CN109865535A - A kind of metastable state cerium oxide or cerium zirconium sosoloid nano material - Google Patents
A kind of metastable state cerium oxide or cerium zirconium sosoloid nano material Download PDFInfo
- Publication number
- CN109865535A CN109865535A CN201711249629.XA CN201711249629A CN109865535A CN 109865535 A CN109865535 A CN 109865535A CN 201711249629 A CN201711249629 A CN 201711249629A CN 109865535 A CN109865535 A CN 109865535A
- Authority
- CN
- China
- Prior art keywords
- cerium
- flame
- zirconium
- precursor
- oxygen
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- RCFVMJKOEJFGTM-UHFFFAOYSA-N cerium zirconium Chemical compound [Zr].[Ce] RCFVMJKOEJFGTM-UHFFFAOYSA-N 0.000 title claims abstract description 52
- 239000002086 nanomaterial Substances 0.000 title claims abstract description 22
- 229910000420 cerium oxide Inorganic materials 0.000 title abstract description 15
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 title abstract description 15
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 63
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 61
- 239000001301 oxygen Substances 0.000 claims abstract description 61
- 238000002360 preparation method Methods 0.000 claims abstract description 31
- 238000002485 combustion reaction Methods 0.000 claims abstract description 26
- 239000002245 particle Substances 0.000 claims abstract description 25
- 239000002243 precursor Substances 0.000 claims abstract description 22
- 239000000463 material Substances 0.000 claims abstract description 12
- 239000006104 solid solution Substances 0.000 claims abstract description 10
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims abstract description 4
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 claims abstract 2
- 239000000243 solution Substances 0.000 claims description 33
- 239000007789 gas Substances 0.000 claims description 24
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 20
- 239000003365 glass fiber Substances 0.000 claims description 19
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 13
- 229910052726 zirconium Inorganic materials 0.000 claims description 13
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 10
- 239000012695 Ce precursor Substances 0.000 claims description 9
- 150000001875 compounds Chemical class 0.000 claims description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- 239000000567 combustion gas Substances 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 239000003960 organic solvent Substances 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- OERNJTNJEZOPIA-UHFFFAOYSA-N zirconium nitrate Chemical compound [Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O OERNJTNJEZOPIA-UHFFFAOYSA-N 0.000 claims 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 claims description 3
- 239000000498 cooling water Substances 0.000 claims description 3
- DUFCMRCMPHIFTR-UHFFFAOYSA-N 5-(dimethylsulfamoyl)-2-methylfuran-3-carboxylic acid Chemical compound CN(C)S(=O)(=O)C1=CC(C(O)=O)=C(C)O1 DUFCMRCMPHIFTR-UHFFFAOYSA-N 0.000 claims description 2
- 229960001759 cerium oxalate Drugs 0.000 claims description 2
- VYLVYHXQOHJDJL-UHFFFAOYSA-K cerium trichloride Chemical compound Cl[Ce](Cl)Cl VYLVYHXQOHJDJL-UHFFFAOYSA-K 0.000 claims description 2
- ZMZNLKYXLARXFY-UHFFFAOYSA-H cerium(3+);oxalate Chemical compound [Ce+3].[Ce+3].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O ZMZNLKYXLARXFY-UHFFFAOYSA-H 0.000 claims description 2
- VGBWDOLBWVJTRZ-UHFFFAOYSA-K cerium(3+);triacetate Chemical compound [Ce+3].CC([O-])=O.CC([O-])=O.CC([O-])=O VGBWDOLBWVJTRZ-UHFFFAOYSA-K 0.000 claims description 2
- GHLITDDQOMIBFS-UHFFFAOYSA-H cerium(3+);tricarbonate Chemical compound [Ce+3].[Ce+3].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O GHLITDDQOMIBFS-UHFFFAOYSA-H 0.000 claims description 2
- 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 2
- UJVRJBAUJYZFIX-UHFFFAOYSA-N nitric acid;oxozirconium Chemical compound [Zr]=O.O[N+]([O-])=O.O[N+]([O-])=O UJVRJBAUJYZFIX-UHFFFAOYSA-N 0.000 claims description 2
- 150000007524 organic acids Chemical class 0.000 claims description 2
- 239000000835 fiber Substances 0.000 claims 2
- YOBOXHGSEJBUPB-MTOQALJVSA-N (z)-4-hydroxypent-3-en-2-one;zirconium Chemical compound [Zr].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O YOBOXHGSEJBUPB-MTOQALJVSA-N 0.000 claims 1
- 238000007664 blowing Methods 0.000 claims 1
- BSDOQSMQCZQLDV-UHFFFAOYSA-N butan-1-olate;zirconium(4+) Chemical compound [Zr+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] BSDOQSMQCZQLDV-UHFFFAOYSA-N 0.000 claims 1
- XMPZTFVPEKAKFH-UHFFFAOYSA-P ceric ammonium nitrate Chemical compound [NH4+].[NH4+].[Ce+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O XMPZTFVPEKAKFH-UHFFFAOYSA-P 0.000 claims 1
- PYPNFSVOZBISQN-LNTINUHCSA-K cerium acetylacetonate Chemical compound [Ce+3].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O PYPNFSVOZBISQN-LNTINUHCSA-K 0.000 claims 1
- CMOAHYOGLLEOGO-UHFFFAOYSA-N oxozirconium;dihydrochloride Chemical compound Cl.Cl.[Zr]=O CMOAHYOGLLEOGO-UHFFFAOYSA-N 0.000 claims 1
- XPGAWFIWCWKDDL-UHFFFAOYSA-N propan-1-olate;zirconium(4+) Chemical compound [Zr+4].CCC[O-].CCC[O-].CCC[O-].CCC[O-] XPGAWFIWCWKDDL-UHFFFAOYSA-N 0.000 claims 1
- 239000008096 xylene Substances 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 18
- 230000008569 process Effects 0.000 abstract description 4
- 238000005516 engineering process Methods 0.000 abstract description 3
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 230000006641 stabilisation Effects 0.000 abstract description 2
- 238000011105 stabilization Methods 0.000 abstract description 2
- 230000007774 longterm Effects 0.000 abstract 1
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 32
- 230000000052 comparative effect Effects 0.000 description 20
- 239000003054 catalyst Substances 0.000 description 16
- 238000000975 co-precipitation Methods 0.000 description 13
- 229910052684 Cerium Inorganic materials 0.000 description 8
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 8
- 239000008246 gaseous mixture Substances 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- 229910002651 NO3 Inorganic materials 0.000 description 7
- 230000003647 oxidation Effects 0.000 description 5
- 238000007254 oxidation reaction Methods 0.000 description 5
- 230000005298 paramagnetic effect Effects 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 238000003760 magnetic stirring Methods 0.000 description 4
- 230000001376 precipitating effect Effects 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- 238000001069 Raman spectroscopy Methods 0.000 description 3
- 238000001237 Raman spectrum Methods 0.000 description 3
- 230000004913 activation Effects 0.000 description 3
- 238000009841 combustion method Methods 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000011065 in-situ storage Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 230000008707 rearrangement Effects 0.000 description 3
- MKYBYDHXWVHEJW-UHFFFAOYSA-N N-[1-oxo-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propan-2-yl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(C(C)NC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 MKYBYDHXWVHEJW-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000006193 liquid solution Substances 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 238000006479 redox reaction Methods 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- FZIZEIAMIREUTN-UHFFFAOYSA-N azane;cerium(3+) Chemical compound N.[Ce+3] FZIZEIAMIREUTN-UHFFFAOYSA-N 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 229910000333 cerium(III) sulfate Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000001239 high-resolution electron microscopy Methods 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 238000001802 infusion Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000011943 nanocatalyst Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 description 1
Landscapes
- Catalysts (AREA)
Abstract
本发明提供了一种亚稳态氧化铈或铈锆固溶体纳米材料，该材料制备的关键技术是保证高结晶度的氧化物颗粒的形成，又避免长时间高温焙烧。本发明利用火焰燃烧产生的高温使前驱体快速分解为氧化物颗粒，同时又引入大量空气将产生的颗粒快速移出高温区域并极速降温，使其避免经过高温焙烧的稳定化过程，将氧化物固定在了亚稳定的状态。所制备的亚稳态氧化铈或铈锆固溶体纳米材料表面存在大量活泼氧，不存在或存在少量氧空位，晶格氧处于亚稳定状态，若经过长时间高温焙烧，可转变为稳定的铈锆固溶体。
The invention provides a metastable cerium oxide or cerium-zirconium solid solution nanomaterial, and the key technology for the preparation of the material is to ensure the formation of oxide particles with high crystallinity and avoid long-term high-temperature roasting. The invention utilizes the high temperature generated by flame combustion to rapidly decompose the precursor into oxide particles, and at the same time introduces a large amount of air to quickly move the generated particles out of the high-temperature area and rapidly cool down, so as to avoid the stabilization process of high-temperature roasting and fix the oxides. in a metastable state. The prepared metastable ceria or cerium zirconium solid solution nanomaterials have a large amount of active oxygen on the surface, no or a small amount of oxygen vacancies, and the lattice oxygen is in a metastable state. solid solution.
Description
Technical field
The present invention relates to a kind of metastable state cerium oxide or cerium zirconium sosoloid nano materials, concretely relate to a kind of oxidation
Cerium or cerium zirconium sosoloid, the core for preparing the metastable state cerium zirconium sosoloid are to arrive stabilized mistake in formation at the beginning of oxide particle
Cheng Zhong extracts the oxide for being also not up to stable state.Key technology is to guarantee the oxide particle shape of high-crystallinity
At, and avoid long-time high-temperature roasting.The present invention makes presoma be rapidly decomposed into oxide using the high temperature that flame combustion generates
Particle, while introducing large quantity of air again and the particle of generation is quickly moved out high-temperature area and very fast cooling, avoid it through excessively high
Oxide, has been fixed on the state of meta-stable by the stabilization procedures of temperature roasting.There are a large amount of active oxygen in the material surface, do not deposit
Or there are a small amount of Lacking oxygen, Lattice Oxygen is in metastable condition, if by long-time high-temperature roasting, it may occur that atomic rearrangement,
It is changed into stable cerium zirconium sosoloid.
Background technique
Nano material and nanocatalyst are related to many fields of national economy all in chemical industry, material, the energy, environmental protection etc.
It is of crucial importance.In redox reaction, the active oxygen in oxide-based nanomaterial determines its redox energy
Power, to influence its activation capacity to oxygen, therefore, exploitation can prepare the preparation of the nano material with a large amount of active oxygen
Method is of great significance.Traditional preparation method, such as traditional infusion process, the precipitation method, hydrothermal synthesis method, ball-milling method and chemistry
Reduction method etc., all unavoidable subsequent high temperature heat treatment, and heat treatment process can make atomic rearrangement, lose active oxygen species.But
If preferable oxide crystal form cannot be formed without high-temperature heat treatment.Flame combustion process of the present invention and tradition side
Method is different, and precursor solution decomposes in thermal-flame, and decomposition temperature can reach 1000-2000 DEG C, it is ensured that it is high to form crystallinity
Oxide crystal.Meanwhile the oxide particle of generation is quickly moved out flame high-temperature area by a large amount of protection gas, and is dropped rapidly
Temperature avoids particle from undergoing long-time high-temperature roasting, solves this contradiction just, oxide has been fixed on to the shape of meta-stable
State, it is possible to provide more active oxygen.
Summary of the invention
The present invention provides a kind of metastable state cerium oxide or cerium zirconium sosoloid nano materials, which is characterized in that its use as
Lower step prepares: 1) preparation of precursor solution: cerium precursor being stirred with solvent and is mixed, and it is molten to form presoma
Liquid；Or the composition according to cerium zirconium sosoloid, cerium precursor and zirconium precursor body and solvent are stirred mixing；It is molten to form presoma
Liquid；2) preparation of sample: lighting the gaseous mixture of methane and oxygen to form flame, will be prepared in 1) step with constant flow pump before
It drives liquid solution and is injected into flame and burn, while flame region is blowed to using air and takes combustion product out of flame region.3) sample
The collection of product: being equipped with the cylinder of two end openings in the side of flame region, and one open end of cylinder is covered with glass fiber filter paper, in
Glass fiber filter paper is equipped with vacuum pump far from cylinder side, and towards glass fiber filter paper, cylinder is another to be opened the air inlet of vacuum pump
Mouth end face blows to another open end end face of the flame region air-flow direction towards cylinder to flame region, auxiliary with vacuum pump
It helps combustion product quickly to leave flame region, rests on it in glass fiber filter paper, circulation is equipped with around glass fiber filter paper
Cooling water removes the collection that filter paper carries out sample after preparation.Precursor solution is injected into flame by pipeline to burn, pipe
Way outlet is located in the middle part of flame.Cerium precursor is the compound that can be dissolved in organic solvent, preferably cerous nitrate, nitric acid in step 1)
One or more of cerium ammonium, cerous sulfate, cerium chloride, cerous carbonate, cerium oxalate, cerous acetate, acetylacetone,2,4-pentanedione cerium；In step 1)
Zirconium precursor body is the compound that can be dissolved in organic solvent, preferably zirconium nitrate, zirconyl nitrate, zirconium-n-propylate, zirconium acetate, levulinic
One or more of ketone zirconium, basic zirconium chloride, zirconium-n-butylate；Solvent is combustible organic solvent in step 1), preferably
For one or more of methanol, ethyl alcohol, dimethylbenzene, organic acid.Combustion gas needed for flame combustion is methane and oxygen
Gaseous mixture, gaseous mixture are sprayed by the nozzle of 1-10mm diameter, and methane and oxygen flow are 0.1-5L/min；Solution is pumped into flame
In speed be 0.1-20ml/min；Flame lights organic solution, and each component precursor compound occurs at the high temperatures of the flame
It is decomposed to form oxide particle, oxide particle is formed by and leaves flame region under the drive of air, air is equal by surface
The gas distribution grid for being furnished with gas via-hole blows to entire flame region from flame side, the radial direction of gas via-hole on gas distribution grid
The sum of area of section is 0.1-10 square centimeters, air mass flow 2-20L/min, is equipped with circulating cooling around glass fiber filter paper
Water, reaching the particulate samples temperature in glass fiber filter paper is 20-70 DEG C.The composition of combustion product is adjustable, wherein mole of zirconium
Percentage is 0-99%；Cerium precursor and zirconium precursor the body total concentration in precursor solution are 0.1-1mol/L.
There are a large amount of active oxygen in metastable state cerium oxide prepared by the present invention or cerium zirconium sosoloid nano-material surface, do not deposit
Metastable condition is in or there are a small amount of Lacking oxygen, Lattice Oxygen.If the nano material is 500 DEG C or more through excess temperature, the time
It is roasted for 1 hour or more condition, it may occur that atomic rearrangement, active oxygen are reduced, and are changed into stable cerium oxide or cerium zirconium solid solution
Body.
Metastable state cerium oxide or cerium zirconium sosoloid nano material prepared by the present invention can be used as catalyst or catalyst carries
Body, in the reaction containing redox cycle, such as CO oxidation, NO oxidation, NOx reduction.As carrier can support Au,
The one or more active metal such as Pt, Cu, Rh, Pd, Fe, Co, Mn, V.This metastable cerium oxide or cerium zirconium sosoloid
It can provide a large amount of active oxygen, can promote the activation of oxygen in redox reaction, show higher activity.
Present invention has an advantage that by high temperature thermal decomposition, with moment, quenching combines the flame combustion process in (1) present invention,
Not only it can ensure that the oxide for generating high-crystallinity, but also can avoid subsequent high temperature roasting, rest on oxide with a large amount of active
The metastable condition of oxygen.(2) in the present invention there are a large amount of active oxygen in metastable state cerium zirconium sosoloid material surface, is not present or exists
A small amount of Lacking oxygen can provide a large amount of active oxygen in catalytic oxidation, promote the activation of oxygen, show higher activity.
(3) this method has universality, can be applied to the preparation of one or more component metals oxide nano particles, improves metal oxygen
The supply capacity of the active oxygen of compound.
Detailed description of the invention
The cerium oxide and cerium zirconium sosoloid (embodiment 1-4) of the preparation of Fig. 1 flame combustion process and the oxidation of coprecipitation preparation
The comparison of the X-ray diffraction spectrogram and lattice parameter of cerium and cerium zirconium sosoloid (comparative example 1-4).
(a) is that the X of the cerium zirconium sosoloid (comparative example 1-4) of cerium oxide and different compositions prepared by coprecipitation is penetrated in Fig. 1
Line diffraction spectrogram；(b) X for the cerium zirconium sosoloid (embodiment 1-4) of the cerium oxide and different compositions of flame combustion process preparation is penetrated
Line diffraction spectrogram；It (c) is the lattice parameter comparison of the nano material of two methods preparation；(d) zirconium for two methods preparation contains
It measures the X-ray diffraction spectrogram before and after the cerium zirconium sosoloid for being 75% roasts 30 hours at 800 DEG C and is obtained by having thanked to equation calculation
The particle size arrived.Fig. 1 is as it can be seen that the cerium oxide of two methods preparation and the cerium zirconium sosoloid of different proportion have higher crystallization
Degree, lattice parameter having the same illustrate their crystal phase structures having the same, and nano material prepared by the present invention is really oxygen
Change cerium and cerium zirconium sosoloid, and cerium zirconium ratio is adjustable.In addition, Fig. 1 (d) illustrates the cerium zirconium solid solution that in comparative example prepared by coprecipitation
Body can be assembled by high-temperature roasting, lead to particle growth, and cerium zirconium sosoloid prepared by the present invention is due to having been subjected to
High temperature, therefore particle thermal stability with higher in high-temperature calcination process.
The high resolution electron microscopy photo of the cerium zirconium sosoloid of Fig. 2 flame combustion process preparation.
Fig. 2 is the electromicroscopic photograph for the nano particle that the Zr molar content of flame combustion process preparation is 50% and 75%, from figure
In can be seen that, grain diameter is respectively positioned between 6-15nm, distribution uniform.Illustrate that the material that this method is prepared is nano cerium
Zirconium solid solution.
The paramagnetic resonance spectra of the cerium zirconium sosoloid of Fig. 3 coprecipitation (a) and the different proportion of flame combustion process (b) preparation
Figure.
(a) is the cerium oxide of coprecipitation preparation and the cerium zirconium sosoloid (comparative example 1,2 and 4) of different compositions in Fig. 3
Paramagnetic resonance spectrogram；It (b) is the cerium oxide of flame combustion process preparation and the cerium zirconium sosoloid (embodiment 1,2 and 4) of different proportion
Paramagnetic resonance spectrogram.Tri- peaks g=2.011, g=2.032 and g=2.049 in Fig. 3 paramagnetic resonance spectra represent O2 -It is adsorbed on
Paramagnetic signal at Lacking oxygen.As it can be seen that the cerium zirconium sosoloid that in comparative example prepared by coprecipitation is there are a large amount of Lacking oxygens, and this hair
Bright prepared cerium zirconium sosoloid material is not present or there are a small amount of Lacking oxygens, and as Zr content increases, Lacking oxygen gradually subtracts
Less until disappearing.
The removing of Fig. 4 Raman spectrum analysis cerium zirconium sosoloid nano material Lattice Oxygen and the generation of Lacking oxygen.
(A) is in-situ Raman spectrogram under 2%CO/He atmosphere: wherein (a) FC-Ce in Fig. 40.75Zr0.25O2；(b)FC-
Ce0.5Zr0.5O2；(c)FC-Ce0.25Zr0.75O2；(d)CP-Ce0.75Zr0.25O2；(e)CP-Ce0.5Zr0.5O2；(f)CP-
Ce0.25Zr0.75O2；It (B) is FC-Ce1-xZrxO2(embodiment 2-4) and CP-Ce1-xZrxO2Lacking oxygen in (comparative example 2-4) material
(Ov) and Ce4+(F2g) peak area ratio；It (C) is CP-Ce0.25Zr0.75O2(comparative example 4) and FC-Ce0.25Zr0.75O2(embodiment
4) the Lacking oxygen quantity that material generates at different temperatures.Fig. 4 (A) in-situ Raman characterization result can be seen that, flame combustion process institute
Lattice Oxygen in the cerium zirconium sosoloid of preparation is more active, can react at a lower temperature with the CO in atmosphere, in same temperature
Under degree, it can produce more Lacking oxygens.Fig. 4 (B) is as it can be seen that the cerium zirconium sosoloid for being co-precipitated preparation in comparative example is only capable of with temperature raising
A small amount of Lacking oxygen is generated, and cerium zirconium sosoloid prepared by embodiment Flame combustion method is increased with temperature, the Lacking oxygen of generation
Amount sharply increases, and illustrates that the Lattice Oxygen in the material is more active.By Fig. 4 (C) it is found that at 20,100 and 200 DEG C, in embodiment
FC-Ce prepared by flame combustion process0.25Zr0.75O2The Lacking oxygen quantity that material generates is respectively CP- in comparative example
Ce0.25Zr0.75O219,13 and 11 times of generated Lacking oxygen quantity, illustrate cerium zirconium prepared by embodiment Flame combustion method
There are more active oxygen on solid solution.
Before cerium zirconium sosoloid nano material prepared by Fig. 5 Raman spectrum analysis flame combustion process is by high-temperature roasting processing
The variation of the removing of Lattice Oxygen and Lacking oxygen afterwards.
Fig. 5 is the cerium zirconium sosoloid FC-Ce of flame combustion method preparation0.25Zr0.75O2After (embodiment 4), high-temperature roasting
Cerium zirconium sosoloid FC-Ce0.25Zr0.75O2The cerium zirconium sosoloid CP- of -800 (comparative examples 5) and traditional co-precipitation method preparation
Ce0.25Zr0.75O2The raman spectrum of (comparative example 4) and Lacking oxygen quantitative comparison.Fig. 5 (A) is in-situ Raman under 2%CO/He atmosphere
Spectrogram；It (B) is Lacking oxygen (Ov) and Ce4+(F2g) peak area ratio；It (C) is Lacking oxygen quantity in different samples: (a) FC-
Ce0.25Zr0.75O2；(b)FC-Ce0.25Zr0.75O2-800；(c)CP-Ce0.25Zr0.75O2.As it can be seen that with the FC- in embodiment 4
Ce0.25Zr0.75O2It compares, the FC-Ce in comparative example 5 after high-temperature roasting0.25Zr0.75O2- 800 cerium zirconium sosoloids are in CO atmosphere
The Lacking oxygen quantity of middle generation is sharply reduced, the cerium zirconium sosoloid of coprecipitation preparation in the quantity and comparative example 4 of active oxygen
Quite.Illustrate that the cerium zirconium sosoloid prepared by the present invention with more active oxygen is in the state of meta-stable, high-temperature roasting
Journey can make it lose active oxygen, reach stable state, at this point, it is suitable with the cerium zirconium sosoloid performance of coprecipitation preparation.
Specific embodiment
The technology of the present invention details is subject to detailed description by following embodiments.It should be noted that for embodiment, make
With only further illustrating technical characteristic of the invention, rather than limit the present invention.
Embodiment 1
116.3g acetylacetone,2,4-pentanedione cerium (Ce content 12%) and 82ml dimethylbenzene are hybridly prepared into precursor solution, cerium precursor
Bulk concentration is 0.5mol/L.Solution is placed on magnetic stirring apparatus, stirring is to obtaining clear solution.Use syringe with 5ml/
The solution prepared is pumped into flame by the speed of min.Flame combustion gas is methane (0.6L/min) and oxygen (1.9L/min) group
At gaseous mixture, gaseous mixture by 2mm diameter nozzle spray.Large quantity of air (6L/min) is blown by flame using gas distribution grid
Region makes combustion product speed away flame region, gas via-hole on gas distribution grid under the drive of high-speed air air-flow
The sum of radial cross-sectional area is 3.5 square centimeters, and sample reaches temperature at glass fiber filter paper and is reduced to 40 DEG C.What burning obtained urges
Catalyst particles are collected using glass fiber filter paper.Particle diameter is between 6-15nm.Obtained catalyst is denoted as FC-
CeO2。
Embodiment 2
Before 65.4g acetylacetone,2,4-pentanedione cerium (Ce content 12%), 9.8ml acetylacetone,2,4-pentanedione zirconium and 74ml dimethylbenzene are hybridly prepared into
Drive liquid solution.Solution is placed on magnetic stirring apparatus, stirring is to obtaining clear solution.Use syringe with the speed of 5ml/min
The solution prepared is pumped into flame.Flame combustion gas is the mixing that methane (0.6L/min) and oxygen (1.9L/min) form
Gas, gaseous mixture are sprayed by the nozzle of 2mm diameter.Large quantity of air (6L/min) is blown by flame region using gas distribution grid,
Under the drive of high-speed air air-flow, combustion product is made to speed away flame region, the radial direction of gas via-hole is cut on gas distribution grid
The sum of face area is 3.5 square centimeters, and sample reaches temperature at glass fiber filter paper and is reduced to 40 DEG C.Burn obtained catalyst particles
Grain is collected using glass fiber filter paper.Particle diameter is between 6-15nm.Obtained catalyst is denoted as FC-
Ce0.75Zr0.25O2。
Embodiment 3
43.6g acetylacetone,2,4-pentanedione cerium (Ce content 12%), 19.6ml acetylacetone,2,4-pentanedione zirconium and 86ml dimethylbenzene are hybridly prepared into
Precursor solution.Solution is placed on magnetic stirring apparatus, stirring is to obtaining clear solution.Use syringe with the speed of 5ml/min
The solution prepared is pumped into flame by degree.Flame combustion gas is the mixing that methane (0.6L/min) and oxygen (1.9L/min) form
Gas, gaseous mixture are sprayed by the nozzle of 2mm diameter.Large quantity of air (6L/min) is blown by flame region using gas distribution grid,
Under the drive of high-speed air air-flow, combustion product is made to speed away flame region, the radial direction of gas via-hole is cut on gas distribution grid
The sum of face area is 3.5 square centimeters, and sample reaches temperature at glass fiber filter paper and is reduced to 40 DEG C.Burn obtained catalyst particles
Grain is collected using glass fiber filter paper.Particle diameter is between 6-15nm.Obtained catalyst is denoted as FC-
Ce0.5Zr0.5O2。
Embodiment 4
21.8g acetylacetone,2,4-pentanedione cerium (Ce content 12%), 29.3ml acetylacetone,2,4-pentanedione zirconium and 98ml dimethylbenzene are hybridly prepared into
Precursor solution.Solution is placed on magnetic stirring apparatus, stirring is to obtaining clear solution.Use syringe with the speed of 5ml/min
The solution prepared is pumped into flame by degree.Flame combustion gas is the mixing that methane (0.6L/min) and oxygen (1.9L/min) form
Gas, gaseous mixture are sprayed by the nozzle of 2mm diameter.Large quantity of air (6L/min) is blown by flame region using gas distribution grid,
Under the drive of high-speed air air-flow, combustion product is made to speed away flame region, the radial direction of gas via-hole is cut on gas distribution grid
The sum of face area is 3.5 square centimeters, and sample reaches temperature at glass fiber filter paper and is reduced to 40 DEG C.Burn obtained catalyst particles
Grain is collected using glass fiber filter paper.Particle diameter is between 6-15nm.Obtained catalyst is denoted as FC-
Ce0.25Zr0.75O2。
Comparative example 1
The preparation of coprecipitation cerium zirconium sosoloid: 15.9g (NH is weighed4)2Ce(NO3)6It is dissolved in 100mL deionized water,
(NH is added dropwise under 50 DEG C of water-baths4)2CO3Solution to generate precipitating, pH value 8-9.Filtration washing will be precipitated, will be moved into crucible,
And baking oven is put it into 110 DEG C of dry 10h, the solid after drying is put into Muffle furnace, 500 DEG C of roasting 4h.Obtained
Catalyst is denoted as CP-CeO2。
Comparative example 2
The preparation of coprecipitation cerium zirconium sosoloid: 12.0g (NH is weighed4)2Ce(NO3)6With 3.1gZr (NO3)4·5H2O in
In 100mL deionized water, (NH is added dropwise under 50 DEG C of water-baths4)2CO3Solution to generate precipitating, pH value 8-9.It will precipitate
Filter washing moves into crucible, and puts it into baking oven in 110 DEG C of dry 10h, the solid after drying is put into Muffle furnace, 500
DEG C roasting 4h.Obtained catalyst is denoted as CP-Ce0.75Zr0.25O2。
Comparative example 3
The preparation of coprecipitation cerium zirconium sosoloid: 9.3g (NH is weighed4)2Ce(NO3)6With 7.3gZr (NO3)4·5H2O in
In 100mL deionized water, (NH is added dropwise under 50 DEG C of water-baths4)2CO3Solution to generate precipitating, pH value 8-9.It will precipitate
Filter washing moves into crucible, and puts it into baking oven in 110 DEG C of dry 10h, the solid after drying is put into Muffle furnace, 500
DEG C roasting 4h.Obtained catalyst is denoted as CP-Ce0.5Zr0.5O2。
Comparative example 4
The preparation of coprecipitation cerium zirconium sosoloid: 6.0g (NH is weighed4)2Ce(NO3)6With 14.1gZr (NO3)4·5H2O in
In 100mL deionized water, (NH is added dropwise under 50 DEG C of water-baths4)2CO3Solution to generate precipitating, pH value 8-9.It will precipitate
Filter washing moves into crucible, and puts it into baking oven in 110 DEG C of dry 10h, the solid after drying is put into Muffle furnace, 500
DEG C roasting 4h.Obtained catalyst is denoted as CP-Ce0.25Zr0.75O2。
Comparative example 5
By the sample in embodiment 4 in Muffle furnace 800 DEG C of roasting 30h.Obtained catalyst is denoted as FC-
Ce0.25Zr0.75O2-800。
Comparative example 6
By the sample in comparative example 4 in Muffle furnace 800 DEG C of roasting 30h.Obtained catalyst is denoted as CP-
Ce0.25Zr0.75O2-800。
Claims (7)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711249629.XA CN109865535B (en) | 2017-12-01 | 2017-12-01 | Metastable state cerium oxide or cerium-zirconium solid solution nano material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711249629.XA CN109865535B (en) | 2017-12-01 | 2017-12-01 | Metastable state cerium oxide or cerium-zirconium solid solution nano material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109865535A true CN109865535A (en) | 2019-06-11 |
| CN109865535B CN109865535B (en) | 2022-03-15 |
Family
ID=66913547
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201711249629.XA Active CN109865535B (en) | 2017-12-01 | 2017-12-01 | Metastable state cerium oxide or cerium-zirconium solid solution nano material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109865535B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112588296A (en) * | 2020-12-23 | 2021-04-02 | 甄崇礼 | Catalyst for VOCs catalytic combustion and preparation method thereof |
| CN112844393A (en) * | 2019-11-27 | 2021-05-28 | 中国科学院大连化学物理研究所 | Cerium-iron-zirconium solid solution oxide catalyst and preparation and application thereof |
| CN114713223A (en) * | 2021-01-04 | 2022-07-08 | 中国科学院大连化学物理研究所 | Method for preparing tetragonal-phase zirconia in one step, copper-based supported catalyst and application thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101966451A (en) * | 2010-11-06 | 2011-02-09 | 大连理工大学 | Preparation method and application of nanometer ceria-zirconia solid solution-based catalyst for selectively catalytically oxidizing ammonia |
| EP2368628A1 (en) * | 2010-03-25 | 2011-09-28 | Paul Scherrer Institut | Catalyst for a DeNOx-application and a process for selective catalytic reduction of nitrogen oxides |
| KR20150043436A (en) * | 2012-08-14 | 2015-04-22 | 바스프 에스이 | Ceria-zirconia-mixed oxide particles and process for their production by pyrolysis |
| CN105983403A (en) * | 2015-02-09 | 2016-10-05 | 有研稀土新材料股份有限公司 | Cerium-zirconium composite oxide, preparation method of cerium-zirconium composite oxide and use of catalyst |
-
2017
- 2017-12-01 CN CN201711249629.XA patent/CN109865535B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2368628A1 (en) * | 2010-03-25 | 2011-09-28 | Paul Scherrer Institut | Catalyst for a DeNOx-application and a process for selective catalytic reduction of nitrogen oxides |
| CN101966451A (en) * | 2010-11-06 | 2011-02-09 | 大连理工大学 | Preparation method and application of nanometer ceria-zirconia solid solution-based catalyst for selectively catalytically oxidizing ammonia |
| KR20150043436A (en) * | 2012-08-14 | 2015-04-22 | 바스프 에스이 | Ceria-zirconia-mixed oxide particles and process for their production by pyrolysis |
| CN105983403A (en) * | 2015-02-09 | 2016-10-05 | 有研稀土新材料股份有限公司 | Cerium-zirconium composite oxide, preparation method of cerium-zirconium composite oxide and use of catalyst |
Non-Patent Citations (2)
| Title |
|---|
| ANTHONY C.SUTORIK 等: "Solid Solution Behavior of CeXZr1-XO2 Nanopowders Prepared by Flame Spray Pyrolysis of Solvent-Borne Precursors", 《JOURNAL OF METASTABLE AND NANOCRYSTALLINE MATERIALS》 * |
| RETO STROBEL 等: "Flame spray synthesis of Pd/Al2O3 catalysts and their behavior in enantioselective hydrogenation", 《JOURNAL OF CATALYSIS》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112844393A (en) * | 2019-11-27 | 2021-05-28 | 中国科学院大连化学物理研究所 | Cerium-iron-zirconium solid solution oxide catalyst and preparation and application thereof |
| CN112588296A (en) * | 2020-12-23 | 2021-04-02 | 甄崇礼 | Catalyst for VOCs catalytic combustion and preparation method thereof |
| CN114713223A (en) * | 2021-01-04 | 2022-07-08 | 中国科学院大连化学物理研究所 | Method for preparing tetragonal-phase zirconia in one step, copper-based supported catalyst and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109865535B (en) | 2022-03-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Le Gal et al. | Catalytic investigation of ceria-zirconia solid solutions for solar hydrogen production | |
| JP5047114B2 (en) | Method for producing powder containing cerium oxide | |
| Dobrosz-Gómez et al. | Au/Ce1− xZrxO2 as effective catalysts for low-temperature CO oxidation | |
| CN108465466B (en) | A kind of spherical catalyst of ceria-wrapped Pd and preparation method thereof | |
| JPH10505786A (en) | Catalyst compositions based on cerium oxide and oxides of manganese, iron or praseodymium, their preparation and their use in automotive afterburning catalysis | |
| CN102351242A (en) | A method for preparing single-phase bismuth titanate Bi2Ti2O7 by solvothermal method | |
| CN109865535B (en) | Metastable state cerium oxide or cerium-zirconium solid solution nano material | |
| CN108452787B (en) | Titanium dioxide hollow microsphere with high visible light activity and preparation method and application thereof | |
| CN103596679B (en) | Composite oxides, its manufacture method and exhaust emission control catalyst | |
| CN104209126B (en) | A kind of preparation method of pencil prism cobaltosic oxide | |
| Divya et al. | Influence of hydrothermal synthesis conditions on lattice defects in cerium oxide | |
| CN109107572A (en) | The method that laser ablation prepares perovskite catalyst | |
| Zhao et al. | NiO/NiAl2O4 oxygen carriers prepared by sol-gel for chemical-looping combustion fueled by gas | |
| CN102728381A (en) | Tourmalinite-containing composite methane catalyst | |
| JP5116276B2 (en) | Powder comprising oxide microcrystal particles, catalyst using the same, and method for producing the same | |
| CN101767997A (en) | Method for preparing NiTiO3 nano-powder by sol-gel | |
| Li et al. | Role of surface species in CO oxidation over CuO@ LaMnO3 nanocomposites: Effect of calcination temperature | |
| CN1214986C (en) | A process for preparing zirconium dioxide nanopowder by hydrolyzing zirconyl nitrate | |
| Gao et al. | Shape control of CeO2 nano-particles and synthesis of nano-metric solid acid SO42−/CeO2 | |
| CN111569922B (en) | Rare earth doped hydrotalcite-like derivative oxide catalyst for catalytic combustion of VOC waste gas and preparation method thereof | |
| JP2001348223A (en) | Ceria-zirconia solid-solution particulate and method for manufacturing the same | |
| KR102059404B1 (en) | Cerium-Praseodymium mixed oxide catalyst with fibrous morphology for combustion of carbon particulate matter, and method for carbon particulate matter combustion using the same | |
| JP5690372B2 (en) | Iron oxide-zirconia composite oxide and method for producing the same | |
| CN107903072B (en) | Method for preparing strontium barium niobate nano powder by two-step coprecipitation method | |
| CN112516989B (en) | Coating material catalyst and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |