CN103566923B - Cerium zirconium aluminum composite oxide oxygen storage material and preparation method thereof - Google Patents
Cerium zirconium aluminum composite oxide oxygen storage material and preparation method thereof Download PDFInfo
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- -1 Cerium zirconium aluminum Chemical compound 0.000 title claims abstract description 29
- 239000002131 composite material Substances 0.000 title claims abstract description 29
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title claims abstract description 25
- 239000001301 oxygen Substances 0.000 title claims abstract description 25
- 229910052760 oxygen Inorganic materials 0.000 title claims abstract description 25
- 239000011232 storage material Substances 0.000 title claims abstract description 18
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 239000011148 porous material Substances 0.000 claims abstract description 30
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical group [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 claims abstract description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 33
- 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 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 21
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 20
- 230000032683 aging Effects 0.000 claims description 17
- 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 11
- 239000006185 dispersion Substances 0.000 claims description 11
- 229910001593 boehmite Inorganic materials 0.000 claims description 10
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- 239000012065 filter cake Substances 0.000 claims description 8
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 7
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 7
- 239000000243 solution Substances 0.000 claims description 7
- 229910052684 Cerium Inorganic materials 0.000 claims description 6
- 230000003213 activating effect Effects 0.000 claims description 6
- 238000010009 beating Methods 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- 229910052751 metal Inorganic materials 0.000 claims description 6
- 239000002184 metal Substances 0.000 claims description 6
- 235000010482 polyoxyethylene sorbitan monooleate Nutrition 0.000 claims description 6
- 229920000053 polysorbate 80 Polymers 0.000 claims description 6
- 239000002002 slurry Substances 0.000 claims description 6
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- RCEAADKTGXTDOA-UHFFFAOYSA-N OS(O)(=O)=O.CCCCCCCCCCCC[Na] Chemical compound OS(O)(=O)=O.CCCCCCCCCCCC[Na] RCEAADKTGXTDOA-UHFFFAOYSA-N 0.000 claims description 3
- 229920002565 Polyethylene Glycol 400 Polymers 0.000 claims description 3
- JLFNLZLINWHATN-UHFFFAOYSA-N pentaethylene glycol Chemical compound OCCOCCOCCOCCOCCO JLFNLZLINWHATN-UHFFFAOYSA-N 0.000 claims description 3
- 239000012190 activator Substances 0.000 claims description 2
- 230000007935 neutral effect Effects 0.000 claims description 2
- RCFVMJKOEJFGTM-UHFFFAOYSA-N cerium zirconium Chemical compound [Zr].[Ce] RCFVMJKOEJFGTM-UHFFFAOYSA-N 0.000 abstract description 9
- 239000002245 particle Substances 0.000 abstract description 6
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 239000002994 raw material Substances 0.000 abstract description 2
- 239000006104 solid solution Substances 0.000 abstract description 2
- 230000003321 amplification Effects 0.000 abstract 1
- 230000003712 anti-aging effect Effects 0.000 abstract 1
- 238000003199 nucleic acid amplification method Methods 0.000 abstract 1
- 238000003860 storage Methods 0.000 abstract 1
- 239000000463 material Substances 0.000 description 17
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical group O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 13
- 239000008367 deionised water Substances 0.000 description 11
- 229910021641 deionized water Inorganic materials 0.000 description 11
- 229910000420 cerium oxide Inorganic materials 0.000 description 10
- 238000009413 insulation Methods 0.000 description 10
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 10
- 238000013019 agitation Methods 0.000 description 5
- 239000013049 sediment Substances 0.000 description 5
- 239000000047 product Substances 0.000 description 3
- 238000005245 sintering Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical group [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 235000019994 cava Nutrition 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
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- Inorganic Compounds Of Heavy Metals (AREA)
- Catalysts (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention discloses a cerium zirconium aluminum composite oxide oxygen storage material and a preparation method thereof. According to the cerium zirconium aluminum composite oxide oxygen storage material, the particle size is 5 to 10 nm; the BET specific surface area is 200 to 240 m<2>/g; the pore volume is 0.50 to 0.70 cm<3>/g; the average pore size is 5 to 10 nm; a cerium zirconium solid solution has a stable cubic fluorite structure. The cerium zirconium aluminum composite oxide oxygen storage material provided by the invention has the characteristics of stable structure, large specific surface area, excellent oxygen storage performance and excellent anti-ageing performance. The preparation method provided by the invention has the advantages of easily accessible raw materials and low production cost, and is suitable for industrialized amplification production.
Description
Technical field
The present invention relates to a kind of hydrogen-storing material and preparation method thereof, the particularly Cerium zirconium aluminum composite oxide oxygen storage material being applied to purifying vehicle exhaust and preparation method thereof.
Background technology
Cerium oxide, as the key component of hydrogen-storing material in three-way catalyst, plays and main stores oxygen effect.But the cerium oxide of one-component just easily sinters at 850 DEG C, and cause specific area sharply to decline, pore passage structure caves in, and stores oxygen degradation.After having there are some researches show that cerium oxide and zirconia form solid solution, along with zirconium atom enters the lattice of cerium oxide, store oxygen ability and high-temperature behavior all obtains larger lifting, but still the environmental requirement of increasingly stringent can not be met.
Up-to-date disclosed result of study shows in cerium zirconium sosoloid, introduce γ-Al
2o
3, the high-temperature stability of hydrogen-storing material can be promoted further and store oxygen performance.γ-Al
2o
3can suppress the agglomeration of cerium zirconium sosoloid particle, cerium zirconium sosoloid can improve γ-Al to a certain extent
2o
3to α-Al
2o
3phase transition temperature, both interact, jointly promote.Such as, Chinese patent CN1695798A discloses a kind of preparation method of Ce-Zr-Al based oxygen stored material, but needs to add stabilizing agent in its preparation process, and preparation method is complicated, higher to the requirement of equipment.Chinese patent CN101112683A discloses the preparation method that one-step method prepares cerium zirconium aluminum composite oxides, surfactant is added before precipitation, what filter cake adopted is roasting after traditional oven dry, and the specific area of product is lower, and high-temperature aging resisting performance still has problems.
Summary of the invention
The object of this invention is to provide a kind of Cerium zirconium aluminum composite oxide oxygen storage material and preparation method thereof, to overcome the defect that prior art exists.
Described Cerium zirconium aluminum composite oxide oxygen storage material, is characterized in that, grain diameter is 5-10nm, and BET specific surface area is 200-240m
2/ g, pore volume is 0.50-0.70cm
3/ g, average pore size is 5-10nm, and cerium zirconium sosoloid has stable cubic fluorite structure, and the mass percent of each component is:
Cerium oxide 10-30%
Zirconia 10-20%
Aluminium oxide 50-80%;
Wherein: aluminium oxide is γ-Al
2o
3;
Described Cerium zirconium aluminum composite oxide oxygen storage material, the BET specific surface area at 1000 DEG C after roasting 4h is greater than 110m
2/ g, pore volume is 0.30-0.50cm
3/ g, average pore size is 13-18nm.
The preparation method of described Cerium zirconium aluminum composite oxide oxygen storage material, comprises the steps:
(1) boehmite is dispersed in the aqueous solution containing first surface activating agent, stirs 1-3h, obtain slurries A;
(2) cerous nitrate, zirconium nitrate is soluble in water, with hydrogen peroxide, trivalent cerium is oxidized to quadrivalent cerium, obtains hybrid metal solion B;
(3) hybrid metal solion B is joined in slurries A, stir 1-3h;
(4) with ammoniacal liquor, pH value is adjusted to 9-10 at the reaction temperatures, continues to stir 1-4h;
(5) still aging 2-4h, filters, and washing is to neutral, and the second surface activator solution making beating dispersion of gained filter cake, roasting, obtains described Cerium zirconium aluminum composite oxide oxygen storage material.
In the slurries of described boehmite dispersion, the mass ratio 1:4-1:8 of aluminium oxide and the aqueous solution.
In described hybrid metal solion, the mass percent concentration of cerium, zirconium nitrate is respectively: cerous nitrate 10-30%, zirconium nitrate 10-20%;
The consumption of hydrogen peroxide is 1.0-2.0 times of cerous nitrate mole, and there is no particular limitation for the concentration of hydrogen peroxide, can adopt the product of commercially available various concentration, preferably 15 ~ 35%(weight).
Described first surface activating agent is one or more in Tween 80, lauryl sodium sulfate or softex kw, and addition is the 10-30wt% of cerium zirconium aluminum composite oxides gross mass.
Described second surface activating agent is one or more in Tween 80, PEG400 or butyl glycol ether, and addition is the 50-100wt% of cerium zirconium aluminum composite oxides gross mass.
Described reaction temperature and ageing are 50-90 DEG C; The temperature of described roasting is 550-700 DEG C, and roasting time is 3-8h, and heating rate is 2-10 DEG C/min.
The washing of described filter cake can adopt the method for water washing, and described water can adopt deionized water, distilled water.
The present inventor surprisingly finds, adopt the cerium zirconium aluminum composite oxides of ad hoc structure, the contradiction of specific area and age stability can be solved, this cerium zirconium aluminum composite oxides has specific structure, also namely boehmite is adopted to be aluminium source, by cerium zirconium sosoloid load at alumina surface, increase specific area on the one hand, make cerium zirconium sosoloid distribution of particles more even; Cerium zirconium sosoloid is distributed in surface on the other hand, can improve the utilization rate of cerium atom.
Feature of the present invention is, according to the difference of surfactant action principle in cerium zirconium aluminum composite oxides preparation process, adds at twice: add the size mainly controlling cerium zirconium sosoloid granular precursor before precipitation, reduces it and reunites; Add before roasting and mainly in roasting process, create abundant pore passage structure for presoma.
Compared with prior art, cerium zirconium aluminum composite oxides of the present invention have Stability Analysis of Structures, specific area high, store oxygen excellent performance, feature that ageing resistace is good.The inventive method raw material is easy to get, production cost is low, and suitability for industrialized amplifies production.
Accompanying drawing explanation
Fig. 1 and Fig. 2 is that the cerium zirconium aluminum composite oxides that in the present invention prepared by embodiment 3 is freshly schemed with the XRD of aged samples respectively.
Fig. 3 and Fig. 4 is that the cerium zirconium aluminum composite oxides that in the present invention prepared by embodiment 3 is freshly schemed with the TEM of aged samples respectively.
Detailed description of the invention
Embodiment 1
By alumina content be 70% boehmite 114.3g join in 216.0g deionized water, add 30.0g Tween 80, in 90 DEG C of water-baths, add thermal agitation 1h; By 25.6g cerous nitrate and 30.3g zirconium nitrate 200g deionized water dissolving, add 26.4g hydrogen peroxide (15wt%), join in above-mentioned solution after fully oxidized, insulation 1h; Adding concentration is the ammoniacal liquor of 25wt%, 10 to be as the criterion to control the pH of terminal, insulation 1h.Then stop stirring, ageing 3h at 90 DEG C, filter and obtain sediment, be washed with water to neutrality, in filter cake, add 50g PEG400, making beating dispersion, is placed in Muffle furnace 550 DEG C of roasting 3h, heating rate is 2 DEG C/min, obtains Cerium zirconium aluminum composite oxide oxygen storage material of the present invention.
Consisting of of this material, cerium oxide 10%, zirconia 10%, aluminium oxide 80%.The fresh specific area of this material is 240m
2/ g, pore volume is 0.70cm
3/ g, average pore size is 5nm; Specific area after 1000 DEG C of roasting 4h is 136m
2/ g, pore volume is 0.50cm
3/ g, average pore size is 13nm.The average grain diameter of this material is 5nm, and dispersion is comparatively even, and aging rear particle is grown up to some extent, only has slight sintering.
Embodiment 2
By alumina content be 70% boehmite 71.4g join in 324.9g deionized water, add 10.0g lauryl sodium sulfate, in 50 DEG C of water-baths, add thermal agitation 3h; By 76.9g cerous nitrate and 60.6g zirconium nitrate 200g deionized water dissolving, add 17.0g hydrogen peroxide (35wt%), join in above-mentioned solution after fully oxidized, insulation 3h; Adding concentration is the ammoniacal liquor of 25wt%, 9 to be as the criterion to control the pH of terminal, insulation 4h.Then stop stirring, ageing 4h at 50 DEG C, filter and obtain sediment, be washed with water to neutrality, in filter cake, add 50g Tween 80, making beating dispersion, is placed in Muffle furnace 700 DEG C of roasting 8h, heating rate is 10 DEG C/min, obtains Cerium zirconium aluminum composite oxide oxygen storage material of the present invention.
Consisting of of this material, cerium oxide 30%, zirconia 20%, aluminium oxide 50%.The fresh specific area of this material is 198m
2/ g, pore volume is 0.50cm
3/ g, average pore size is 10nm; Specific area after 1000 DEG C of roasting 4h is 111m
2/ g, pore volume is 0.30cm
3/ g, average pore size is 18nm.The average grain diameter of this material is 10nm, and dispersion is comparatively even, and aging rear particle is grown up to some extent, only has slight sintering.
Embodiment 3
By alumina content be 70% boehmite 85.7g join in 200g deionized water, add 20.0g softex kw, in 70 DEG C of water-baths, add thermal agitation 2h; By 59.0g cerous nitrate and 51.5g zirconium nitrate 200g deionized water dissolving, add 18.2g hydrogen peroxide (30wt%), join in above-mentioned solution after fully oxidized, insulation 2h; Dripping concentration is the ammoniacal liquor of 25wt%, 9.5 to be as the criterion to control the pH of terminal, insulation 2h.Then stop stirring, 70
dEG Clower ageing 2h, filters and obtains sediment, is washed with water to neutrality, add 80g butyl glycol ether in filter cake, and making beating dispersion, be placed in Muffle furnace 600 DEG C of roasting 4h, heating rate is 5 DEG C/min, obtains Cerium zirconium aluminum composite oxide oxygen storage material of the present invention.
Consisting of of this material, cerium oxide 23%, zirconia 17%, aluminium oxide 60%.Accompanying drawing 1 is shown in by this material XRD collection of illustrative plates, and fresh specific area is 216m
2/ g, pore volume is 0.63cm
3/ g, average pore size is 8nm; Specific area after 1000 DEG C of roasting 4h is 138m
2/ g, pore volume is 0.42cm
3/ g, average pore size is 16nm, and accompanying drawing 2 is shown in by the XRD collection of illustrative plates after aging.The average grain diameter of this material is 8nm, and comparatively evenly (see accompanying drawing 3TEM photo), aging rear particle is grown up to some extent, only has slight sintering (see accompanying drawing 4TEM photo) in dispersion.
Comparative example 1
By alumina content be 70% boehmite 85.7g join in 200g deionized water, add 20.0g softex kw, in 70 DEG C of water-baths, add thermal agitation 2h; By 59.0g cerous nitrate and 51.5g zirconium nitrate 200g deionized water dissolving, add 18.2g hydrogen peroxide (30wt%), join in above-mentioned solution after fully oxidized, insulation 2h; Dripping concentration is the ammoniacal liquor of 25wt%, 9.5 to be as the criterion to control the pH of terminal, insulation 2h.Then stop stirring, ageing 2h at 70 DEG C, filter and obtain sediment, be washed with water to neutrality, 110 DEG C of oven dry, be then placed in Muffle furnace 600 DEG C of roasting 4h, heating rate is 5 DEG C/min, and products therefrom is Cerium zirconium aluminum composite oxide oxygen storage material.
Consisting of of this material, cerium oxide 23%, zirconia 17%, aluminium oxide 60%.The fresh specific area of this material is 171m
2/ g, pore volume is 0.21cm
3/ g, average pore size is 14nm; Specific area after 1000 DEG C of roasting 4h is 92m
2/ g, pore volume is 0.12cm
3/ g, average pore size is 28nm.Fresh and aging specific area is all lower than the specific area of same composition sample in the present invention.
Comparative example 2
By alumina content be 70% boehmite 85.7g join in 200g deionized water, in 70 DEG C of water-baths, add thermal agitation 2h; By 59.0g cerous nitrate and 51.5g zirconium nitrate 200g deionized water dissolving, add 18.2g hydrogen peroxide (30wt%), join in above-mentioned solution after fully oxidized, insulation 2h; Dripping concentration is the ammoniacal liquor of 25wt%, 9.5 to be as the criterion to control the pH of terminal, insulation 2h.Then stop stirring, ageing 2h at 70 DEG C, filter and obtain sediment, be washed with water to neutrality, in filter cake, add 80g butyl glycol ether, making beating dispersion, is placed in Muffle furnace 600 DEG C of roasting 4h, heating rate is 5 DEG C/min, gained Cerium zirconium aluminum composite oxide oxygen storage material.
Consisting of of this material, cerium oxide 23%, zirconia 17%, aluminium oxide 60%.The fresh specific area of this material is 182m
2/ g, pore volume is 0.32cm
3/ g, average pore size is 13nm; Specific area after 1000 DEG C of roasting 4h is 98m
2/ g, pore volume is 0.21cm
3/ g, average pore size is 25nm.Fresh and aging specific area is all starkly lower than the specific area of same composition sample in the present invention.
Claims (4)
1. the preparation method of Cerium zirconium aluminum composite oxide oxygen storage material, is characterized in that, comprises the steps:
(1) boehmite is dispersed in the aqueous solution containing first surface activating agent, obtains slurries A;
(2) cerous nitrate, zirconium nitrate is soluble in water, with hydrogen peroxide, trivalent cerium is oxidized to quadrivalent cerium, obtains hybrid metal solion B;
(3) hybrid metal solion B is joined in slurries A, stir 1-3h;
(4) with ammoniacal liquor, pH value is adjusted to 9-10 at the reaction temperatures, stirs 1-4h;
(5) still aging 2-4h, filters, and washing is extremely neutral, the second surface activator solution making beating dispersion of gained filter cake, and roasting, obtains described Cerium zirconium aluminum composite oxide oxygen storage material; Grain diameter is 5-10nm, and BET specific surface area is 200-240m
2/ g, pore volume is 0.50-0.70cm
3/ g, average pore size is 5-10nm, has stable cubic fluorite structure;
Described first surface activating agent is one or more in Tween 80, lauryl sodium sulfate or softex kw, and addition is the 10-30wt% of cerium zirconium aluminum composite oxides gross mass;
Described second surface activating agent is one or more in Tween 80, PEG400 or butyl glycol ether, and addition is the 50-100wt% of cerium zirconium aluminum composite oxides gross mass;
Reaction temperature and ageing are 50-90 DEG C, and the temperature of roasting is 550-700 DEG C, and roasting time is 3-8h, and heating rate is 2-10 DEG C/min.
2. method according to claim 1, is characterized in that, in the slurries of described boehmite dispersion, and the mass ratio 1:4-1:8 of aluminium oxide and the aqueous solution.
3. method according to claim 1, is characterized in that, in described hybrid metal solion, the mass percent concentration of cerium, zirconium nitrate is respectively: cerous nitrate 10-30%, zirconium nitrate 10-20%.
4. method according to claim 1, is characterized in that, the consumption of hydrogen peroxide is 1.0-2.0 times of cerous nitrate mole.
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| CN103908959B (en) * | 2014-03-27 | 2017-01-25 | 台州欧信环保净化器有限公司 | Ce-Zr composite alumina oxide material and preparation method thereof |
| CN104043441A (en) * | 2014-04-28 | 2014-09-17 | 广东工业大学 | High-performance cerium-zirconium-silicon composite oxide oxygen-storage material and preparation method |
| CN104226295B (en) * | 2014-09-10 | 2016-06-29 | 济南大学 | Cerium zirconium aluminum composite oxides, tail-gas from gasoline automobiles three-way catalyst and their preparation method |
| CN104525180B (en) * | 2014-12-30 | 2017-02-22 | 长沙矿冶研究院有限责任公司 | Preparation method for cerium-zirconium-aluminum-lanthanum-based oxygen storage material of mesoporous structure |
| CN106732578B (en) * | 2016-11-14 | 2019-06-14 | 北京工业大学 | A kind of mesoporous cerium zirconium aluminum composite oxides carried noble metal nanocatalyst of efficient cryogenic, preparation method and applications |
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| CN109529802B (en) * | 2018-11-12 | 2021-12-28 | 山东国瓷功能材料股份有限公司 | Cerium-zirconium composite oxide and preparation method and application thereof |
| CN111744490A (en) * | 2019-03-28 | 2020-10-09 | 苏州华加星光环保工程技术有限公司 | Iron-based denitration catalyst and preparation method thereof |
| CN114797836B (en) * | 2022-05-27 | 2023-08-08 | 珠海格力电器股份有限公司 | Chromium cerium zirconium aluminum solid solution material and preparation method and application thereof |
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