CN113813954B - Layered CeO 2-x Material, preparation method and application thereof - Google Patents
Layered CeO 2-x Material, preparation method and application thereof Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title abstract description 17
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- 239000007787 solid Substances 0.000 claims description 20
- 238000000034 method Methods 0.000 claims description 12
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- 238000006243 chemical reaction Methods 0.000 claims description 10
- 239000011259 mixed solution Substances 0.000 claims description 10
- 239000008367 deionised water Substances 0.000 claims description 9
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- 238000001291 vacuum drying Methods 0.000 claims description 9
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- 239000000843 powder Substances 0.000 claims description 6
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- 229910052760 oxygen Inorganic materials 0.000 abstract description 17
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- FHYLEJSGUQBKRQ-UHFFFAOYSA-N 6-methyl-7-oxabicyclo[4.1.0]hepta-2,4-diene Chemical compound C1=CC=CC2(C)C1O2 FHYLEJSGUQBKRQ-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
- B01J23/10—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of rare earths
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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
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Abstract
The invention discloses a layered CeO 2‑x A material and a preparation method and application thereof belong to the technical fields of material preparation and photocatalytic oxidation of VOCs. The invention uses Ce (NO) 3 ) 3 ·6H 2 O、NaCl、C 6 H 12 N 4 And (NH) 4 ) 2 S 2 O 8 Dissolving in water, heating under inert gas protection, condensing and refluxing to obtain suspension, washing, centrifuging, drying, grinding, roasting, and naturally cooling to obtain layered CeO 2‑x A material. Through experiments, the layered CeO provided by the invention 2‑x The material has high oxygen vacancy concentration on the surface, good light absorption capacity and high-efficiency photogenerated carrier separation efficiency, can generate more active oxygen free radicals to attack pollutant molecules, and can remove VOCs more thoroughly. The preparation method has the advantages of simple preparation process, simple equipment, low-cost and easily-obtained raw materials, mass production and potential application prospect 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, and in particular relates to layered CeO 2-x Materials, and methods of making and using the same.
Background
Volatile Organic Compounds (VOCs) released by indoor furniture, decoration building materials, kitchen fume and the like have the characteristics of low concentration, long release time and the like, and can enter human bodies through modes of skin contact, respiratory tract ingestion, digestive tract ingestion and the like to directly influence the health of the human bodies. Therefore, it is very important and urgent to develop an environmental remediation technology that efficiently eliminates indoor VOCs. In recent years, photocatalytic oxidation is considered as a control technology with wide practical application prospect due to mild conditions, high efficiency and few byproducts.
Layered Double Hydroxide (LDH) is an important two-dimensional layered nano-size material, the main layer plate, interlayer anion composition and crystal structure of the LDH can be flexibly regulated and controlled, the structure (crystal face, defect and the like) of an active center can be regulated on an atomic scale, and metals on the layer plate are uniformly distributed in an atomic scale manner, so that active sites are highly dispersed, and the structural characteristics enable the LDH to be a novel catalytic material system with potential application prospect. The LDH nanosheets can be baked at high temperature to obtain Layered Metal Oxide (LMO) nanosheets with relatively stable physicochemical properties. In the LDH roasting process, the obtained LMO nanosheets have certain defects of nanopores and structures due to the removal of water molecules and the decomposition of interlayer anions. The nanopores and surface defects not only can be used as proper adsorption sites for reactant molecules, but also can adjust band gap energy, and reduce the activation barrier of reaction, so that the conversion efficiency of pollutant molecules is improved. At present, ultrathin LMO materials have been widely developed for photocatalytic oxidative degradation of VOCs due to the 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 transition, medium band gap (eg=2.92 eV), light radiation resistance and excellent oxygen storage capacity, and is favorable for VOCs and O 2 And adsorption and activation of water molecules, is an ideal photocatalyst for eliminating VOCs.
Disclosure of Invention
The technical problem to be solved by the invention is to provide a layered CeO which is efficient, environment-friendly and has good activity and stability 2-x A photocatalyst. Another technical problem to be solved by the present invention is to provide the layered CeO 2-x A specific preparation method of the photocatalyst. The final technical problem to be solved by the invention is to provide the layered CeO 2-x The photocatalyst is particularly applied.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows:
layered CeO 2-x The preparation method of the material comprises the following steps: ce (NO) 3 ) 3 ·6H 2 O、NaCl、C 6 H 12 N 4 And (NH) 4 ) 2 S 2 O 8 Dissolving in water, heating under inert gas protection, condensing and refluxing to obtain suspension, washing, centrifuging, drying, grinding, roasting and cooling to obtain layered CeO 2-x A material.
Further, the layered CeO 2-x The preparation method of the material specifically comprises the following steps:
(1) Solid Ce (NO) 3 ) 3 ·6H 2 O、NaCl、C 6 H 12 N 4 And (NH) 4 ) 2 S 2 O 8 Dissolving 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 absolute ethanol and deionized water respectively, and centrifuging for several times to no Cl - 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 after finishing to obtain layered CeO 2-x A photocatalyst.
The layered CeO 2-x Preparation method of material, (NH) 4 ) 2 S 2 O 8 And Ce (NO) 3 ) 3 The molar ratio of (2) is 3:5.
The layered CeO 2-x The preparation method of the material comprises the following steps of (2), wherein the heating temperature of an oil bath is 110 ℃; the condensation reflux time was 20h.
The layered CeO 2-x And (3) the preparation method of the material, wherein the centrifuged sample is dried in vacuum at 60 ℃ for 24 hours.
The layered CeO 2-x A method for preparing a material, said step (4) Roasting for 6 hours at 750-950 ℃ respectively at a heating rate of 5 ℃/min.
Lamellar CeO prepared by the method 2-x A material.
The above layered CeO 2-x The application of the material in photocatalytic oxidation of VOCs.
Compared with the prior art, the invention has the beneficial effects that:
(1) The invention provides layered CeO 2-x The preparation process of the material is simple and convenient to operate, can realize large-scale production, has low energy consumption, little pollution and environmental friendliness, and has the advantages of cheap and easily available raw materials, abundant resources and potential application prospect in solving the environmental problem of indoor VOCs;
(2) The invention provides layered CeO 2-x The material has good light absorption capacity and high-efficiency photon-generated carrier separation efficiency;
(3) The invention provides layered CeO 2-x The oxygen vacancy concentration on the surface of the material is high, so that gaseous oxygen can be effectively captured, and the promotion of O 2 - Is generated. The material has good hydrophilicity on the surface, is favorable for adsorbing more oxygen-containing species and generates more OH. These reactive oxygen radicals attack the contaminant molecules, inhibiting the accumulation of byproducts, and thereby more thoroughly removing the contaminant molecules.
Drawings
FIG. 1A is CeO 2-0 -L750，CeO 2-x -L850 and CeO 2-x XRD pattern of L950 catalyst, FIG. 1B is CeO 2-x -SEM image of L850 catalyst;
FIG. 2 is CeO 2-x -L750，CeO 2-x -L850 and CeO 2-x Ce 3d XPS (fig. 2A) and ESR (fig. 2B) spectra of the L950 samples;
FIG. 3 is CeO 2-x -L750，CeO 2-x -L850 and CeO 2-x -water contact angle plot of L950 sample;
FIG. 4 is CeO 2-x -L750，CeO 2-x -L850 and CeO 2-x UV-Vis DRS (fig. 4A) and EIS (fig. 4B) spectra of L950 samples;
FIG. 5 CeO under light irradiation 2-x -L750，CeO 2-x -L850 and CeO 2-x E of the L950 sampleAn SR spectrogram;
FIG. 6 is a graph of the catalytic performance of the prepared samples for the oxidation of toluene under full spectrum irradiation.
Detailed Description
In order that the above-recited objects, features and advantages of the present invention will become more apparent, a more particular description of the invention will be rendered by reference to specific embodiments thereof.
Example 1:
lamellar CeO by alkalization distillation method 2-x -a process for the preparation of L750 material comprising the steps of:
(1) 0.4342g Ce (NO) 3 ) 3 ·6H 2 O、0.7597g NaCl、0.7010g C 6 H 12 N 4 And 0.1369g (NH) 4 ) 2 S 2 O 8 Placing the solid into a flat-bottom flask containing 200mL of deionized water, and magnetically stirring uniformly to obtain a clear mixed solution;
(2) Under the protection of high-purity argon, heating the clarified mixed solution to 110 ℃ in an oil bath, condensing and refluxing for 20 hours, and naturally cooling to room temperature after finishing to obtain a suspension;
(3) Centrifugally washing the suspension with absolute ethanol and deionized water for several times to obtain a suspension free of Cl - Vacuum drying in vacuum drying oven at 60deg.C for 24 hr to obtain white solid (layered cerium hydroxide);
(4) Grinding white solid into powder, dispersing in a porcelain boat, placing in a muffle furnace, roasting at 750deg.C for 6 hr at a heating rate of 5deg.C/min under air atmosphere, and naturally cooling to room temperature to obtain pale yellow solid (layered CeO) 2-x -L750 photocatalyst.
Example 2:
lamellar CeO by alkalization distillation method 2-x -a process for the preparation of L850 material comprising the steps of:
(1) 0.4342g Ce (NO) 3 ) 3 ·6H 2 O、0.7597g NaCl、0.7010g C 6 H 12 N 4 And 0.1369g (NH) 4 ) 2 S 2 O 8 Placing the solid into a flat bottom burn containing 200mL of deionized waterIn a bottle, magnetically stirring uniformly to obtain a clear mixed solution;
(2) Under the protection of high-purity argon, heating the clarified mixed solution to 110 ℃ in an oil bath, condensing and refluxing for 20 hours, and naturally cooling to room temperature after finishing to obtain a suspension;
(3) Centrifugally washing the suspension with absolute ethanol and deionized water for several times to obtain a suspension free of Cl - Vacuum drying in vacuum drying oven at 60deg.C for 24 hr to obtain white solid (layered cerium hydroxide);
(4) Grinding white solid into powder, dispersing in a porcelain boat, placing in a muffle furnace, roasting at 850 deg.C for 6 hr at a heating rate of 5 deg.C/min under air atmosphere, and naturally cooling to room temperature to obtain pale yellow solid (layered CeO) 2-x -L850 photocatalyst.
Example 3:
lamellar CeO by alkalization distillation method 2-x -a process for the preparation of L950 material comprising the steps of:
(1) 0.4342g Ce (NO) 3 ) 3 ·6H 2 O、0.7597g NaCl、0.7010g C 6 H 12 N 4 And 0.1369g (NH) 4 ) 2 S 2 O 8 Placing the solid into a flat-bottom flask containing 200mL of deionized water, and magnetically stirring uniformly to obtain a clear mixed solution;
(2) Under the protection of high-purity argon, heating the clarified mixed solution to 110 ℃ in an oil bath, condensing and refluxing for 20 hours, and naturally cooling to room temperature after finishing to obtain a suspension;
(3) Centrifugally washing the suspension with absolute ethanol and deionized water for several times to obtain a suspension free of Cl - Vacuum drying in vacuum drying oven at 60deg.C for 24 hr to obtain white solid (layered cerium hydroxide);
(4) Grinding white solid into powder, dispersing in a porcelain boat, placing in a muffle furnace, roasting at 950 ℃ for 6h at a heating rate of 5 ℃/min under air atmosphere, and naturally cooling to room temperature to obtain light yellow solid, namely lamellar CeO 2-x -L950 photocatalyst.
Example 4:
by usingOrdinary CeO of roasting method 2-x -850 material, comprising the steps of:
0.4342g Ce (NO) 3 ) 3 ·6H 2 Grinding O into powder, dispersing in a porcelain boat, placing in a muffle furnace, roasting at 850 ℃ for 6h at a heating rate of 5 ℃/min under air atmosphere, and naturally cooling to room temperature after finishing to obtain light yellow solid, namely common CeO 2-x -850 photocatalyst.
FIG. 1A is CeO 2-x -L750，CeO 2-x -L850 and CeO 2-x XRD pattern of L950 catalyst, FIG. 1B is CeO 2-x SEM image of L850 catalyst. As can be seen from FIG. 1A, all diffraction peaks of the three samples were compared with cubic fluorite CeO 2 (JCPLDS card number 34-0394) and, in addition, as can be clearly seen from FIG. 1B, ceO 2-x L850 presents a lamellar structure consisting of lamellar nanoplates, which suggests that we have successfully synthesized lamellar CeO 2-x A material.
FIG. 2 is CeO 2-x -L750，CeO 2-x -L850 and CeO 2-x Ce 3d XPS (fig. 2A) and ESR (fig. 2B) results for L950 samples. As can be seen from FIG. 2A, ceO 2-x Ce of-L850 3+ The higher surrounding electron cloud density indicates more oxygen defects. Meanwhile, the presence of oxygen vacancies was confirmed by the symmetrical EPR signal peak occurring at g=1.998, in which CeO 2-x The signal intensity of L850 is obviously higher than CeO 2-x -L750 and CeO 2-x -L950, indicating CeO 2-x L850 has the highest oxygen vacancy concentration, and oxygen vacancies not only can be used as electron donors to effectively capture gaseous oxygen and enhance the migration capability of lattice oxygen, but also can accelerate the separation and migration of photogenerated carriers and promote O 2 Is one of the main reasons for the best photocatalytic performance.
FIG. 3 is CeO 2-x -L750，CeO 2-x -L850 and CeO 2-x As can be seen from the water contact angle results of the L950 sample, ceO 2-x The L850 has smaller water contact angle, which shows that the catalyst has better hydrophilicity and is beneficial to adsorbing more oxygen-containing species, thereby promoting the generation of active oxygen free radicals and improving the photocatalytic oxidation performance.
FIG. 4 is CeO 2-x -L750，CeO 2-x -L850 and CeO 2-x UV-Vis DRS (FIG. 4A) and EIS (FIG. 4B) results for L950 samples. As can be seen from FIG. 4, ceO 2-x L850 has a stronger light absorption capacity and high carrier separation and transfer efficiency, indicating CeO 2-x L850 may better utilize solar energy and generate more efficient photo-generated electrons and holes, thus exhibiting the highest photocatalytic performance.
FIG. 5 CeO under light irradiation 2-x -L750，CeO 2-x -L850 and CeO 2-x ESR spectrum of L950 sample, wherein for DMPO-O 2 - The sample was dispersed in aqueous methanol (FIG. 5A), and for DMPO-OH, the sample was dispersed in aqueous solution (FIG. 5B). As can be seen from FIG. 5, ceO was irradiated with light 2-x DMPO-O of the L850 catalyst 2 - And DMPO-OH signal intensity is higher than CeO 2-x -L750 and CeO 2-x -L950, indicating CeO 2-x The L850 sample has more active oxygen free radicals to participate in the photocatalytic oxidation toluene reaction, so that the sample has excellent photocatalytic performance.
Example 5:
the photocatalysts prepared in examples 1-4 were applied to toluene oxide, and the experimental steps were:
the photocatalytic oxidation toluene reaction test was performed in a continuous flow reactor. 50mg of lamellar CeO was weighed 2-x Samples were uniformly dispersed on a 400 mesh screen and placed in a 650mL stainless steel reactor covered with a stainless steel lid having a quartz open window with a diameter of 4.5 cm. Continuously introducing a mixed gas of toluene/air with the humidity of 20% RH and about 23ppm into a reactor, firstly carrying out dark treatment to reach a toluene adsorption and desorption equilibrium state, then opening a 280W xenon lamp to carry out photocatalysis reaction, and detecting and analyzing a product by gas chromatography GC-7920, wherein the toluene conversion rate and the toluene mineralization rate are calculated by the following formula:
FIG. 6 is a graph of the catalytic performance of the prepared samples for the oxidation of toluene under full spectrum irradiation. As can be seen from FIG. 6, after 3 hours of illumination, ceO 2-x The toluene conversion rate and the toluene mineralization rate of the L850 sample are obviously higher than those of other materials, and the life test is carried out by continuous illumination, so that CeO is found 2-x The reduction in toluene conversion and toluene mineralization of the L850 sample was small, while other materials were gradually deactivated after prolonged use. Thus, ceO 2-x The L850 material has the best photo-oxidative toluene activity and stability.
Claims (1)
1. Lamellar CeO x2- The application of the material in photocatalytic oxidation of VOCs;
the layered CeO x2- The material is lamellar CeO 2-x -L850 material, prepared by the steps of:
(1) 0.4342g Ce (NO) 3 ) 3 ·6H 2 O、0.7597g NaCl、0.7010g C 6 H 12 N 4 And 0.1369g (NH) 4 ) 2 S 2 O 8 Placing the solid into a flat-bottom flask containing 200mL of deionized water, and magnetically stirring uniformly to obtain a clear mixed solution;
(2) Under the protection of high-purity argon, heating the clarified mixed solution to 110 ℃ in an oil bath, condensing and refluxing for 20 hours, and naturally cooling to room temperature after finishing to obtain a suspension;
(3) Centrifugally washing the suspension with absolute ethanol and deionized water for several times to obtain a suspension free of Cl - Vacuum drying in vacuum drying oven at 60deg.C for 24 hr to obtain white solid (layered cerium hydroxide);
(4) Grinding white solid into powder, dispersing in a porcelain boat, placing in a muffle furnace, roasting at 850 deg.C for 6 hr at a heating rate of 5 deg.C/min under air atmosphere, and naturally cooling to room temperature to obtain pale yellow solid (layered CeO) 2-x -L850 photocatalyst;
the application process comprises the following steps: photocatalytic oxidation toluene reaction test in continuous flow reactionsIn a reactor; 50mg of lamellar CeO was weighed 2-x -L850 photocatalyst samples, uniformly dispersed 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; and continuously introducing a mixed gas of 23ppm of toluene/air with the humidity of 20% RH into the reactor, performing dark treatment to reach a toluene adsorption and desorption equilibrium state, and then turning on a 280W xenon lamp to perform photocatalysis reaction.
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