CN113101964A - Mesoporous cerium oxide photocatalyst and preparation method and application thereof - Google Patents
Mesoporous cerium oxide photocatalyst and preparation method and application thereof Download PDFInfo
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- CN113101964A CN113101964A CN202110453499.1A CN202110453499A CN113101964A CN 113101964 A CN113101964 A CN 113101964A CN 202110453499 A CN202110453499 A CN 202110453499A CN 113101964 A CN113101964 A CN 113101964A
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- 239000011941 photocatalyst Substances 0.000 title claims abstract description 30
- 229910000420 cerium oxide Inorganic materials 0.000 title claims abstract description 23
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 75
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 52
- 239000003054 catalyst Substances 0.000 claims abstract description 37
- 238000001035 drying Methods 0.000 claims abstract description 26
- 239000002808 molecular sieve Substances 0.000 claims abstract description 26
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 26
- 238000000034 method Methods 0.000 claims abstract description 20
- 238000001354 calcination Methods 0.000 claims abstract description 18
- 238000002156 mixing Methods 0.000 claims abstract description 16
- 239000002243 precursor Substances 0.000 claims abstract description 16
- 230000001699 photocatalysis Effects 0.000 claims abstract description 15
- 238000010438 heat treatment Methods 0.000 claims abstract description 14
- 239000002904 solvent Substances 0.000 claims abstract description 14
- 229910052684 Cerium Inorganic materials 0.000 claims abstract description 10
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims abstract description 10
- 230000004913 activation Effects 0.000 claims abstract description 9
- 239000003513 alkali Substances 0.000 claims abstract description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- 239000008367 deionised water Substances 0.000 claims description 7
- 229910021641 deionized water Inorganic materials 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- 238000005119 centrifugation Methods 0.000 claims description 6
- 239000011148 porous material Substances 0.000 claims description 6
- QQZMWMKOWKGPQY-UHFFFAOYSA-N cerium(3+);trinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O QQZMWMKOWKGPQY-UHFFFAOYSA-N 0.000 claims description 4
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 3
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 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
- 239000003599 detergent Substances 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- KPZSTOVTJYRDIO-UHFFFAOYSA-K trichlorocerium;heptahydrate Chemical compound O.O.O.O.O.O.O.Cl[Ce](Cl)Cl KPZSTOVTJYRDIO-UHFFFAOYSA-K 0.000 claims description 2
- 239000000758 substrate Substances 0.000 abstract description 3
- 230000000052 comparative effect Effects 0.000 description 10
- 239000000843 powder Substances 0.000 description 8
- 239000007787 solid Substances 0.000 description 8
- 239000007789 gas Substances 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 230000009286 beneficial effect Effects 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 230000003197 catalytic effect Effects 0.000 description 4
- 238000003837 high-temperature calcination Methods 0.000 description 4
- 229910000510 noble metal Inorganic materials 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 230000003213 activating effect Effects 0.000 description 3
- 238000005286 illumination Methods 0.000 description 3
- 229910052741 iridium Inorganic materials 0.000 description 3
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 238000007146 photocatalysis Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 239000012670 alkaline solution Substances 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 1
- 239000005751 Copper oxide Substances 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- FHKNFXAIEAYRKQ-UHFFFAOYSA-N [Cu].[Ir] Chemical compound [Cu].[Ir] FHKNFXAIEAYRKQ-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 229910000428 cobalt oxide Inorganic materials 0.000 description 1
- 239000000498 cooling water Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 229910000431 copper oxide Inorganic materials 0.000 description 1
- -1 copper-zirconium-aluminum Chemical group 0.000 description 1
- HTXDPTMKBJXEOW-UHFFFAOYSA-N dioxoiridium Chemical compound O=[Ir]=O HTXDPTMKBJXEOW-UHFFFAOYSA-N 0.000 description 1
- 239000010436 fluorite Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229910000457 iridium oxide Inorganic materials 0.000 description 1
- 239000012263 liquid product Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000000527 sonication Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- XLOMVQKBTHCTTD-UHFFFAOYSA-N zinc oxide Inorganic materials [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/03—Catalysts comprising molecular sieves not having base-exchange properties
- B01J29/0308—Mesoporous materials not having base exchange properties, e.g. Si-MCM-41
-
- 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
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
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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
- 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
- B01J35/61—Surface area
- B01J35/613—10-100 m2/g
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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
- 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
- B01J35/61—Surface area
- B01J35/615—100-500 m2/g
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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
- 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
- B01J35/64—Pore diameter
- B01J35/647—2-50 nm
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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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
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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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
- B01J37/088—Decomposition of a metal salt
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/48—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by oxidation reactions with formation of hydroxy groups
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- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
- B01J2229/186—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself not in framework positions
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Abstract
The invention provides a mesoporous cerium oxide photocatalyst and a preparation method and application thereof, wherein the preparation method comprises the following steps: (1) mixing a mesoporous molecular sieve with a solvent, adding a cerium source, and heating and drying to obtain a precursor; (2) calcining the precursor obtained in the step (1), mixing the calcined precursor with alkali liquor, and drying to obtain the mesoporous cerium oxide photocatalyst; wherein, the mesoporous molecular sieve is KIT-6. The invention prepares mesoporous CeO by using KIT-6 molecular sieve as a substrate through a template roasting method2The catalyst is used as a catalyst for preparing methanol by photocatalytic methane activation, and has regular shape and mesoporous structureStable structure, good crystallinity, high purity, high photocatalytic activity under visible light and the like.
Description
Technical Field
The invention belongs to the technical field of inorganic nano materials, and relates to a mesoporous cerium oxide photocatalyst, and a preparation method and application thereof.
Background
The conversion of methane to methanol has always been a hot research direction in the field of catalysis. The traditional thermal catalytic methane activation method for preparing methanol is limited by thermodynamic equilibrium, high-temperature and high-pressure conditions are often needed, the operation is complex, the cost is high, and the yield and the selectivity of methanol cannot simultaneously reach ideal levels. The reaction of converting methane into methanol by utilizing solar-driven photocatalysis can reduce the energy barrier of the reaction and realize the preparation of methanol by methane activation under mild conditions.
CN110038591A discloses a copper-iridium composite oxide catalyst for preparing methanol by directly oxidizing methane and a preparation method thereof. The catalyst consists of iridium oxide, copper oxide and promoter zinc, cobalt or iron oxide. Based on 100 percent of the weight of the catalyst, the weight percentage of the noble metal iridium is 0.1 to 10.0 percent, and the cocatalyst MOxThe weight percentage of the iridium-containing catalyst is 0-20.0%, and the catalyst has the characteristics of simple preparation method, high methanol yield and repeated recycling in the reaction of preparing methanol by methane oxidation, but uses noble metal iridium, is expensive in manufacturing cost and is not suitable for industrial production.
CN110252302A discloses a catalyst for preparing methanol by catalyzing methane to be selectively oxidized at low temperature, wherein the catalyst is a copper-zirconium-aluminum composite metal oxide, and has the following structural general formula: cuaZrbAlcOdWherein a, b, c and d are the atomic numbers of Cu, Zr, Al and O elements in the catalyst, the value range of a is 1-2, the value range of b is 1-2, and the value range of c is 1-2; d is the number of oxygen atoms required to satisfy the oxidation state of the other elements. The disclosed catalyst has simple synthesis method, can catalyze methane at the temperature of 100-200 ℃ to prepare methanol, and has high methane conversion rate and good methanol selectivity.
The above-mentioned scheme has the disadvantages of using noble metals or requiring high temperature conditions, and therefore, it is necessary to develop a photocatalyst which can convert methane into methanol at normal temperature without adding noble metals.
Disclosure of Invention
The invention aims to provide a mesoporous cerium oxide photocatalyst and a preparation method and application thereof, wherein the preparation method comprises the following steps: (1) mixing a mesoporous molecular sieve with a solvent, adding a cerium source, and heating and drying to obtain a precursor; (2) calcining the precursor obtained in the step (1), mixing the calcined precursor with alkali liquor, and drying to obtain the mesoporous oxygenA cerium-oxide photocatalyst; wherein, the mesoporous molecular sieve is KIT-6. The mesoporous CeO with regular appearance, stable mesoporous structure, good crystallinity and high purity is obtained by a template roasting method2The photocatalyst has outstanding excellent performance of preparing methanol by photocatalytic methane activation.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a preparation method of a mesoporous cerium oxide photocatalyst, comprising the following steps:
(1) mixing a mesoporous molecular sieve with a solvent, adding a cerium source, and heating and drying to obtain a precursor;
(2) calcining the precursor obtained in the step (1), mixing the calcined precursor with alkali liquor, and drying to obtain the mesoporous cerium oxide photocatalyst;
wherein, the mesoporous molecular sieve is KIT-6.
The invention prepares mesoporous CeO by using KIT-6 molecular sieve as a substrate through a template roasting method2The catalyst is used as a catalyst for preparing methanol by photocatalytic methane activation, and has the characteristics of regular shape, stable mesoporous structure, good crystallinity, high purity, high photocatalytic activity under visible light and the like. Mesoporous CeO2The product is dispersed into a closed quartz glass reactor filled with water, methane is introduced after the air in the reactor is exhausted, and the methane can be activated to prepare methanol through a photocatalysis process under the illumination condition, so that the method is beneficial to practical application.
Preferably, the ratio of the mass of the mesoporous molecular sieve to the volume of the solvent in step (1) is (0.1-1) g/10mL, for example: 0.1g/10mL, 0.2g/10mL, 0.3g/10mL, 0.5g/10mL, 0.7g/10mL, 0.8g/10mL, or 1g/10 mL.
Preferably, the solvent comprises deionized water and/or ethanol.
Preferably, the mesoporous molecular sieve is mixed with the solvent while stirring.
Preferably, the stirring speed is 150-600 r/min, such as: 150r/min, 200r/min, 250r/min, 300r/min, 400r/min, 500r/min or 600r/min, preferably 200-400 r/min.
Preferably, the cerium source of step (1) comprises any one of cerous nitrate hexahydrate, cerous chloride heptahydrate or cerous acetate hydrate, or a combination of at least two of them.
Preferably, the mass ratio of the cerium source to the mesoporous molecular sieve is 1 (0.1-1), such as 1: 0.1, 1: 0.3, 1: 0.4, 1: 0.5, 1: 0.6, 1: 0.7, 1: 0.8, 1: 0.9 or 1: 1, etc., preferably 1 (0.25 to 0.75).
Preferably, the heating and drying in the step (1) are carried out in a standing way.
Preferably, the standing time is 0.5-12 h, such as 0.5h, 1.5h, 8h or 12h, and the like, and preferably 1-3 h.
Preferably, the temperature for heating and drying in step (1) is 40-120 ℃, such as 40 ℃, 60 ℃, 65 ℃, 80 ℃ or 120 ℃, preferably 50-80 ℃.
Preferably, the time for heating and drying in step (1) is 8-48 h, such as 8h, 14h, 16h, 24h, 30h or 48h, and the like, and preferably 10-24 h.
Preferably, the temperature of the calcination in step (2) is 400 to 900 ℃, for example, 400 ℃, 440 ℃, 480 ℃, 520 ℃, 560 ℃, 600 ℃, 640 ℃, 660 ℃, 680 ℃, 700 ℃, 720 ℃, 800 ℃, 860 ℃, or 900 ℃, preferably 750 to 800 ℃.
Preferably, the temperature rise rate of the calcination is 1-20 ℃/min, such as 1 ℃/min, 4 ℃/min, 6 ℃/min, 8 ℃/min, 10 ℃/min, 12 ℃/min, 14 ℃/min, 16 ℃/min or 20 ℃/min, and the like, preferably 3-5 ℃/min.
Preferably, the calcination time is 3-12 h, such as 3h, 5h, 7h, 9h, 10h or 12h, etc., preferably 4-8 h.
Preferably, the alkali solution in step (2) comprises any one or a combination of two of NaOH solution and KOH solution.
Preferably, the concentration of the alkali liquor is 1-5 mol/L, such as: 1mol/L, 2mol/L, 3mol/L, 4mol/L or 5mol/L, etc., preferably 2 to 3 mol/L.
Preferably, the drying in step (2) is preceded by centrifugation, filtration and washing.
Preferably, the rotation speed during centrifugation is 6000 to 12000r/min, such as 6000r/min, 8000r/min, 900r/min, 10000r/min or 12000r/min, and preferably 8000 to 10000 r/min.
Preferably, the centrifugation time is 3-15 min, preferably 5-10 min.
Preferably, the washing detergent comprises ethanol and/or deionized water.
Preferably, the number of washing is 2 to 5, for example: 2, 3, 4 or 5 times, etc.
Preferably, the drying temperature in step (2) is 50-150 ℃, for example 50 ℃, 60 ℃, 70 ℃, 100 ℃ or 150 ℃, preferably 60-90 ℃.
Preferably, the drying time in the step (2) is 8-48 h, such as 8h, 10h, 13h, 14h, 16h, 20h, 25h, 32h, 36h, 40h or 48h, and the like, and preferably 10-24 h.
As a preferable scheme of the invention, the preparation method comprises the following steps:
(1) mixing a mesoporous molecular sieve and a solvent according to the ratio of the mass of the mesoporous molecular sieve to the volume of the solvent being (0.1-1):10, adding a cerium source, and heating and drying to obtain a precursor;
(2) calcining the precursor obtained in the step (1) at 400-900 ℃ for 3-12 h, mixing with alkali liquor, and drying to obtain the mesoporous cerium oxide photocatalyst;
wherein, the mesoporous molecular sieve is KIT-6.
In a second aspect, the present invention provides a mesoporous ceria photocatalyst, the catalyst being obtainable by a process as described in the first aspect; the specific surface area of the catalyst is 75-100cm2,/g, for example: 75cm2/g、80cm2/g、85cm2/g、90cm2/g、95cm2G or 100cm2The catalyst has an average pore diameter of 5 to 30nm, such as: 5nm, 10nm, 15nm, 20nm, 25nm or 30nm, etc.
The mesoporous cerium oxide photocatalyst has an adjustable band gap and can effectively absorb ultraviolet or visible light. Mesoporous CeO of nanometer scale2Oxidation of carbon dioxide compared to bulkCerium has large specific surface area, ordered pore channel structure, more excellent optical property and catalytic performance.
In a third aspect, the invention provides an application of the mesoporous cerium oxide photocatalyst as described in the second aspect, and the mesoporous cerium oxide photocatalyst is used for preparing methanol by photocatalytic methane activation.
Compared with the prior art, the invention has the following beneficial effects:
(1) the invention prepares mesoporous CeO by using KIT-6 molecular sieve as a substrate through a template roasting method2As a photocatalyst for preparing methanol by activating methane, the catalyst has the characteristics of regular shape, stable mesoporous structure, good crystallinity, high purity, high photocatalytic activity under visible light and the like. Mesoporous CeO2The product is dispersed into a closed quartz glass reactor filled with water, methane is introduced after the air in the reactor is exhausted, and the methane can be activated to prepare methanol through a photocatalysis process under the illumination condition, so that the method is beneficial to practical application.
(2) The preparation method disclosed by the invention is simple to operate, environment-friendly, low in cost and beneficial to practical application.
Drawings
FIG. 1 is a TEM image of a catalyst obtained in example 1 of the present invention.
FIG. 2 is an XRD pattern of the catalyst obtained in example 1 of the present invention.
FIG. 3 is a graph showing the comparison of the performance of the catalyst of the present invention obtained in example 1 and the performance of the catalyst of comparative example 1 for methanol production by photocatalytic methane activation.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
Example 1
The embodiment provides a mesoporous cerium oxide photocatalyst, and a preparation method of the catalyst comprises the following steps:
(1) mixing 0.25g of KIT-6 mesoporous molecular sieve with 10mL of water;
(2) adding 1g of cerous nitrate hexahydrate into the mixed solution, and heating the liquid after standing for 2 hours at 60 ℃ for 12 hours to obtain dry solid powder;
(3) calcining dried solid powder at high temperature of 800 ℃, mixing the calcined solid powder with 2mol/L alkaline solution at the stirring speed of 300r/min, reacting for 0.5h, centrifuging the liquid without the template at the speed of 8000r/min for 6min, washing the obtained precipitate with ethanol and deionized water for 3 times in sequence, drying at 80 ℃ for 12h to obtain the solid powder with the specific surface area of 85cm2(ii) a mesoporous cerium oxide photocatalyst having an average pore diameter of 11 nm.
The TEM image of the catalyst is shown in FIG. 1, and it can be seen from FIG. 1 that the catalyst has regular morphology and uniform and stable mesoporous structure.
The XRD pattern of the catalyst is shown in figure 2, and as can be seen from figure 2, the catalyst is in a face-centered cubic fluorite crystal form, does not have other crystal forms, and has high purity.
Example 2
The embodiment provides a mesoporous cerium oxide photocatalyst, and a preparation method of the catalyst comprises the following steps:
(1) mixing 0.8g of KIT-6 mesoporous molecular sieve with 10mL of water;
(2) adding 3g of cerous nitrate hexahydrate into the mixed solution, and heating the liquid after standing for 2 hours at 80 ℃ for 12 hours to obtain dry solid powder;
(3) calcining dried solid powder at the high temperature of 830 ℃, mixing the calcined solid powder with 2.5mol/L alkaline solution at the stirring speed of 300r/min, reacting for 0.5h, centrifuging the liquid without the template at the speed of 8000r/min for 6min, washing the obtained precipitate with ethanol and deionized water for 3 times in sequence, drying at the temperature of 80 ℃ for 12h to obtain the solid powder with the specific surface area of 75cm2(ii) a mesoporous cerium oxide photocatalyst having an average pore diameter of 10 nm.
Example 3
This example differs from example 1 only in that the temperature of the high-temperature calcination in step (3) is 400 ℃ and the other conditions and parameters are exactly the same as those in example 1.
Example 4
This example differs from example 1 only in that the temperature of the high-temperature calcination in step (3) is 900 ℃, and other conditions and parameters are exactly the same as those in example 1.
Example 5
This example is different from example 1 only in that the temperature of the high-temperature calcination in step (3) is 300 ℃, and other conditions and parameters are exactly the same as those in example 1.
Example 6
This example is different from example 1 only in that the temperature of the high-temperature calcination in step (3) is 950 ℃, and other conditions and parameters are exactly the same as those of example 1.
Comparative example 1
This comparative example differs from example 1 only in that KIT-6 described in step (1) was replaced with SBA-15, and the other conditions and parameters were exactly the same as those of example 1.
Comparative example 2
The present comparative example is different from example 1 only in that KIT-6 described in step (1) is replaced by mesoporous silicon, and other conditions and parameters are exactly the same as those of example 1.
And (3) performance testing:
10mg of the photocatalyst described in examples 1 to 6 and comparative examples 1 to 2 was added to 30mL of deionized water and uniformly dispersed by sonication for 10 minutes. The photocatalyst dispersion was transferred to a 50mL reactor, which was sealed with a rubber stopper. Argon gas was passed into the reactor for 30 minutes and the reactor was purged of air. Then methane gas is introduced into the dispersion liquid for 10min by adopting a bubbling method, the speed is 100mL/min, and the methane is fully dissolved in the water and is closely contacted with the photocatalyst. Then, the reactor was placed under the xenon lamp light source at a distance of about 10cm from the lamp socket, and stirring and cooling water was started to irradiate light for 1 hour. And (3) sucking the gas in the reactor by using a gas-tight needle, injecting the gas into a gas chromatograph, and detecting the content of the gas product. And (4) extracting the reacted liquid, and detecting the content of the liquid product through a nuclear magnetic resonance hydrogen spectrum. The test results are shown in table 1:
TABLE 1
| Methanol yield/. mu.mol/g/h | |
| Example 1 | 27.8 |
| Example 2 | 27.5 |
| Example 3 | 24.3 |
| Example 4 | 26.1 |
| Example 5 | 22.7 |
| Example 6 | 22.9 |
| Comparative example 1 | 0 |
| Comparative example 2 | 0 |
As can be seen from Table 1, the yield of methanol prepared by activating methane using the catalyst prepared by the method of the present invention can reach more than 22.7 mu mol/g/h, as can be seen from examples 1-6.
By comparing the embodiment 1 with the embodiments 3-6, the calcination temperature in the step (2) can affect the catalytic activity of the prepared catalyst, and the calcination temperature is controlled to be 400-900 ℃, so that the catalyst with higher catalytic activity can be prepared. If the calcination temperature is lower than 400 ℃, the catalyst has poor crystallinity, low purity, and unstable and easily collapsed mesoporous structure. If the calcination temperature is higher than 900 ℃, the specific surface area of the catalyst is significantly reduced and the pore size is not uniform.
The comparison graph of the performance of the catalyst prepared in example 1 and the performance of the catalyst prepared in comparative example 1 for preparing methanol by photocatalytic methane activation is shown in fig. 3, and the comparison between example 1 and comparative example 1 can show that the mesoporous cerium oxide prepared by using a KIT-6 mesoporous molecular sieve as a carrier can have high photocatalytic activity under visible light, and can prepare methanol by activating methane under the illumination condition through a photocatalytic process, thereby being beneficial to practical application.
The applicant declares that the above description is only a specific embodiment of the present invention, but the scope of the present invention is not limited thereto, and it should be understood by those skilled in the art that any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are within the scope and disclosure of the present invention.
Claims (10)
1. A preparation method of a mesoporous cerium oxide photocatalyst is characterized by comprising the following steps:
(1) mixing a mesoporous molecular sieve with a solvent, adding a cerium source, and heating and drying to obtain a precursor;
(2) calcining the precursor obtained in the step (1), mixing the calcined precursor with alkali liquor, and drying to obtain the mesoporous cerium oxide photocatalyst;
wherein, the mesoporous molecular sieve is KIT-6.
2. The method of claim 1, wherein the ratio of the mass of the mesoporous molecular sieve to the volume of the solvent in step (1) is (0.1-1) g/10 mL;
preferably, the solvent comprises deionized water and/or ethanol;
preferably, the mesoporous molecular sieve is mixed with a solvent while stirring;
preferably, the stirring speed is 150-600 r/min, preferably 200-400 r/min.
3. The method according to claim 1 or 2, wherein the cerium source of step (1) comprises any one of cerous nitrate hexahydrate, cerous chloride heptahydrate, or cerous acetate hydrate, or a combination of at least two thereof;
preferably, the mass ratio of the cerium source to the mesoporous molecular sieve is 1 (0.1-1), preferably 1 (0.25-0.75).
4. The production method according to any one of claims 1 to 3, wherein the heating and drying in step (1) is preceded by standing;
preferably, the standing time is 0.5-12 h, preferably 1-3 h;
preferably, the temperature for heating and drying in the step (1) is 40-120 ℃, and preferably 50-80 ℃;
preferably, the time for heating and drying in the step (1) is 8-48 h, preferably 10-24 h.
5. The method according to any one of claims 1 to 4, wherein the calcination in step (2) is carried out at a temperature of 400 to 900 ℃, preferably 750 to 800 ℃;
preferably, the temperature rise rate of the calcination is 1-20 ℃/min, preferably 3-5 ℃/min;
preferably, the calcining time is 3-12 h, preferably 4-8 h.
6. The method according to any one of claims 1 to 4, wherein the lye of step (2) comprises either or a combination of NaOH solution or KOH solution;
preferably, the concentration of the alkali liquor is 1-5 mol/L, and preferably 2-3 mol/L.
7. The method according to any one of claims 1 to 6, wherein the drying in step (2) is preceded by centrifugation, filtration and washing;
preferably, the rotation speed during centrifugation is 6000 to 12000r/min, preferably 8000 to 10000 r/min;
preferably, the centrifugation time is 3-15 min, preferably 5-10 min;
preferably, the washing detergent comprises ethanol and/or deionized water;
preferably, the washing times are 2-5 times;
preferably, the drying temperature in the step (2) is 50-150 ℃, preferably 60-90 ℃;
preferably, the drying time in the step (2) is 8-48 h, preferably 10-24 h.
8. The method of any one of claims 1 to 7, comprising the steps of:
(1) mixing a mesoporous molecular sieve and a solvent according to the ratio of the mass of the mesoporous molecular sieve to the volume of the solvent being (0.1-1):10, adding a cerium source, and heating and drying to obtain a precursor;
(2) calcining the precursor obtained in the step (1) at 400-900 ℃ for 3-12 h, mixing with alkali liquor, and drying to obtain the mesoporous cerium oxide photocatalyst;
wherein, the mesoporous molecular sieve is KIT-6.
9. A mesoporous ceria photocatalyst, wherein the catalyst is prepared by the method of any one of claims 1 to 8;
the specific surface area of the catalyst is 75-100cm2The average pore diameter of the catalyst is 5-30 nm.
10. The application of the mesoporous cerium oxide photocatalyst as claimed in claim 9, wherein the mesoporous cerium oxide photocatalyst is used for preparing methanol by photocatalytic methane activation.
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