min is reacted at 160 DEG C, reaction drops to room temperature, taken out after terminating
Filter, the sample after washing with distillation water washing 3 times, be then put into 80 DEG C of drying boxes and be dried 6h, obtains hollow ball-shape dioxy
Change cerium precursor；
3) dried hollow ball-shape ceria precursor is placed in tube furnace, under air atmosphere, with 2 DEG C/min's
Heating rate is raised to 400 DEG C, is incubated 2h, and insulation cools to room temperature with the furnace, obtains ceria hollow ball powder after terminating.
CeO prepared by the present embodiment microwave hydrothermal2The outward appearance of precursor be pale yellow powder, the CeO after heat treatment2It is hollow
The outward appearance of ball powder is yellow powder.
Embodiment 9
1) it is 1 according to the ratio of the amount of material with cerium chloride and malic acid as raw material:1, it is made into the water that concentration is 0.5mol/L
Solution, at room temperature, magnetic agitation 0.5h is sufficiently mixed；
2) mixed liquor is put into microwave reaction bottle, 5min is reacted at 150 DEG C, reaction drops to room temperature, taken out after terminating
Filter, the sample after washing with distillation water washing 3 times, be then put into 80 DEG C of drying boxes and be dried 2h, obtains hollow ball-shape dioxy
Change cerium precursor；
3) dried hollow ball-shape ceria precursor is placed in tube furnace, under an ar atmosphere, with 1 DEG C/min's
Heating rate is raised to 800 DEG C, is incubated 1h, and insulation cools to room temperature with the furnace, obtains ceria/carbon hollow ball powder after terminating.
CeO prepared by the present embodiment microwave hydrothermal2The outward appearance of precursor be pale yellow powder, the CeO after heat treatment2/ carbon is multiple
The outward appearance of condensation material hollow ball powder is black powder.
Embodiment 10
1) it is 1 according to the ratio of the amount of material with cerous sulfate and oxalic acid as raw material:1.5, it is made into the water that concentration is 0.2mol/L
Solution, at room temperature, magnetic agitation 4h is sufficiently mixed；
2) mixed liquor is put into microwave reaction bottle, 1min is reacted at 170 DEG C, reaction drops to room temperature, taken out after terminating
Filter, the sample after washing with distillation water washing 3 times, be then put into 80 DEG C of drying boxes and be dried 24h, obtains hollow ball-shape dioxy
Change cerium precursor；
3) dried hollow ball-shape ceria precursor is placed in tube furnace, in N2Under atmosphere, with 2 DEG C/min's
Heating rate is raised to 800 DEG C, is incubated 2h, and insulation cools to room temperature with the furnace, obtains ceria/carbon hollow ball powder after terminating.
CeO prepared by the present embodiment microwave hydrothermal2The outward appearance of precursor be pale yellow powder, the CeO after heat treatment2/ carbon is multiple
The outward appearance of condensation material hollow ball powder is black powder.
Embodiment 11
1) it is 1 according to the ratio of the amount of material with bromination cerium and citric acid as raw material:2, it is made into the water that concentration is 0.1mol/L
Solution, at room temperature, magnetic agitation 4h is sufficiently mixed；
2) mixed liquor is put into microwave reaction bottle, 4min is reacted at 150 DEG C, reaction drops to room temperature, taken out after terminating
Filter, the sample after washing with distillation water washing 3 times, be then put into 80 DEG C of drying boxes and be dried 12h, obtains hollow ball-shape dioxy
Change cerium precursor；
3) dried hollow ball-shape ceria precursor is placed in tube furnace, under air atmosphere, with 0.5 DEG C/min
Heating rate be raised to 500 DEG C, be incubated 1h, insulation cools to room temperature with the furnace, obtains ceria hollow ball powder after terminating.
CeO prepared by the present embodiment microwave hydrothermal2The outward appearance of precursor be pale yellow powder, the CeO after heat treatment2It is hollow
The outward appearance of ball powder is yellow powder.
Embodiment 12
1) it is 1.5 according to the ratio of the amount of material with cerium chloride and oxalic acid as raw material:1, it is made into the water that concentration is 0.5mol/L
Solution, at room temperature, magnetic agitation 2h is sufficiently mixed；
2) mixed liquor is put into microwave reaction bottle, 10min is reacted at 150 DEG C, reaction drops to room temperature, taken out after terminating
Filter, the sample after washing with distillation water washing 3 times, be then put into 80 DEG C of drying boxes and be dried 24h, obtains hollow ball-shape dioxy
Change cerium precursor；
3) dried hollow ball-shape ceria precursor is placed in tube furnace, under air atmosphere, with 0.5 DEG C/min
Heating rate be raised to 600 DEG C, be incubated 2h, insulation cools to room temperature with the furnace, obtains ceria hollow ball powder after terminating.
CeO prepared by the present embodiment microwave hydrothermal2The outward appearance of precursor be pale yellow powder, the CeO after heat treatment2It is hollow
The outward appearance of ball powder is yellow powder.
Embodiment 13
1) it is 1 according to the ratio of the amount of material with six nitric hydrate ceriums and malic acid as raw material:3, being made into concentration is
The aqueous solution of 0.1mol/L, at room temperature, magnetic agitation 4h is sufficiently mixed；
2) mixed liquor is put into microwave reaction bottle, 1s is reacted at 200 DEG C, reaction drops to room temperature, carries out suction filtration after terminating,
With distillation water washing 3 times, then the sample after washing is put into 80 DEG C of drying boxes and is dried 8h, obtain hollow ball-shape ceria
Precursor；
3) dried hollow ball-shape ceria precursor is placed in tube furnace, in N2Under atmosphere, with 2 DEG C/min's
Heating rate is raised to 600 DEG C, is incubated 4h, and insulation cools to room temperature with the furnace, obtains ceria/carbon hollow ball powder after terminating.
CeO prepared by the present embodiment microwave hydrothermal2The outward appearance of precursor be pale yellow powder, the CeO after heat treatment2/ carbon is multiple
The outward appearance of condensation material hollow ball powder is black powder.
The preparation method of intermediary hole ceria sky of the present invention and ceria/carbon composite hollow ball, the phase of product
The Nomenclature Composition and Structure of Complexes is easily controlled, and raw material is simple, preparation process is simple, and repeatability is high, and whole preparation process is pollution-free.The present invention
A diameter of 0.1～1.92 μm of the obtained mesoporous ceria hollow ball or mesoporous ceria/carbon composite hollow ball,
Wall thickness is 35～90nm.
The invention discloses the preparation method of a kind of ceria and ceria/carbon composite hollow ball, including with
Lower step：1) a kind of cerium salt and a kind of organic acid are dissolved in distilled water according to the ratio of the amount of certain material, make mixing
Solution；2) mixed liquor is placed in into microwave hydrothermal instrument reaction a period of time under uniform temperature, reacts and terminate rear filtering and washing, 80
DEG C it is dried to obtain hollow ball-type ceria precursor；3) dried precursor is heat-treated in atmosphere under uniform temperature, and
Insulation a period of time, obtain porous silica cerium hollow ball or ceria/carbon hollow ball powder.Prepared by the present invention mesoporous
Ceria (/ carbon) hollow ball powder has the characteristics of phase composition is controllable, sphere diameter is controllable, wall thickness is controllable.Meanwhile, the method
There is low cost, preparation process is simple and easily controllable and environment protection energy-saving efficient.
Claims (10)
1. the preparation method of a kind of mesoporous ceria hollow ball or mesoporous ceria/carbon composite hollow ball, its feature
It is：Comprise the following steps：
1) it is (1～1.5) according to the ratio of the amount of material by cerium salt and organic acid：During (0.1～3) is dissolved in distilled water, fully stir
Mixing obtains mixed solution；
2) mixed solution is reacted into 1s～10min at 150～200 DEG C, reacts and terminate rear filtering and washing and be dried to obtain hollow
Ball-type ceria presoma；
3) in atmosphere, hollow ball-type ceria presoma is incubated into 0.5～4h at 280～1000 DEG C, is subsequently cooled to room
Temperature, obtains mesoporous ceria hollow ball or mesoporous ceria/carbon composite hollow ball.
2. a kind of mesoporous ceria hollow ball according to claim 1 or mesoporous ceria/carbon composite are hollow
The preparation method of ball, it is characterised in that：Step 1) in cerium salt be six nitric hydrate ceriums, cerium chloride, cerous sulfate or bromination cerium.
3. a kind of mesoporous ceria hollow ball according to claim 1 or mesoporous ceria/carbon composite are hollow
The preparation method of ball, it is characterised in that：Step 1) in organic acid be monohydrate potassium, lactic acid, malic acid or oxalic acid.
4. a kind of mesoporous ceria hollow ball according to claim 1 or mesoporous ceria/carbon composite are hollow
The preparation method of ball, it is characterised in that：Step 1) in the well-beaten time be 0.5～4h.
5. a kind of mesoporous ceria hollow ball according to claim 1 or mesoporous ceria/carbon composite are hollow
The preparation method of ball, it is characterised in that：Step 1) mixed solution in cerium salt and organic acid total concentration be 0.05～2mol/L.
6. a kind of mesoporous ceria hollow ball according to claim 1 or mesoporous ceria/carbon composite are hollow
The preparation method of ball, it is characterised in that：Step 2) in reaction terminate rear filtering and washing 3 times, obtain sky in 80 DEG C of 1～24h of drying
Bulbus cordis type ceria precursor.
7. a kind of mesoporous ceria hollow ball according to claim 1 or mesoporous ceria/carbon composite are hollow
The preparation method of ball, it is characterised in that：Step 3) in atmosphere be air, N2Or Ar；When atmosphere is air, ceria is obtained empty
Bulbus cordis；Atmosphere is N2Or during Ar, obtain mesoporous ceria/carbon composite hollow ball.
8. a kind of mesoporous ceria hollow ball according to claim 1 or mesoporous ceria/carbon composite are hollow
The preparation method of ball, it is characterised in that：Step 3) in hollow ball type ceria precursor be from room temperature, with 0.5～5 DEG C/
The heating rate of min, is warming up to 280～1000 DEG C.
9. it is a kind of to utilize mesoporous ceria hollow ball obtained in preparation method described in claim 1 or mesoporous ceria/carbon
Composite material hollow ball, it is characterised in that：The mesoporous ceria hollow ball is yellow powder, and mesoporous ceria/carbon is combined
Material hollow ball is black powder.
10. mesoporous ceria hollow ball according to claim 9 or mesoporous ceria/carbon composite hollow ball,
It is characterized in that：A diameter of the 0.1 of the mesoporous ceria hollow ball or mesoporous ceria/carbon composite hollow ball～
1.92 μm, wall thickness is 35～90nm.
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107335422A (en) * | 2017-06-06 | 2017-11-10 | 浙江师范大学 | A kind of preparation method of carbon functionalization cerium oxide |
| CN107349928A (en) * | 2017-08-29 | 2017-11-17 | 江苏师范大学 | A kind of SiO2The preparation method of@CeMnO composite photo-catalysts |
| CN108722391A (en) * | 2018-06-04 | 2018-11-02 | 中国科学院海洋研究所 | A kind of 3D C/CeO2Hollow nanostructured frame material and the preparation method and application thereof |
| CN108807943A (en) * | 2018-07-19 | 2018-11-13 | 齐鲁工业大学 | A kind of hollow-core construction CeO2@C core-shell structure copolymer nanocomposites and the preparation method and application thereof |
| CN108927135A (en) * | 2018-06-27 | 2018-12-04 | 上海上惠纳米科技有限公司 | Ceria/titanium dioxide composite mesopore ball preparation method |
| WO2020119717A1 (en) * | 2018-12-14 | 2020-06-18 | 深圳先进技术研究院 | Hollow ceric oxide preparation method |
| US20220040675A1 (en) * | 2019-10-23 | 2022-02-10 | Guangdong University Of Technology | Three-dimensionally ordered macroporous oxygen-deficient cerium dioxide catalyst, and preparation method and application thereof |
| CN115449345A (en) * | 2022-08-29 | 2022-12-09 | 内蒙古科技大学 | Preparation method of mesoporous cerium oxide coated polystyrene nano composite abrasive under microwave condition |
| CN115888686A (en) * | 2022-12-27 | 2023-04-04 | 安徽师范大学 | Cerium oxide @ carbon composite catalyst and synthesis method and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101857260A (en) * | 2010-06-29 | 2010-10-13 | 上海大学 | Method for preparing spherical cerium dioxide nano material with square-sheet surface structure by hydrothermal method |
| CN102942206A (en) * | 2012-11-20 | 2013-02-27 | 陕西科技大学 | Method for preparing cerium dioxide nanometer hollow spheres |
| CN103387256A (en) * | 2013-07-19 | 2013-11-13 | 山东大学 | Method for preparing ceria mesoporous hollow ball |
-
2016
- 2016-12-30 CN CN201611262763.9A patent/CN106622206B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101857260A (en) * | 2010-06-29 | 2010-10-13 | 上海大学 | Method for preparing spherical cerium dioxide nano material with square-sheet surface structure by hydrothermal method |
| CN102942206A (en) * | 2012-11-20 | 2013-02-27 | 陕西科技大学 | Method for preparing cerium dioxide nanometer hollow spheres |
| CN103387256A (en) * | 2013-07-19 | 2013-11-13 | 山东大学 | Method for preparing ceria mesoporous hollow ball |
Non-Patent Citations (3)
| Title |
|---|
| XIAOYUN WU等: ""Core–shell CeO2@C nanospheres as enhanced anode materials for lithium ion batteries"", 《JOURNAL OF MATERIALS CHEMISTRY A》 * |
| ZHIJIE YANG等: ""Mesoporous CeO2 Hollow Spheres Prepared by Ostwald Ripening and Their Environmental Applications"", 《EUROPEAN JOURNAL OF INORFANIC CHEMISTRY》 * |
| 何蕾等: ""无模板溶剂热法合成高吸附活性的CeO2纳米空心球"", 《稀有金属》 * |
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107335422A (en) * | 2017-06-06 | 2017-11-10 | 浙江师范大学 | A kind of preparation method of carbon functionalization cerium oxide |
| CN107335422B (en) * | 2017-06-06 | 2020-07-31 | 浙江师范大学行知学院 | Preparation method of carbon functionalized cerium oxide |
| CN107349928A (en) * | 2017-08-29 | 2017-11-17 | 江苏师范大学 | A kind of SiO2The preparation method of@CeMnO composite photo-catalysts |
| CN108722391A (en) * | 2018-06-04 | 2018-11-02 | 中国科学院海洋研究所 | A kind of 3D C/CeO2Hollow nanostructured frame material and the preparation method and application thereof |
| CN108927135A (en) * | 2018-06-27 | 2018-12-04 | 上海上惠纳米科技有限公司 | Ceria/titanium dioxide composite mesopore ball preparation method |
| CN108807943A (en) * | 2018-07-19 | 2018-11-13 | 齐鲁工业大学 | A kind of hollow-core construction CeO2@C core-shell structure copolymer nanocomposites and the preparation method and application thereof |
| CN108807943B (en) * | 2018-07-19 | 2020-12-25 | 齐鲁工业大学 | CeO with hollow structure2@ C core-shell nano composite material and preparation method and application thereof |
| WO2020119717A1 (en) * | 2018-12-14 | 2020-06-18 | 深圳先进技术研究院 | Hollow ceric oxide preparation method |
| US20220040675A1 (en) * | 2019-10-23 | 2022-02-10 | Guangdong University Of Technology | Three-dimensionally ordered macroporous oxygen-deficient cerium dioxide catalyst, and preparation method and application thereof |
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| CN115449345B (en) * | 2022-08-29 | 2023-08-22 | 内蒙古科技大学 | Preparation method of mesoporous cerium oxide coated polystyrene nano-composite abrasive under microwave condition |
| CN115888686A (en) * | 2022-12-27 | 2023-04-04 | 安徽师范大学 | Cerium oxide @ carbon composite catalyst and synthesis method and application thereof |
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