CN111804303A - Preparation method of cerium dioxide/cobalt aluminum hydrotalcite material with core-shell structure - Google Patents
Preparation method of cerium dioxide/cobalt aluminum hydrotalcite material with core-shell structure Download PDFInfo
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- CN111804303A CN111804303A CN202010614630.3A CN202010614630A CN111804303A CN 111804303 A CN111804303 A CN 111804303A CN 202010614630 A CN202010614630 A CN 202010614630A CN 111804303 A CN111804303 A CN 111804303A
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- cerium dioxide
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- shell structure
- aluminum hydrotalcite
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- 229910000422 cerium(IV) oxide Inorganic materials 0.000 title claims abstract description 49
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 title claims abstract description 37
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 title claims abstract description 33
- 229960001545 hydrotalcite Drugs 0.000 title claims abstract description 33
- 229910001701 hydrotalcite Inorganic materials 0.000 title claims abstract description 33
- 239000000463 material Substances 0.000 title claims abstract description 29
- 239000011258 core-shell material Substances 0.000 title claims abstract description 24
- 229910052782 aluminium Inorganic materials 0.000 title claims abstract description 16
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 title claims abstract description 15
- 229910017052 cobalt Inorganic materials 0.000 title claims abstract description 15
- 239000010941 cobalt Substances 0.000 title claims abstract description 15
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 title claims abstract description 15
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000003756 stirring Methods 0.000 claims abstract description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000008367 deionised water Substances 0.000 claims abstract description 11
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 11
- JLDSOYXADOWAKB-UHFFFAOYSA-N aluminium nitrate Chemical compound [Al+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O JLDSOYXADOWAKB-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000005406 washing Methods 0.000 claims abstract description 9
- 238000006243 chemical reaction Methods 0.000 claims abstract description 8
- 238000001816 cooling Methods 0.000 claims abstract description 8
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 6
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 6
- LDDQLRUQCUTJBB-UHFFFAOYSA-N ammonium fluoride Chemical compound [NH4+].[F-] LDDQLRUQCUTJBB-UHFFFAOYSA-N 0.000 claims abstract description 6
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 6
- 239000004202 carbamide Substances 0.000 claims abstract description 6
- 238000010438 heat treatment Methods 0.000 claims abstract description 5
- 238000001291 vacuum drying Methods 0.000 claims abstract description 5
- 238000009210 therapy by ultrasound Methods 0.000 claims abstract description 4
- 239000011259 mixed solution Substances 0.000 claims abstract description 3
- 239000000243 solution Substances 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 7
- 239000000126 substance Substances 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 2
- KFVLFWWLSIOANK-UHFFFAOYSA-N cerium cobalt Chemical compound [Co].[Co].[Co].[Co].[Co].[Ce] KFVLFWWLSIOANK-UHFFFAOYSA-N 0.000 claims 1
- 238000011065 in-situ storage Methods 0.000 abstract description 4
- 239000002086 nanomaterial Substances 0.000 abstract description 4
- BLJNPOIVYYWHMA-UHFFFAOYSA-N alumane;cobalt Chemical compound [AlH3].[Co] BLJNPOIVYYWHMA-UHFFFAOYSA-N 0.000 abstract description 3
- 239000002131 composite material Substances 0.000 abstract description 3
- 239000013078 crystal Substances 0.000 abstract description 3
- ZJHHPAUQMCHPRB-UHFFFAOYSA-N urea urea Chemical compound NC(N)=O.NC(N)=O ZJHHPAUQMCHPRB-UHFFFAOYSA-N 0.000 abstract 1
- 230000015556 catabolic process Effects 0.000 description 7
- 238000006731 degradation reaction Methods 0.000 description 7
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 description 7
- 229940043267 rhodamine b Drugs 0.000 description 7
- 230000001699 photocatalysis Effects 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 5
- 239000011162 core material Substances 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 239000011941 photocatalyst Substances 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 150000001450 anions Chemical class 0.000 description 3
- 229910000420 cerium oxide Inorganic materials 0.000 description 3
- 239000007771 core particle Substances 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 3
- 238000007146 photocatalysis Methods 0.000 description 3
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 3
- 239000010453 quartz Substances 0.000 description 3
- 239000011257 shell material Substances 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000004809 Teflon Substances 0.000 description 2
- 229920006362 Teflon® Polymers 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 description 2
- 239000006228 supernatant Substances 0.000 description 2
- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical compound C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-UHFFFAOYSA-N 0.000 description 1
- -1 CO3 2- Chemical class 0.000 description 1
- 235000005881 Calendula officinalis Nutrition 0.000 description 1
- 240000000785 Tagetes erecta Species 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 150000001449 anionic compounds Chemical class 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 238000013475 authorization Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 238000004925 denaturation Methods 0.000 description 1
- 230000036425 denaturation Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000002149 hierarchical pore Substances 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 229910001412 inorganic anion Inorganic materials 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- STZCRXQWRGQSJD-GEEYTBSJSA-M methyl orange Chemical compound [Na+].C1=CC(N(C)C)=CC=C1\N=N\C1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-GEEYTBSJSA-M 0.000 description 1
- 229940012189 methyl orange Drugs 0.000 description 1
- 229960000907 methylthioninium chloride Drugs 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
- 239000002057 nanoflower Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000002135 nanosheet Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000013032 photocatalytic reaction Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 239000010420 shell particle Substances 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- YNJBWRMUSHSURL-UHFFFAOYSA-N trichloroacetic acid Chemical compound OC(=O)C(Cl)(Cl)Cl YNJBWRMUSHSURL-UHFFFAOYSA-N 0.000 description 1
- 238000003911 water pollution 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
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- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/83—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with rare earths or actinides
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Abstract
A preparation method of a cerium dioxide/cobalt aluminum hydrotalcite material with a core-shell structure comprises the following steps: adding Ce (NO)3)3·6H2Dissolving O in ethylene glycol, stirring for 30-40min, adding ammonia water, stirring at 50-60 deg.C for 30-60min, and heatingReacting at 150 ℃ and 180 ℃ for 2-4h to obtain spherical cerium dioxide, and reacting with Co (NO)3)2·6H2O、Al(NO3)3·6H2O、NH4F. Adding urea into deionized water to obtain a mixed solution, performing ultrasonic treatment for 10-20min, stirring for 30-40min, heating to 100-120 ℃ for reaction for 10-12h, cooling to room temperature, centrifuging, washing, and performing vacuum drying to obtain the urea-urea composite material; the preparation method is simple, can obtain a material with a better crystal form, and utilizes the characteristic that the cobalt-aluminum hydrotalcite is of a two-dimensional nano structure to lead the hydrotalcite sheet to grow on the surface of the cerium dioxide in situ.
Description
Technical Field
The invention relates to the technical field of catalysis, in particular to a preparation method of a cerium dioxide/cobalt aluminum hydrotalcite material with a core-shell structure.
Background
With the continuous and rapid development of modern industry, the problem of water pollution is increasingly severe. Therefore, it is one of the important issues to provide an efficient and economical water treatment technology. The photocatalysis technology directly driven by solar energy attracts attention by people due to the advantages of low cost, high efficiency, no secondary pollution and the like.
Hydrotalcite (LDHs), as an excellent photocatalyst, is an anionic clay material having a layered structure, and has a general formula: [ M ] A2+ 1-xM3+ x(OH)2]x+(An-)x/n·mH2O, wherein M2+Is Mg2+，Ni2+，Cu2+，Zn2+Divalent metal cations; m3+Is Al3+，Cr3+，Fe3+An iso-trivalent metal cation; a. then-Being anions, e.g. CO3 2-，NO3 -，Cl-，SO4 2-And inorganic anions. The interlayer anions of the hydrotalcite have adjustable denaturation, and different anions can be introduced between the layers by an ion exchange method. However, hydrotalcite has the disadvantages of low light utilization rate, large forbidden bandwidth and the like.
In recent years, the attention of people is attracted by the hydrotalcite with a multilevel structure, such as the preparation of structural materials with rosette, marigold and velvet ball shapes, and the special morphology can make the performance of the hydrotalcite more excellent. Therefore, the hydrotalcite material with the core-shell structure is prepared based on the layered structure of hydrotalcite, and the light absorption performance, stability and dispersibility of the material can be greatly improved, so that the photocatalytic performance of the material is improved.
The core-shell structure is a hybrid structure with two or more materials assembled orderly as a core and a shell outside, and is a higher-level nano composite structure. The core in the core-shell structure is usually a reaction unit, and the shell is usually used for protecting the stability of the core particles, so that the surface charge density, the surface activity, the functional group, the reactivity, the biocompatibility, the stability, the dispersibility and the like of the core particles are not changed; meanwhile, the shell forms a special gradient structure through surface coating, and the special electromagnetic property, optical property and catalytic property of the shell particles can be endowed to the core particles. This new material has a number of outstanding advantages, which are mainly reflected in:
(1) the existence of the inner core improves the stability of the core-shell material and shows better physical and chemical properties, such as toughness, shear resistance and the like.
(2) The hierarchical pore structure in the core-shell structure is beneficial to direct absorption of photons or multiple reflection utilization in the pore channel, promotes photon absorption, and provides more photon electron hole pairs to participate in the photocatalytic reaction.
(3) The core-shell nano-structure catalytic material can realize controllable catalytic reaction, and the structure can protect the core material from the influence of external environment and solve the problems of agglomeration, inactivation and the like of nano particles.
According to the invention, the structural characteristics of cerium dioxide spheres and hydrotalcite two-dimensional lamellar layers are utilized to grow hydrotalcite on the surface of cerium dioxide in situ, so that the core-shell structure cerium dioxide/cobalt aluminum hydrotalcite material is prepared.
Disclosure of Invention
The invention aims to provide a cerium dioxide/cobalt aluminum hydrotalcite material (which can be recorded as CeO) with a core-shell structure2@ CoAl-LDHs). The method comprises preparing spherical cerium dioxide, making full use of the characteristic of cobalt-aluminum hydrotalcite as two-dimensional nanostructure, growing hydrotalcite sheet on the surface of cerium dioxide in situ, and centrifuging and washing to obtain CeO2@ CoAl-LDHs material.
The technical scheme of the invention is as follows:
a preparation method of a cerium dioxide/cobalt aluminum hydrotalcite material with a core-shell structure comprises the following steps:
(1) adding Ce (NO)3)3·6H2Dissolving O in ethylene glycol, stirring for 30-40min, adding ammonia water (25-28 wt%), stirring for 30-60min at 50-60 ℃, then heating to 150 ℃ and reacting for 2-4h at 180 ℃, then naturally cooling to room temperature (20-30 ℃), centrifuging, washing (washing with deionized water), and drying (drying for 4-5h at 60-70 ℃) to obtain spherical cerium dioxide;
the Ce (NO)3)3·6H2The concentration of the solution of O dissolved in ethylene glycol is 0.1-0.2mol/L, preferably 0.18 mol/L;
the volume dosage of the ammonia water is Ce (NO)3)3·6H2The mass of the O is 3-5mL/g, preferably 3.75 mL/g;
(2) mixing the spherical cerium dioxide obtained in the step (1) with Co (NO)3)2·6H2O、Al(NO3)3·6H2O、NH4F. Adding urea into deionized water to obtain a mixed solution, performing ultrasonic treatment for 10-20min, stirring for 30-40min, heating to 100-120 ℃, reacting for 10-12h, cooling to room temperature, centrifuging, washing (sequentially washing with deionized water and absolute ethyl alcohol), and performing vacuum drying (vacuum drying at 50-60 ℃ for 10-16h) to obtain the core-shell structure cerium dioxide/cobalt aluminum hydrotalcite material;
the Co (NO)3)2·6H2O、Al(NO3)3·6H2O、NH4F. The mass ratio of urea is 3: 1: 4: 10 m;
the mass amount of the spherical cerium dioxide is Co (NO)3)2·6H2The amount of substance O is 3-6mg/mmol, preferably 5 mg/mmol;
the volume dosage of the deionized water is Co (NO)3)2·6H2The amount of O substance is 5 to 10mL/mmol, preferably 6 to 7 mL/mmol.
The invention has the advantages that:
1. the preparation method is simple, and CeO with better crystal form can be obtained2@CoAl-LDHs；
2. The method utilizes the characteristic that the cobalt-aluminum hydrotalcite is of a two-dimensional nano structure to lead the hydrotalcite sheet to grow on the surface of the cerium dioxide in situ.
Drawings
FIG. 1 shows CeO of example 12XRD pattern of (a);
FIG. 2 shows CeO of example 12XRD pattern of @ CoAl-LDHs;
FIG. 3 shows CeO in example 12SEM picture of (1);
FIGS. 4 and 5 show the CeO in example 12SEM image of @ CoAl-LDHs
FIG. 6 shows CeO2And (3) degrading the rhodamine B map by adopting the @ CoAl-LDHs photocatalysis.
Detailed Description
The present invention is further illustrated by the following specific examples, but the scope of the invention is not limited thereto.
Example 1: a preparation method of a cerium dioxide/cobalt aluminum hydrotalcite material with a core-shell structure comprises the following steps:
A. preparation of spherical cerium dioxide
(1) 4.0g of Ce (NO)3)3·6H2Dissolving O in 50mL of glycol, and stirring for 30 min;
(2) adding 15mL of ammonia water into the solution, and then continuously stirring in a water bath at 50 ℃ for 40 min;
(3) after the stirring, the mixture was transferred to a Teflon reaction vessel and reacted at 150 ℃ for 3 hours.
(4) And after the reaction is finished, taking out the reaction kettle, and naturally cooling to room temperature.
(5) After cooling to room temperature, centrifugation is carried out, and washing is carried out for 2-3 times by using 50-100mL of deionized water, and drying is carried out for 4h at 60 ℃.
B. Preparation of core-shell structure cerium dioxide/cobalt aluminum hydrotalcite material
(1) 15mg of the prepared cerium oxide, 3mmol of Co (NO)3)2·6H2O, 1mmol of Al (NO)3)3·6H2O, 4mmol of NH4F. Dissolving 10mmol of urea in 20mL of deionized water, performing ultrasonic treatment for 15min, and then stirring for 30 min.
(2) The solution was transferred to a Teflon reactor and reacted at 100 ℃ for 10 h.
(3) And after the reaction is finished, taking out the reaction kettle, and cooling to room temperature.
(4) The solution was centrifuged and washed 3 times with 50mL of deionized water and then 5 times with 150mL of absolute ethanol.
(5) Vacuum drying at 50 deg.C for 10 h.
Characterization of XRD
A Shimadzu XRD-6000X-ray powder diffractometer is adopted, wherein the characteristic parameters are set as follows: cu target, Kalpha ray, lambda of 0.15405nm, angle range of 5-70 deg, and scanning speed of 4 deg/min.
From FIG. 1, CeO can be seen2Strong diffraction peak of (A), indicating CeO2And (4) successfully synthesizing. FIG. 2 shows CeO2The XRD pattern of @ CoAl-LDHs clearly shows the characteristic peaks of hydrotalcite (003), (006) and (009), and CeO is also present in the material2Diffraction peak of (D) indicating CeO2Synthesis of @ CoAl-LDHs.
SEM characterization
The surface morphology of the material was characterized using a Hitachi S-4700 scanning electron microscope (SEM, acceleration voltage 15 kV).
FIG. 3 shows CeO2In the SEM photograph, CeO was observed2The morphology of (A) is spherical and the dispersion is uniform. FIG. 4 and FIG. 5 are CeO2SEM picture of @ CoAl-LDHs clearly shows that hydrotalcite nano-sheets are uniformly distributed in CeO2Surface, thereby forming a core-shell structure.
Photocatalytic experiment
To test CeO2The photocatalytic performance of @ CoAl-LDHs adopts a 300W xenon lamp (360W) in the experiment<λ<780nm) was used to simulate a visible light source for photocatalytic degradation experiments. 50mg of CeO2Adding the @ CoAl-LDHs and 50mL of rhodamine B solution (5mg/L) into a double-layer quartz tube (the distance between the quartz tube and a light source is 15cm), and stirring for 30min for dark treatment to achieve adsorption-desorption balance between the catalyst and the rhodamine B solution. Then, a simulated light source is turned on, and a photocatalytic degradation experiment is carried out under magnetic stirring. Taking 3mL of rhodamine B solution from the quartz tube every 1h, centrifuging, taking the supernatant, and measuring the absorbance of the supernatant.
FIG. 6 shows that CeO2The @ CoAl-LDHs has high-efficiency visible light degradation performance on rhodamine B, and the degradation rate reaches 93.1% in 240 min.
Comparative example
At present, cerium dioxide has been studied as a photocatalyst, but the cerium dioxide generally has the defect of low degradation efficiency.
In a patent (a preparation method of a high activity cerium oxide photocatalyst, application publication No. CN 109046313 a), a cerium oxide catalyst was prepared, which has degradation rates of 62% and 83% for methylene blue and methyl orange, respectively, when irradiated for 9 hours under visible light.
In a patent (a cerium dioxide/graphite phase carbon nitride composite material and application thereof in photocatalysis, application publication No. CN 109794277A), a cerium dioxide/graphite phase carbon nitride composite material is prepared, and the degradation rate of the catalyst to trichloroacetic acid is 52% when the catalyst is irradiated by visible light for 60 min.
A manganese-doped cerium dioxide material is prepared in a patent (a preparation method of a manganese-doped cerium dioxide nanoflower visible light photocatalyst, an authorization publication number: CN106732540B), and the degradation rate of the catalyst to rhodamine B under visible light is 50%.
In the text, the prepared core-shell cerium dioxide @ CoAl-LDHs has a good crystal form and high photocatalytic degradation efficiency, and the degradation rate of rhodamine B under visible light irradiation for 240min reaches 93.1%.
Claims (5)
1. A preparation method of a cerium dioxide/cobalt aluminum hydrotalcite material with a core-shell structure is characterized by comprising the following steps:
(1) adding Ce (NO)3)3·6H2Dissolving O in ethylene glycol, stirring for 30-40min, adding ammonia water, stirring for 30-60min at 50-60 ℃, then heating to 150 ℃. 180 ℃ for reaction for 2-4h, then naturally cooling to room temperature, centrifuging, washing, and drying to obtain spherical cerium dioxide;
the Ce (NO)3)3·6H2The concentration of the solution obtained by dissolving O in ethylene glycol is 0.1-0.2 mol/L;
the ammoniaThe volume amount of water is Ce (NO)3)3·6H2The mass of the O is 3-5 mL/g;
(2) mixing the spherical cerium dioxide obtained in the step (1) with Co (NO)3)2·6H2O、Al(NO3)3·6H2O、NH4F. Adding urea into deionized water to obtain a mixed solution, performing ultrasonic treatment for 10-20min, stirring for 30-40min, heating to 100-120 ℃, reacting for 10-12h, cooling to room temperature, centrifuging, washing, and performing vacuum drying to obtain the core-shell structure cerium dioxide/cobalt-aluminum hydrotalcite material;
the Co (NO)3)2·6H2O、Al(NO3)3·6H2O、NH4F. The mass ratio of urea is 3: 1: 4: 10;
the mass amount of the spherical cerium dioxide is Co (NO)3)2·6H2The amount of O is 3-6 mg/mmol;
the volume dosage of the deionized water is Co (NO)3)2·6H2The amount of O substance is 5-10 mL/mmol.
2. The method for preparing the ceria/cobalt aluminum hydrotalcite material with core-shell structure according to claim 1, wherein in step (1), the Ce (NO) is added3)3·6H2The concentration of the solution of O dissolved in ethylene glycol was 0.18 mol/L.
3. The method for preparing the ceria/cobalt aluminum hydrotalcite material with core-shell structure according to claim 1, wherein in step (1), the volume amount of the ammonia water is Ce (NO)3)3·6H2The mass of O was 3.75 mL/g.
4. The method for preparing the core-shell structure cerium dioxide/cobalt aluminum hydrotalcite material according to claim 1, wherein in the step (2), the amount of the spherical cerium dioxide is Co (NO) by mass3)2·6H2The amount of O substance was 5 mg/mmol.
5. The method for preparing the ceria/cobalt aluminum hydrotalcite material with core-shell structure according to claim 1, wherein in step (2), the volume of the deionized water is Co (NO)3)2·6H2The amount of O substance is 6-7 mL/mmol.
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