CN113117663A - Porous cerium oxide doped zirconia material and preparation method and application thereof - Google Patents
Porous cerium oxide doped zirconia material and preparation method and application thereof Download PDFInfo
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- CN113117663A CN113117663A CN202110431987.2A CN202110431987A CN113117663A CN 113117663 A CN113117663 A CN 113117663A CN 202110431987 A CN202110431987 A CN 202110431987A CN 113117663 A CN113117663 A CN 113117663A
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- 239000000463 material Substances 0.000 title claims abstract description 74
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 title claims abstract description 66
- 229910000420 cerium oxide Inorganic materials 0.000 title claims abstract description 31
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 239000001257 hydrogen Substances 0.000 claims abstract description 30
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 30
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 28
- 238000004519 manufacturing process Methods 0.000 claims abstract description 21
- 238000010438 heat treatment Methods 0.000 claims description 71
- 239000000243 solution Substances 0.000 claims description 24
- 239000000843 powder Substances 0.000 claims description 22
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 21
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 20
- 238000005245 sintering Methods 0.000 claims description 17
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 16
- 238000001816 cooling Methods 0.000 claims description 16
- 239000011812 mixed powder Substances 0.000 claims description 16
- 238000003756 stirring Methods 0.000 claims description 16
- 229920002472 Starch Polymers 0.000 claims description 15
- 235000019698 starch Nutrition 0.000 claims description 15
- 239000008107 starch Substances 0.000 claims description 15
- 238000000227 grinding Methods 0.000 claims description 14
- 238000001354 calcination Methods 0.000 claims description 12
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 10
- 229910052684 Cerium Inorganic materials 0.000 claims description 9
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 9
- 229910017604 nitric acid Inorganic materials 0.000 claims description 9
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 8
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 7
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 7
- -1 cerium ion Chemical class 0.000 claims description 7
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 7
- 235000006408 oxalic acid Nutrition 0.000 claims description 7
- 238000000498 ball milling Methods 0.000 claims description 6
- 238000003825 pressing Methods 0.000 claims description 6
- 238000007873 sieving Methods 0.000 claims description 6
- GBNDTYKAOXLLID-UHFFFAOYSA-N zirconium(4+) ion Chemical compound [Zr+4] GBNDTYKAOXLLID-UHFFFAOYSA-N 0.000 claims description 6
- 238000002425 crystallisation Methods 0.000 claims description 3
- 230000008025 crystallization Effects 0.000 claims description 3
- 239000007789 gas Substances 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 2
- 238000001704 evaporation Methods 0.000 claims description 2
- 238000000465 moulding Methods 0.000 claims description 2
- 238000000746 purification Methods 0.000 claims description 2
- 238000005984 hydrogenation reaction Methods 0.000 claims 1
- 239000011148 porous material Substances 0.000 abstract description 17
- 230000000694 effects Effects 0.000 abstract description 9
- 238000002474 experimental method Methods 0.000 abstract description 5
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 abstract description 5
- 229910001928 zirconium oxide Inorganic materials 0.000 abstract description 5
- 239000001301 oxygen Substances 0.000 description 16
- 229910052760 oxygen Inorganic materials 0.000 description 16
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 15
- 239000011259 mixed solution Substances 0.000 description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 8
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- 229910001868 water Inorganic materials 0.000 description 5
- 230000009286 beneficial effect Effects 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 238000009740 moulding (composite fabrication) Methods 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 3
- 238000009792 diffusion process Methods 0.000 description 3
- 229910002804 graphite Inorganic materials 0.000 description 3
- 239000010439 graphite Substances 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000003980 solgel method Methods 0.000 description 2
- 239000011232 storage material Substances 0.000 description 2
- 240000003183 Manihot esculenta Species 0.000 description 1
- 235000016735 Manihot esculenta subsp esculenta Nutrition 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- VGBWDOLBWVJTRZ-UHFFFAOYSA-K cerium(3+);triacetate Chemical compound [Ce+3].CC([O-])=O.CC([O-])=O.CC([O-])=O VGBWDOLBWVJTRZ-UHFFFAOYSA-K 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000010431 corundum Substances 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 239000004005 microsphere Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
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- 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
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/04—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of inorganic compounds, e.g. ammonia
- C01B3/042—Decomposition of water
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/02—Processes for making hydrogen or synthesis gas
- C01B2203/0266—Processes for making hydrogen or synthesis gas containing a decomposition step
- C01B2203/0277—Processes for making hydrogen or synthesis gas containing a decomposition step containing a catalytic decomposition step
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
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- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Combustion & Propulsion (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The invention relates to the technical field of hydrogen production, and particularly relates to a porous cerium oxide doped zirconium oxide material and a preparation method and application thereof. The porous cerium oxide doped zirconia material comprises Ce0.97Zr0.03O2(ii) a Preferably, the porous ceria-doped zirconia material has a porosity of 55-65%. The porous cerium oxide doped zirconia material has the advantages of stable structure, high material strength, good hydrogen production effect and the like, and the problem that the pore structure is damaged at high temperature caused by high material strength is avoided. In addition, experiments prove that the porous cerium oxide doped zirconium oxide material has an excellent hydrogen production effect.
Description
Technical Field
The invention relates to the technical field of hydrogen production, and particularly relates to a porous cerium oxide doped zirconium oxide material and a preparation method and application thereof.
Background
Because the valence of cerium element is converted from +4 valence to +3 valence, the zirconia-doped cerium oxide material is generally used as an oxygen storage material, and the performance of the zirconia-doped cerium oxide material determines the catalytic effect of a three-way catalyst, so that the zirconia-doped cerium oxide material is widely applied to the field of automobile exhaust catalysts.
However, zirconia-doped ceria materials are new proposals which have been proposed in the last 10 years, domestic patents are very rare, and few patent documents are available at present, for example, patent CN110252275A discloses a ceria-zirconia composite oxide comprising ceria, zirconia and at least one oxide of a rare earth metal element other than cerium. For another example, patent CN110292920A filed by the academy of salt city, discloses a three-step method for preparing zirconium-doped ceria porous beads, comprising the following steps: preparing cerium acetate sol by adopting a sol-gel method; adding a monomer, an initiator and a promoter to prepare gel, and extruding gel pellets; the pellets are sintered to form porous microspheres.
However, the above preparation method has the following disadvantages: first, burning off the organic material by sintering results in a single pore size, likely closed pores, and a reduction in material strength. Second, thermodynamic calculations and effects of hydrogen production are not described.
In view of the above, the present invention is particularly proposed.
Disclosure of Invention
The first purpose of the invention is to provide a porous cerium oxide doped zirconia material which has the advantages of stable structure, high material strength, good hydrogen production effect and the like, and the problem that the pore structure is damaged at high temperature due to high material strength is avoided.
The second purpose of the present invention is to provide a preparation method of the porous cerium oxide doped zirconia material, wherein the preparation method has the advantages of simple operation, mild conditions, etc.
In order to achieve the above purpose of the present invention, the following technical solutions are adopted:
a porous cerium oxide doped zirconia material is composed of Ce0.97Zr0.03O2。
In the prior art, when a zirconia-doped ceria material is prepared, organic matters are burnt out through sintering, so that the shape and size of a hole are single, a closed hole is likely to be formed, and the strength of the material is reduced. Moreover, the material prepared by the prior art does not perform thermodynamic calculation on hydrogen production, and does not explain the hydrogen production effect.
The invention provides a porous cerium oxide doped Zirconia (ZDC) material, which utilizes starch and graphite to form a stable structure combining large pores and small pores in the ZDC material, is beneficial to the diffusion of oxygen and hydrogen, and avoids the problem that the crystal structure of the material is damaged at high temperature due to overhigh porosity. The porous cerium oxide doped zirconia material comprises Ce0.97Zr0.03O2(hereinafter, abbreviated as "ZDC 03"), ZDC03 releases oxygen at 1500 ℃ to form oxygen vacancies, and introduces water at 800 ℃ to remove oxygen ions in the water to fill the oxygen vacancies and release hydrogen. The whole circulation process is shown in formulas (1) and (2).
(Zr/Ce)O2→Zr/CeO2·δ+δ/2O2 (1)
H2O(ɡ)+1/δ(Zr/Ce)O2-δ→1/δ(Zr/Ce)O2-δ+H2(ɡ) (2)
The ZDC03 is a very promising material for preparing clean energy hydrogen, and experiments prove that the ZDC03 material has excellent hydrogen production effect.
Preferably, the porous ceria-doped zirconia material has a porosity of 55-65%.
More preferably, the porous ceria doped zirconia material has a porosity of 60%.
Whether the ZDC material can effectively and rapidly produce hydrogen or not determines the value of the ZDC material in industrial application, and the hydrogen production efficiency and the porosity of the ZDC material are closely related. According to the invention, the porosity is optimized, and the combination of the large holes and the small holes ensures that the strength of the material is not obviously reduced, and particularly the hole structure is not damaged at high temperature.
The preparation method of the porous cerium oxide doped zirconia material comprises the following steps:
(1) mixing the zirconium ion solution and the cerium ion solution with EDTA and oxalic acid, adjusting the pH value, heating and stirring, evaporating for crystallization, and calcining to obtain powder;
(2) mixing the powder with ethanol, adding starch, grinding, sieving, and heating to dry to obtain mixed powder;
(3) and mixing and grinding the mixed powder and graphite powder, pressing and molding, and sintering to obtain the graphite powder.
The preparation method of the porous zirconia doped cerium oxide material provided by the invention comprises the steps of firstly preparing powder by adopting a sol-gel method, then adding a pore-forming agent, and finally sintering to obtain a final product.
The preparation method has the advantages of simple operation, mild conditions and the like, and is favorable for further popularization and use of the product.
Preferably, in the step (1), the molar ratio of the zirconium ion solution to the cerium ion solution to the EDTA to the oxalic acid is 3: 97: 145-147: 320-323.
The doping of zirconia plays a critical role in the oxygen evolution and oxygen vacancy formation of ZDC materials, mainly due to the fact that the ionic radius of zirconium is smaller than that of cerium, resulting in a reduction of the binding force of cations to anions. However, the increase in the amount of zirconia doping is ineffective after the number of oxygen vacancies is saturated, and rather, insufficient power is generated when hydrogen is released at low temperature. Thus, a 3 mol% zirconia doping level is an optimum result.
Preferably, in the step (1), the zirconium ion solution is ZrO (NO)3)2·2.3H2Nitric acid solution of O.
Preferably, the mass fraction of the nitric acid is 8-15%.
More preferably, the mass fraction of the nitric acid is 10%.
Preferably, the cerium ion solution is Ce (NO)3)3·6H2An aqueous solution of O.
More preferably, the water is deionized water.
Preferably, in the step (1), the step of adjusting the pH comprises: adding ammonia water to adjust the pH to 9-11.
More preferably, the step of adjusting the pH comprises: ammonia was added slowly to adjust the pH to 10.
More preferably, the mass fraction of the ammonia water is 3-5%.
Preferably, the heating and stirring conditions include: stirring for 5-10h at 70-90 deg.C and rotation speed of 300-500 rpm.
More preferably, the heating and stirring conditions include: stirring for 6-8h at 80 ℃ and 400 rpm.
Preferably, the operation of evaporative crystallization comprises: and transferring the heated and stirred mixed solution into a crucible, and then placing the crucible in a microwave heating device for heating until the mixed solution is evaporated to dryness.
More preferably, the crucible is a corundum crucible.
Preferably, the calcination conditions include: calcining at 500-950 deg.c for 4-6 hr.
More preferably, the conditions of the calcination include: calcining at 800-950 deg.c for 4.5-5.5 hr.
Preferably, in the step (2), the adding amount of the ethanol is 2-4 times of the mass of the powder.
Preferably, the mass fraction of the ethanol is 30-40%.
Preferably, the starch is added in an amount of 2-4% by mass of the powder.
More preferably, the starch is added in an amount of 3% by mass of the powder.
Wherein the starch functions to make large pores, with a pore size of about 5-10 microns.
More preferably, the starch is tapioca starch.
Preferably, in the step (2), the grinding is ball milling.
Preferably, the grinding time is 20-28 h.
More preferably, the grinding time is 22-26 h.
Further preferably, the grinding time is 24 h.
Preferably, the aperture of the sieved screen is 1 mm.
Preferably, the temperature for heating and drying is 50-70 ℃ and the time is 20-30 h.
More preferably, the temperature for heating and drying is 55-65 ℃ and the time is 22-26 h.
Further preferably, the temperature for heating and drying is 60 ℃ and the time is 24 h.
Preferably, in the step (3), the adding amount of the graphite powder is 10-30% of the mass of the mixed powder.
More preferably, the adding amount of the graphite powder is 15-25% of the mass of the mixed powder.
More preferably, the adding amount of the graphite powder is 20% of the mass of the mixed powder.
Wherein the graphite functions to make pores with a pore size of about 1-2 microns.
The stable structure combining large holes and small holes is formed in the ZDC material by utilizing starch and graphite, so that the diffusion of oxygen and hydrogen is facilitated, and the problem that the material is damaged at high temperature due to overhigh porosity is solved.
Preferably, in the step (3), the sintering conditions include: (a) heating to 400-600 ℃ at the heating rate of 5 ℃/second; (b) heating to 900-; (c) heating to 1400 ℃ and 1600 ℃ at the heating rate of 3 ℃/s, and preserving the heat for 4-6 hours; (d) cooling to room temperature at a cooling rate of 5 ℃/sec.
More preferably, the sintering conditions include: (a) heating to 500 ℃ at the heating rate of 5 ℃/second; (b) heating to 1000 ℃ at the heating rate of 1 ℃/second, and keeping the temperature for 2 hours; (c) heating to 1500 ℃ at the heating rate of 3 ℃/second, and keeping the temperature for 5 hours; (d) cooling to room temperature at a cooling rate of 5 ℃/sec.
The porous cerium oxide doped zirconium oxide material is applied to hydrogen production and tail gas purification.
Preferably, the porous cerium oxide doped zirconium oxide material is used as an oxygen storage material and a promoter for tail gas treatment.
According to the invention, hydrogen production experiments show that the ZDC03 material has excellent hydrogen production effect.
Compared with the prior art, the invention has the beneficial effects that:
(1) the invention provides a porous cerium oxide doped zirconia material ZDC03, which utilizes starch and graphite to create a stable structure with large and small holes in the ZDC material, thereby being beneficial to the diffusion of oxygen and hydrogen and avoiding the problem that the crystal structure of the material is damaged at high temperature due to overhigh porosity.
(2) The porous cerium oxide doped zirconia material provided by the invention consists of 97% mol of cerium oxide and 3% mol of zirconia, and thermodynamic experiments prove that the ZDC03 material meets the condition of capturing oxygen from water to produce hydrogen thermodynamically, and experiments prove that the ZDC03 material has an excellent hydrogen production effect.
(3) The invention provides a preparation method of the porous cerium oxide doped zirconia material, which has the advantages of simple operation, mild conditions and the like and is beneficial to further popularization and use of products.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and other drawings can be obtained by those skilled in the art without creative efforts.
Fig. 1 is a schematic scanning electron microscope diagram of a ZDC03 material provided in embodiment 1 of the present invention.
Detailed Description
The technical solutions of the present invention will be clearly and completely described below with reference to the accompanying drawings and the detailed description, but those skilled in the art will understand that the following described embodiments are some, not all, of the embodiments of the present invention, and are only used for illustrating the present invention, and should not be construed as limiting the scope of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
Example 1
The preparation method of the porous cerium oxide doped zirconia material provided by the embodiment comprises the following steps:
(1) weighing 0.96 g ZrO (NO)3)2·2.3H2O was dissolved in 35ml of a 10% nitric acid solution, and 49.25 g of Ce (NO) was weighed3)3·6H2Dissolving O in 800ml of deionized water, mixing, adding 51.29 g of EDTA and 33.72 g of oxalic acid, stirring uniformly, slowly adding ammonia water with the mass fraction of 4%, adjusting the pH value of the mixed solution to 10, stirring for 6 hours at 80 ℃ and 400rpm, transferring the mixed solution into a crucible, heating the mixed solution in a microwave heating device to 8mim to evaporate the liquid, transferring the obtained powder into a muffle furnace, calcining for 5 hours at 500 ℃, and collecting 18g of powder;
(2) adding 60g of 30% ethanol into the powder, adding 0.54g of starch, ball-milling for 24 hours, sieving by using a sieve with the aperture of 1mm, and heating and drying the sieved slurry at 60 ℃ for 24 hours to obtain mixed powder;
(3) adding 3.6g of graphite powder into the mixed powder, uniformly grinding, pressing and forming by using a dry press, and sintering in a muffle furnace, wherein the sintering conditions comprise: (a) heating to 500 ℃ at the heating rate of 5 ℃/second; (b) heating to 1000 ℃ at the heating rate of 1 ℃/second, and keeping the temperature for 2 hours; (c) heating to 1500 ℃ at the heating rate of 3 ℃/second, and keeping the temperature for 5 hours; (d) cooling to room temperature at the cooling speed of 5 ℃/second to obtain the ZDC03 material.
Example 2
The preparation method of the porous cerium oxide doped zirconia material provided by the embodiment comprises the following steps:
(1) weighing 0.96 g ZrO (NO)3)2·2.3H2O was dissolved in 35ml of a nitric acid solution having a mass fraction of 8%, and 49.25 g of Ce (NO) was weighed3)3·6H2Dissolving O in 400ml deionized water, mixing, adding 51.29 g EDTA and 33.72 g grassAcid, slowly adding ammonia water with the mass concentration of 3% after uniformly stirring, adjusting the pH value of the mixed solution to 9, stirring for 5 hours at the temperature of 70 ℃ and the rotation speed of 300rpm, transferring the mixed solution into a crucible, placing the crucible in a microwave heating device to heat 9mim to evaporate liquid, transferring the obtained powder into a muffle furnace, calcining for 4 hours at the temperature of 950 ℃, and collecting 17g of powder;
(2) adding 34g of 40% ethanol by mass into the powder, adding 0.34g of starch, ball-milling for 20 hours, sieving by using a sieve with the aperture of 1mm, and heating and drying the sieved slurry at 50 ℃ for 30 hours to obtain mixed powder;
(3) adding 1.7g of graphite powder into the mixed powder, uniformly grinding, pressing and forming by using a dry press, and sintering in a muffle furnace, wherein the sintering conditions comprise: (a) heating to 400 ℃ at the heating rate of 5 ℃/second; (b) heating to 900 ℃ at the heating rate of 1 ℃/second, and preserving heat for 3 hours; (c) heating to 1400 ℃ at the heating rate of 3 ℃/second, and keeping the temperature for 6 hours; (d) cooling to room temperature at the cooling speed of 5 ℃/second to obtain the ZDC03 material.
Example 3
The preparation method of the porous cerium oxide doped zirconia material provided by the embodiment comprises the following steps:
(1) weighing 0.32 g ZrO (NO)3)2·2.3H2O was dissolved in 35ml of a 15% nitric acid solution, and 16.42 g of Ce (NO) was weighed3)3·6H2Dissolving O in 800ml of deionized water, mixing, adding 17.10 g of EDTA and 11.24 g of oxalic acid, stirring uniformly, slowly adding ammonia water with the mass concentration of 5%, adjusting the pH value of the mixed solution to 11, stirring for 10 hours at the temperature of 90 ℃ and the rotation speed of 500rpm, transferring the mixed solution into a crucible, placing the crucible into a microwave heating device, heating 10mim of evaporated liquid, transferring the obtained powder into a muffle furnace, calcining for 6 hours at the temperature of 800 ℃, and collecting 18g of powder;
(2) adding 72g of 35% ethanol into the powder, adding 7.2g of starch, ball-milling for 28h, sieving by using a sieve with the aperture of 1mm, and heating and drying the sieved slurry at 70 ℃ for 20h to obtain mixed powder;
(3) adding 5.4g of graphite powder into the mixed powder, uniformly grinding, pressing and forming by using a dry press, and sintering in a muffle furnace, wherein the sintering conditions comprise: (a) heating to 600 ℃ at the heating rate of 5 ℃/second; (b) heating to 1100 ℃ at the heating rate of 1 ℃/second, and keeping the temperature for 1 hour; (c) heating to 1600 ℃ at the heating rate of 3 ℃/s, and keeping the temperature for 4 hours; (d) cooling to room temperature at the cooling speed of 5 ℃/second to obtain the ZDC03 material.
Comparative example 1
The preparation method of the porous cerium oxide doped zirconia material provided by the comparative example is the same as that of the example 1, and the difference is only that the doping amount of the zirconia is 20 mol%, and the preparation method specifically comprises the following steps:
(1) 6.7 g ZrO (NO) are weighed3)2·2.3H2O was dissolved in 35ml of a 10% nitric acid solution, and 42.8 g of Ce (NO) was weighed3)3·6H2Dissolving O in 800ml of deionized water, mixing, adding 53.9 g of EDTA and 37.5 g of oxalic acid, stirring uniformly, slowly adding 4% ammonia water by mass, adjusting the pH value of the mixed solution to 10, stirring for 6 hours at 80 ℃ and 400rpm, transferring the mixed solution into a crucible, heating 8mim of evaporated liquid in a microwave heating device, transferring the obtained powder into a muffle furnace, calcining for 5 hours at 500 ℃, and collecting 18g of powder;
(2) adding 60g of 30% ethanol into the powder, adding 0.54g of starch, ball-milling for 24 hours, sieving by using a sieve with the aperture of 1mm, and heating and drying the sieved slurry at 60 ℃ for 24 hours to obtain mixed powder;
(3) adding 3.6g of graphite powder into the mixed powder, uniformly grinding, pressing and forming by using a dry press, and sintering in a muffle furnace, wherein the sintering conditions comprise: (a) heating to 500 ℃ at the heating rate of 5 ℃/second; (b) heating to 1000 ℃ at the heating rate of 1 ℃/second, and keeping the temperature for 2 hours; (c) heating to 1500 ℃ at the heating rate of 3 ℃/second, and keeping the temperature for 5 hours; (d) cooling to room temperature at the cooling speed of 5 ℃/second to obtain the ZDC03 material.
Comparative example 2
The material provided by the comparative example is a cerium oxide material, and the cerium oxide material is an experimental grade material of Shanghai Aladdin Biotechnology Co., Ltd, the purity is 99.99%, and the particle size is less than 5 microns.
Test example 1
The result of the scanning electron microscope test on the ZDC03 material prepared in example 1 is shown in fig. 1, and it can be seen that the pore structure in the ZDC03 material is a stable structure combining large pores and small pores, wherein the pore size of the large pores is about 5-10 microns, the pore size of the small pores is about 1-2 microns, and the porosity is about 60%.
Test example 2
The ZDC03 materials prepared in examples 1-3 and comparative examples 1-2 were subjected to hydrogen production tests.
The test method comprises the following steps: an infrared heating furnace is used to simulate the effect of solar energy to instantaneously generate heat, the furnace is heated by halogen, and gold foil is used for reflection. The prepared porous ZDC03 material was placed in an alumina tube covered with quartz glass. The mass percentages of hydrogen and oxygen produced were quantified using a mass spectrometer (pfeiffer thermoostergsd 301).
The result shows that the furnace is heated to 1500 ℃ to release oxygen to form oxygen vacancy, then the temperature is reduced to 800 ℃, hydrogen is produced, and the mass spectrometer monitors that the hydrogen production amount is not obviously increased. The entire process was continued for 12 minutes, and the hydrogen production per gram of material was calculated and converted in units as shown in table 1 below.
TABLE 1 Hydrogen yield for materials of examples 1-3 and comparative examples 1-2
| Group of | Example 1 | Example 2 | Example 3 | Comparative example 1 | Comparative example 2 |
| Hydrogen production (mL/g) | 10.2 | 10.9 | 10.1 | 7.2 | 10.4 |
While particular embodiments of the present invention have been illustrated and described, it will be appreciated that the above embodiments are merely illustrative of the technical solution of the present invention and are not restrictive; those of ordinary skill in the art will understand that: modifications may be made to the above-described embodiments, or equivalents may be substituted for some or all of the features thereof without departing from the spirit and scope of the present invention; the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention; it is therefore intended to cover in the appended claims all such alternatives and modifications that are within the scope of the invention.
Claims (10)
1. The porous cerium oxide doped zirconia material is characterized in that the porous cerium oxide doped zirconia material consists of Ce0.97Zr0.03O2；
Preferably, the porous ceria-doped zirconia material has a porosity of 55-65%.
2. The method of preparing a porous ceria-doped zirconia material of claim 1, comprising the steps of:
(1) mixing the zirconium ion solution and the cerium ion solution with EDTA and oxalic acid, adjusting the pH value, heating and stirring, evaporating for crystallization, and calcining to obtain powder;
(2) mixing the powder with ethanol, adding starch, grinding, sieving, and heating to dry to obtain mixed powder;
(3) and mixing and grinding the mixed powder and graphite powder, pressing and molding, and sintering to obtain the graphite powder.
3. The method according to claim 2, wherein in the step (1), the molar ratio of the zirconium ion solution, the cerium ion solution, the EDTA, and the oxalic acid is 3: 97: 145-147: 320-323.
4. The method according to claim 2, wherein in the step (1), the zirconium ion solution is ZrO (NO)3)2·2.3H2Nitric acid solution of O;
preferably, the mass fraction of the nitric acid is 8-15%;
preferably, the cerium ion solution is Ce (NO)3)3·6H2An aqueous solution of O.
5. The method according to claim 2, wherein in the step (1), the step of adjusting the pH comprises: adding ammonia water to adjust the pH value to 9-11;
preferably, the heating and stirring conditions include: stirring for 5-10h at the temperature of 70-90 ℃ and the rotation speed of 300-500 rpm;
preferably, the calcination conditions include: calcining at 500-950 deg.c for 4-6 hr.
6. The preparation method according to claim 2, wherein in the step (2), the adding amount of the ethanol is 2-4 times of the mass of the powder;
preferably, the mass fraction of the ethanol is 30-40%;
preferably, the starch is added in an amount of 2-4% by mass of the powder.
7. The production method according to claim 2, wherein in the step (2), the grinding is ball milling;
preferably, the grinding time is 20-28 h;
preferably, the aperture of the sieved screen mesh is 1 mm;
preferably, the temperature for heating and drying is 50-70 ℃ and the time is 20-30 h.
8. The preparation method according to claim 2, wherein in the step (3), the adding amount of the graphite powder is 10-30% of the mass of the mixed powder.
9. The production method according to claim 2, wherein in the step (3), the sintering conditions include: (a) heating to 400-600 ℃ at the heating rate of 5 ℃/second; (b) heating to 900-; (c) heating to 1400 ℃ and 1600 ℃ at the heating rate of 3 ℃/s, and preserving the heat for 4-6 hours; (d) cooling to room temperature at a cooling rate of 5 ℃/second;
preferably, the sintering conditions include: (a) heating to 500 ℃ at the heating rate of 5 ℃/second; (b) heating to 1000 ℃ at the heating rate of 1 ℃/second, and keeping the temperature for 2 hours; (c) heating to 1500 ℃ at the heating rate of 3 ℃/second, and keeping the temperature for 5 hours; (d) cooling to room temperature at a cooling rate of 5 ℃/sec.
10. The use of the porous ceria doped zirconia material of claim 1 in the production of hydrogen and purification of tail gas.
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