CN113813954A - Layered CeO2-xMaterial, preparation method and application thereof - Google Patents
Layered CeO2-xMaterial, preparation method and application thereof Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 239000000463 material Substances 0.000 claims abstract description 41
- 229910020200 CeO2−x Inorganic materials 0.000 claims abstract description 37
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 20
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims abstract description 16
- 239000000725 suspension Substances 0.000 claims abstract description 16
- 239000012855 volatile organic compound Substances 0.000 claims abstract description 14
- 238000001816 cooling Methods 0.000 claims abstract description 13
- 230000001699 photocatalysis Effects 0.000 claims abstract description 13
- 238000010992 reflux Methods 0.000 claims abstract description 13
- 238000010438 heat treatment Methods 0.000 claims abstract description 11
- 230000003647 oxidation Effects 0.000 claims abstract description 11
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 11
- 238000000227 grinding Methods 0.000 claims abstract description 8
- 239000011780 sodium chloride Substances 0.000 claims abstract description 8
- 238000001035 drying Methods 0.000 claims abstract description 6
- 238000005406 washing Methods 0.000 claims abstract description 5
- 239000011261 inert gas Substances 0.000 claims abstract description 3
- 239000007787 solid Substances 0.000 claims description 17
- 239000011941 photocatalyst Substances 0.000 claims description 11
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 10
- 239000008367 deionised water Substances 0.000 claims description 10
- 229910021641 deionized water Inorganic materials 0.000 claims description 10
- 239000011259 mixed solution Substances 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 8
- 229910052573 porcelain Inorganic materials 0.000 claims description 6
- 239000000843 powder Substances 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 5
- 229910052786 argon Inorganic materials 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- 238000001291 vacuum drying Methods 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 abstract description 18
- 229910052760 oxygen Inorganic materials 0.000 abstract description 18
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 17
- 238000000926 separation method Methods 0.000 abstract description 4
- 230000031700 light absorption Effects 0.000 abstract description 3
- 238000012360 testing method Methods 0.000 abstract description 3
- 239000003344 environmental pollutant Substances 0.000 abstract description 2
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 2
- 231100000719 pollutant Toxicity 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 42
- 238000006243 chemical reaction Methods 0.000 description 7
- 238000001354 calcination Methods 0.000 description 5
- 239000003054 catalyst Substances 0.000 description 5
- 230000007547 defect Effects 0.000 description 5
- 239000000203 mixture Substances 0.000 description 4
- 239000002135 nanosheet Substances 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- 229910052684 Cerium Inorganic materials 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 230000033558 biomineral tissue development Effects 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 3
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 3
- 238000009833 condensation Methods 0.000 description 3
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- 239000013078 crystal Chemical group 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 3
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- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 2
- 239000000356 contaminant Substances 0.000 description 2
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- 238000001362 electron spin resonance spectrum Methods 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
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- 238000003860 storage Methods 0.000 description 2
- VCUVETGKTILCLC-UHFFFAOYSA-N 5,5-dimethyl-1-pyrroline N-oxide Chemical compound CC1(C)CCC=[N+]1[O-] VCUVETGKTILCLC-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 description 1
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
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- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
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- C01F17/00—Compounds of rare earth metals
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Abstract
The invention discloses a layered CeO2‑xA material and a preparation method and application thereof belong to the technical field of material preparation and photocatalytic oxidation of VOCs. The invention adds Ce (NO)3)3·6H2O、NaCl、C6H12N4And (NH)4)2S2O8Dissolving in water, heating under the protection of inert gas, condensing and refluxing to obtain suspension, washing, centrifuging, drying, grinding, roasting, and naturally cooling to obtain layered CeO2‑xA material. Through tests, the layered CeO provided by the invention2‑xThe material has high surface oxygen vacancy concentration, good light absorption capacity and high efficiency of light generationThe carrier separation efficiency can generate more active oxygen free radicals to attack pollutant molecules, and VOCs can be removed more thoroughly. The preparation method is simple and convenient in preparation process, simple in equipment, cheap and easily available in used raw materials, capable of realizing large-scale production and having potential application prospects in the aspect of photocatalytic oxidation of VOCs.
Description
Technical Field
The invention belongs to the technical field of material preparation and photocatalytic oxidation of VOCs (volatile organic compounds), and particularly relates to layered CeO2-xA material and a preparation method and application thereof.
Background
Volatile Organic Compounds (VOCs) released by indoor furniture, decoration and building materials, kitchen oil smoke and the like have the characteristics of low concentration, long release time and the like, and can enter human bodies through skin contact, respiratory tract intake, digestive tract intake and other modes to directly influence the health of the human bodies. Therefore, it is very important and urgent to develop environmental remediation techniques that efficiently eliminate VOCs in the room. In recent years, photocatalytic oxidation is considered as a control technology with a wide practical application prospect due to mild conditions, high efficiency and few byproducts.
Layered Double Hydroxides (LDH) are important two-dimensional layered nano-sized materials, the composition of a main layer plate, interlayer anions and a crystal structure of the Layered Double Hydroxides (LDH) can be flexibly regulated, the structure (crystal faces, defects and the like) of an active center can be regulated on an atomic scale, metals on the layer plate are uniformly distributed in an atomic-level mode, active sites are highly dispersed, and the LDH becomes a novel catalytic material system with a potential application prospect due to the structural characteristics. The LDH nano-sheet can be baked at high temperature to obtain a Layered Metal Oxide (LMO) nano-sheet with relatively stable physical and chemical properties. In the LDH roasting process, due to the removal of water molecules and the decomposition of interlayer anions, the obtained LMO nanosheet has certain defects of nanopores and structures. The nano-pores and the surface defects can be used as suitable adsorption sites of reactant molecules, and can also adjust band gap energy and reduce activation potential barrier of reaction, thereby improving the conversion efficiency of pollutant molecules. At present, ultrathin LMO materials have been widely developed for photocatalytic oxidative degradation of VOCs due to their ability to expose more active sites. As is well known, ceria (CeO)2) Is an n-type semiconductor which is rich in surface oxygen defects, 4f electron transitions, medium band gap (Eg. 2.92eV), resistant to light radiation and excellentThe oxygen storage capacity of the oxygen storage tank is favorable for VOCs and O2And the adsorption and activation of water molecules, is an ideal photocatalyst for eliminating VOCs.
Disclosure of Invention
Aiming at the problems in the prior art, the invention aims to provide a layered CeO with high efficiency, environmental friendliness, good activity and stability2-xA photocatalyst. Another technical problem to be solved by the present invention is to provide the above-mentioned layered CeO2-xA specific preparation method of the photocatalyst. The invention finally aims to provide the layered CeO2-xSpecific applications of the photocatalyst are disclosed.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows:
layered CeO2-xThe preparation method of the material comprises the following steps: adding Ce (NO)3)3·6H2O、NaCl、C6H12N4And (NH)4)2S2O8Dissolving in water, heating under the protection of inert gas, condensing and refluxing to obtain suspension, washing, centrifuging, drying, grinding, roasting and cooling to obtain layered CeO2-xA material.
Further, the layered CeO2-xThe preparation method of the material specifically comprises the following steps:
(1) solid Ce (NO)3)3·6H2O、NaCl、C6H12N4And (NH)4)2S2O8Dissolving in deionized water, and stirring to obtain mixed solution.
(2) Under the protection of argon, heating the mixed solution in an oil bath, condensing and refluxing, and naturally cooling to room temperature to obtain a suspension;
(3) centrifuging the suspension, washing with anhydrous ethanol and deionized water respectively, and centrifuging for several times until no Cl is formed-Drying in a vacuum drying oven to obtain solid;
(4) grinding the solid into powder, dispersing in porcelain boat, placing in muffle furnace, calcining in air atmosphere, and sinteringCooling to room temperature to obtain layered CeO2-xA photocatalyst.
The layered CeO2-xMethod for producing a material, (NH)4)2S2O8And Ce (NO)3)3The molar ratio of (A) to (B) is 3: 5.
The layered CeO2-xThe preparation method of the material comprises the step (2), wherein the oil bath heating temperature is 110 ℃; the condensing reflux time was 20 h.
The layered CeO2-xThe preparation method of the material, the step (3), the centrifuged sample is dried in vacuum at 60 ℃ for 24 h.
The layered CeO2-xAnd (4) roasting the materials at the temperature rise rate of 5 ℃/min for 6h at the temperature of 750-950 ℃ respectively.
The layered CeO prepared by the method2-xA material.
The above-mentioned layered CeO2-xThe material is applied to photocatalytic oxidation of VOCs.
Compared with the prior art, the invention has the beneficial effects that:
(1) the invention provides a layered CeO2-xThe preparation process of the material is simple and convenient to operate, can be used for large-scale production, is low in energy consumption, small in pollution, environment-friendly, cheap and easily available in used raw materials, rich in resources and has a potential application prospect in the aspect of solving the environmental problem of indoor VOCs;
(2) the invention provides a layered CeO2-xThe material has good light absorption capacity and high photo-generated carrier separation efficiency;
(3) the invention provides a layered CeO2-xThe oxygen vacancy concentration on the surface of the material is high, and the material can effectively capture gaseous oxygen and promote O2 -Is generated. The material has good hydrophilicity on the surface, is beneficial to adsorbing more oxygen-containing species and generating more OH. These reactive oxygen radicals attack the contaminant molecules, inhibiting the accumulation of byproducts, and thereby more completely removing the contaminant molecules.
Drawings
FIG. 1A is CeO2-0-L750，CeO2-x-L850 and CeO2-xXRD pattern of-L950 catalyst, FIG. 1B is CeO2-x-SEM picture of L850 catalyst;
FIG. 2 is CeO2-x-L750，CeO2-x-L850 and CeO2-x-Ce 3d XPS (fig. 2A) and ESR (fig. 2B) spectra of the L950 sample;
FIG. 3 is CeO2-x-L750，CeO2-x-L850 and CeO2-x-water contact angle plot of L950 sample;
FIG. 4 is CeO2-x-L750，CeO2-x-L850 and CeO2-x-UV-Vis DRS (fig. 4A) and EIS (fig. 4B) spectra of L950 samples;
FIG. 5 shows CeO under light irradiation2-x-L750，CeO2-x-L850 and CeO2-x-ESR spectrum of the L950 sample;
FIG. 6 is a graph of the catalytic performance of the prepared samples for toluene oxidation under full spectrum illumination.
Detailed Description
In order to make the aforementioned objects, features and advantages of the present invention comprehensible, embodiments accompanied with examples are described in detail below.
Example 1:
laminar CeO by alkalization distillation2-x-a method for preparing an L750 material, comprising the steps of:
(1) 0.4342g of Ce (NO) were accurately weighed3)3·6H2O、0.7597g NaCl、0.7010g C6H12N4And 0.1369g (NH)4)2S2O8Putting the solid into a flat-bottomed flask containing 200mL of deionized water, and uniformly stirring by magnetic force to obtain a clear mixed solution;
(2) under the protection of high-purity argon, heating the clear mixed solution in an oil bath to 110 ℃, condensing and refluxing for 20 hours, and naturally cooling to room temperature after the condensation and refluxing are finished to obtain a suspension;
(3) the suspension is centrifugally washed for several times with absolute ethyl alcohol and deionized water respectively until the suspension is free of Cl-Putting the mixture into a vacuum drying oven to be dried for 24 hours in vacuum at the temperature of 60 ℃ to obtain white solid, namely hydroxide of the layered cerium;
(4) mixing white solidGrinding into powder, dispersing in porcelain boat, placing in muffle furnace, calcining at 750 deg.C for 6h at a temperature rise rate of 5 deg.C/min in air atmosphere, and naturally cooling to room temperature to obtain yellowish solid (layered CeO)2-x-L750 photocatalyst.
Example 2:
laminar CeO by alkalization distillation2-x-a method for preparing an L850 material, comprising the steps of:
(1) 0.4342g of Ce (NO) were accurately weighed3)3·6H2O、0.7597g NaCl、0.7010g C6H12N4And 0.1369g (NH)4)2S2O8Putting the solid into a flat-bottomed flask containing 200mL of deionized water, and uniformly stirring by magnetic force to obtain a clear mixed solution;
(2) under the protection of high-purity argon, heating the clear mixed solution in an oil bath to 110 ℃, condensing and refluxing for 20 hours, and naturally cooling to room temperature after the condensation and refluxing are finished to obtain a suspension;
(3) the suspension is centrifugally washed for several times with absolute ethyl alcohol and deionized water respectively until the suspension is free of Cl-Putting the mixture into a vacuum drying oven to be dried for 24 hours in vacuum at the temperature of 60 ℃ to obtain white solid, namely hydroxide of the layered cerium;
(4) grinding white solid into powder, dispersing in a porcelain boat, placing in a muffle furnace, calcining at 850 deg.C for 6h at a temperature rise rate of 5 deg.C/min in air atmosphere, and naturally cooling to room temperature to obtain yellowish solid (layered CeO)2-x-an L850 photocatalyst.
Example 3:
laminar CeO by alkalization distillation2-x-a method for preparing an L950 material, comprising the steps of:
(1) 0.4342g of Ce (NO) were accurately weighed3)3·6H2O、0.7597g NaCl、0.7010g C6H12N4And 0.1369g (NH)4)2S2O8Putting the solid into a flat-bottomed flask containing 200mL of deionized water, and uniformly stirring by magnetic force to obtain a clear mixed solution;
(2) under the protection of high-purity argon, heating the clear mixed solution in an oil bath to 110 ℃, condensing and refluxing for 20 hours, and naturally cooling to room temperature after the condensation and refluxing are finished to obtain a suspension;
(3) the suspension is centrifugally washed for several times with absolute ethyl alcohol and deionized water respectively until the suspension is free of Cl-Putting the mixture into a vacuum drying oven to be dried for 24 hours in vacuum at the temperature of 60 ℃ to obtain white solid, namely hydroxide of the layered cerium;
(4) grinding white solid into powder, dispersing in a porcelain boat, placing in a muffle furnace, calcining at 950 deg.C for 6h at a temperature rise rate of 5 deg.C/min in air atmosphere, and naturally cooling to room temperature to obtain yellowish solid (layered CeO)2-x-L950 photocatalyst.
Example 4:
ordinary CeO by roasting2-x-850 a method of preparing a material comprising the steps of:
0.4342g of Ce (NO) were accurately weighed3)3·6H2Grinding O into powder, dispersing in a porcelain boat, placing in a muffle furnace, calcining at 850 deg.C for 6h at a temperature rise rate of 5 deg.C/min in air atmosphere, and naturally cooling to room temperature to obtain light yellow solid (ordinary CeO)2-x-850 photocatalyst.
FIG. 1A is CeO2-x-L750，CeO2-x-L850 and CeO2-xXRD pattern of-L950 catalyst, FIG. 1B is CeO2-xSEM image of L850 catalyst. As can be seen from FIG. 1A, all diffraction peaks of the three samples were correlated with the cubic fluorite CeO2(JCPDS card number 34-0394) and, in addition, as is clear from FIG. 1B, CeO2-xL850 presents a layered structure consisting of thin-layer nanosheets, indicating that we succeeded in synthesizing layered CeO2-xA material.
FIG. 2 is CeO2-x-L750，CeO2-x-L850 and CeO2-xCe 3d XPS (FIG. 2A) and ESR (FIG. 2B) results for the L950 sample. As can be seen from FIG. 2A, CeO2-xCe of-L8503+The higher density of the surrounding electron cloud indicates more oxygen defects. Meanwhile, the presence of oxygen vacancies was confirmed by the symmetrical EPR signal peak appearing at g ═ 1.998, where CeO2-xThe signal intensity of-L850 is significantly stronger than that of CeO2-x-L750 and CeO2-x-L950, indicating CeO2-xThe L850 has the highest oxygen vacancy concentration, and oxygen vacancies not only can be used as an electron donor to effectively capture gaseous oxygen and enhance the migration capability of crystal lattice oxygen, but also can accelerate the separation and migration of photon-generated carriers and promote O2Is one of the main reasons for its best photocatalytic performance.
FIG. 3 is CeO2-x-L750，CeO2-x-L850 and CeO2-xWater contact Angle results for the-L950 sample, from which it can be seen that CeO2-xThe water contact angle of the-L850 is smaller, which shows that the water contact angle is better in hydrophilicity, and the water contact angle is favorable for adsorbing more oxygen-containing species, so that the generation of active oxygen free radicals is promoted, and the photocatalytic oxidation performance is improved.
FIG. 4 is CeO2-x-L750，CeO2-x-L850 and CeO2-xUV-Vis DRS (FIG. 4A) and EIS (FIG. 4B) results for the L950 sample. As can be seen from FIG. 4, CeO2-xThe L850 has a greater light absorption capacity and a high efficiency of carrier separation and transfer, which indicates that CeO2-xL850 can better utilize solar energy and generate more efficient photogenerated electrons and holes, thus exhibiting the highest photocatalytic performance.
FIG. 5 shows CeO under light irradiation2-x-L750，CeO2-x-L850 and CeO2-xESR spectra of the L950 sample, with DMPO. O2 -The sample was dispersed in aqueous methanol (FIG. 5A) and in aqueous DMPO-. OH (FIG. 5B). As can be seen from FIG. 5, CeO was irradiated with light2-xDMPO-O-of the L850 catalyst2 -And DMPO-OH signal intensity is higher than that of CeO2-x-L750 and CeO2-x-L950, indicating CeO2-xthe-L850 sample has more active oxygen free radicals participating in the photocatalytic oxidation toluene reaction, thereby showing excellent photocatalytic performance.
Example 5:
the photocatalysts prepared in examples 1-4 were applied to oxidized toluene with the experimental procedure:
the photocatalytic oxidation toluene reaction test was conducted in a continuous flow reactor. 50mg of layered CeO was weighed2-xSample, uniform divisionScattered on a 400 mesh screen, placed in a 650mL stainless steel reactor, covered with a stainless steel lid with a quartz open window of 4.5cm diameter. Continuously introducing a toluene/air mixed gas with the humidity of 20% RH and the concentration of about 23ppm into a reactor, performing dark treatment to reach a toluene adsorption and desorption equilibrium state, turning on a 280W xenon lamp to perform a photocatalytic reaction, detecting and analyzing a product by a gas chromatography GC-7920, and calculating the toluene conversion rate and the toluene mineralization rate by the following formulas:
FIG. 6 is a graph of the catalytic performance of the prepared samples for toluene oxidation under full spectrum illumination. As can be seen from FIG. 6, after 3 hours of light irradiation, CeO was added2-xThe toluene conversion rate and the toluene mineralization rate of the-L850 sample are both obviously higher than those of other materials, and the service life test is carried out by continuing illumination, so that CeO is found2-xThe toluene conversion and toluene mineralization of the-L850 sample decreased less, while other materials were gradually deactivated after prolonged use. Thus, CeO2-xThe L850 material has the best photooxidation toluene activity and stability.
Claims (8)
1. Layered CeO2-xA method for producing a material, characterized in that Ce (NO) is added3)3·6H2O、NaCl、C6H12N4And (NH)4)2S2O8Dissolving in water, heating under the protection of inert gas, condensing and refluxing to obtain suspension, washing, centrifuging, drying, grinding, roasting and cooling to obtain layered CeO2-xA material.
2. Layered CeO according to claim 12-xThe preparation method of the material is characterized by comprising the following steps:
(1) will be provided withSolid Ce (NO)3)3·6H2O、NaCl、C6H12N4And (NH)4)2S2O8Dissolving in deionized water, and stirring to obtain mixed solution.
(2) Under the protection of argon, heating the mixed solution in an oil bath, condensing and refluxing, and naturally cooling to room temperature to obtain a suspension;
(3) centrifuging the suspension, washing with anhydrous ethanol and deionized water respectively, and centrifuging for several times until no Cl is formed-Drying in a vacuum drying oven to obtain solid;
(4) grinding the solid into powder, dispersing in a porcelain boat, placing in a muffle furnace, roasting in air atmosphere, cooling to room temperature to obtain layered CeO2-xA photocatalyst.
3. The layered CeO of claim 22-xA method for producing a material, characterized in that (NH)4)2S2O8And Ce (NO)3)3The molar ratio of (A) to (B) is 3: 5.
4. The layered CeO of claim 22-xThe preparation method of the material is characterized in that in the step (2), the oil bath heating temperature is 110 ℃; the condensing reflux time was 20 h.
5. The layered CeO of claim 22-xThe preparation method of the material is characterized in that in the step (3), the drying is carried out for 24 hours under vacuum at the temperature of 60 ℃.
6. The layered CeO of claim 22-xThe preparation method of the material is characterized in that in the step (4), the material is roasted for 6 hours at 750-950 ℃ at the heating rate of 5 ℃/min.
7. Layered CeO prepared by the method of any one of claims 1 to 62-xA material.
8.The layered CeO according to claim 72-xThe material is applied to photocatalytic oxidation of VOCs.
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