CN116159597A - Cerium oxide hydrogel microsphere, preparation method and application thereof - Google Patents
Cerium oxide hydrogel microsphere, preparation method and application thereof Download PDFInfo
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- 239000000017 hydrogel Substances 0.000 title claims abstract description 112
- 239000004005 microsphere Substances 0.000 title claims abstract description 111
- 229910000420 cerium oxide Inorganic materials 0.000 title claims abstract description 89
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 title claims abstract description 89
- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims abstract description 28
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims abstract description 28
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims abstract description 27
- 229920000642 polymer Polymers 0.000 claims abstract description 12
- 239000011148 porous material Substances 0.000 claims abstract description 9
- 239000011259 mixed solution Substances 0.000 claims description 15
- 150000000703 Cerium Chemical class 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 13
- 238000010894 electron beam technology Methods 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 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 10
- 230000001699 photocatalysis Effects 0.000 claims description 10
- 238000005516 engineering process Methods 0.000 claims description 9
- 238000001914 filtration Methods 0.000 claims description 8
- 230000003647 oxidation Effects 0.000 claims description 8
- 238000007254 oxidation reaction Methods 0.000 claims description 8
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 claims description 6
- 238000004108 freeze drying Methods 0.000 claims description 6
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims description 5
- 239000003054 catalyst Substances 0.000 claims description 4
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 9
- 230000002776 aggregation Effects 0.000 abstract description 7
- 238000005054 agglomeration Methods 0.000 abstract description 6
- 238000011068 loading method Methods 0.000 abstract description 5
- 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 15
- 229940012189 methyl orange Drugs 0.000 description 15
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 11
- 239000000843 powder Substances 0.000 description 11
- 230000015556 catabolic process Effects 0.000 description 10
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- 229910052760 oxygen Inorganic materials 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 238000009827 uniform distribution Methods 0.000 description 3
- 229910052684 Cerium Inorganic materials 0.000 description 2
- 238000002835 absorbance Methods 0.000 description 2
- 230000006978 adaptation Effects 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
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- -1 oxygen ion Chemical class 0.000 description 2
- 239000002957 persistent organic pollutant Substances 0.000 description 2
- 238000007146 photocatalysis Methods 0.000 description 2
- STZCRXQWRGQSJD-UHFFFAOYSA-M sodium;4-[[4-(dimethylamino)phenyl]diazenyl]benzenesulfonate Chemical compound [Na+].C1=CC(N(C)C)=CC=C1N=NC1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-UHFFFAOYSA-M 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- YLZOPXRUQYQQID-UHFFFAOYSA-N 3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]propan-1-one Chemical compound N1N=NC=2CN(CCC=21)CCC(=O)N1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F YLZOPXRUQYQQID-UHFFFAOYSA-N 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
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- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
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- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
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- 230000010494 opalescence Effects 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 238000007539 photo-oxidation reaction Methods 0.000 description 1
- 239000011941 photocatalyst Substances 0.000 description 1
- 238000013032 photocatalytic reaction Methods 0.000 description 1
- 238000001782 photodegradation Methods 0.000 description 1
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- 238000007639 printing Methods 0.000 description 1
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- 229910052761 rare earth metal Inorganic materials 0.000 description 1
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
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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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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
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- B01J35/39—Photocatalytic properties
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Abstract
The invention provides a cerium oxide hydrogel microsphere, which consists of porous three-dimensional network hydrogel microsphere formed by high molecular polymer polyvinylpyrrolidone and nano cerium oxide, wherein the nano cerium oxide is distributed on the pores and/or the surface of the hydrogel microsphere. The application also provides a preparation method and application of the cerium oxide hydrogel microsphere. The cerium oxide hydrogel microsphere provided by the application is a three-dimensional network structure formed by taking polyvinylpyrrolidone as a microsphere main body bracket and loading nano cerium oxide in the interior and/or on the surface. The nano cerium oxide in the cerium oxide hydrogel microsphere provided by the invention is uniformly distributed, has no agglomeration, and has high catalytic efficiency and wide application prospect.
Description
Technical Field
The invention relates to the technical field of new rare earth element processing materials, in particular to a cerium oxide hydrogel microsphere, a preparation method and application thereof.
Background
Photocatalysis is a green technology, and has the advantages of convenient implementation, low energy consumption, mild reaction conditions, no secondary pollution and the like. In recent years, the photocatalytic oxidation technology is used for wastewater treatment, and compared with the traditional water treatment technology, the photocatalytic oxidation technology has remarkable advantages on solid wastes such as refractory organic matters in printing and dyeing wastewater, microbial pollution in water bodies and the like, so that the photocatalytic oxidation technology becomes a novel water treatment technology with great application prospects.
CeO 2 The catalyst has unique physical and chemical properties, and is very suitable for the field of photocatalysts. Such as a large number of oxygen vacancies, high oxygen storage capacity, high oxygen ion conductivity, ce 3+ And Ce (Ce) 4+ The rapid oxidation-reduction capability and the strong metal carrier interaction effect and the like make the metal carrier have excellent degradation capability. Thus, ceO 2 In photooxidation reductionThe reaction, in particular to photodegradation of organic pollutants, photocatalytic selective oxidation and photocatalytic decomposition of water to produce hydrogen, plays an important role. The existing research is mostly focused on increasing the specific surface area to improve the catalytic efficiency, but the catalytic efficiency is lower because the nano cerium oxide particles are easy to agglomerate in the preparation process. Therefore, how to prepare the nano cerium oxide material with uniform distribution is an urgent problem to be solved at present.
Disclosure of Invention
The technical problem solved by the invention is to provide the cerium oxide hydrogel microsphere which has the characteristic of uniform distribution of nano cerium oxide and avoids agglomeration of nano cerium oxide; the application also provides a preparation method of the cerium oxide hydrogel microsphere, which can realize uniform distribution of the nano cerium oxide and avoid agglomeration of the nano cerium oxide.
In view of this, the present application provides a cerium oxide hydrogel microsphere, which is composed of porous, three-dimensional network hydrogel microsphere formed by high molecular polymer polyvinylpyrrolidone and nano cerium oxide, wherein the nano cerium oxide is distributed on the pores and/or the surface of the hydrogel microsphere.
Preferably, the radius of the cerium oxide hydrogel microsphere is 20-60 nm, and the specific surface area is 100-140 m 2 /g。
The application also provides a preparation method of the cerium oxide hydrogel microsphere, which comprises the following steps:
mixing polyvinylpyrrolidone, cerium salt and water to obtain a mixed solution; the concentration of polyvinylpyrrolidone in the mixed solution is 1-5 g/L;
and (3) carrying out high-energy ray irradiation on the mixed solution to obtain the cerium oxide hydrogel microsphere.
Preferably, the high-energy ray irradiation further comprises:
and filtering the microspheres obtained by high-energy ray irradiation, and freeze-drying.
Preferably, the concentration of the cerium salt is 5 to 30mmol/L.
Preferably, the cerium salt is selected from one or both of cerium nitrate and cerium acetate.
Preferably, the high-energy ray is an electron beam.
Preferably, the energy of the electron beam irradiated is 1-10 MeV, and the dosage is 30-50 kGy.
Preferably, the filtration is carried out by using a filter with a pore size of 10-120 nm.
The application also provides the application of the cerium oxide hydrogel microsphere or the cerium oxide hydrogel microsphere prepared by the preparation method as a catalyst of a photocatalytic oxidation technology.
The application provides a cerium oxide hydrogel microsphere, which consists of porous three-dimensional reticular hydrogel microsphere formed by high molecular polymer polyvinylpyrrolidone and nano cerium oxide, wherein the nano cerium oxide is uniformly distributed on the pores and/or the surface of the hydrogel microsphere, and agglomeration does not occur.
The application provides a preparation method of cerium oxide hydrogel microspheres, which comprises the steps of mixing polyvinylpyrrolidone, cerium salt and water to obtain a mixed solution, and then carrying out high-energy ray irradiation on the mixed solution to obtain the cerium oxide hydrogel microspheres; in the process of preparing the cerium oxide hydrogel microsphere, cerium salt in the mixed solution is attacked by hydroxyl free radicals generated by water radiolysis under the irradiation condition of high-energy rays to form nano cerium oxide, meanwhile, a high-molecular polymer is irradiated by high-energy rays under the critical concentration (1-5 g/L) to form a plurality of initial chain free radicals on a high-molecular chain, and the polymer concentration is under the critical concentration, so that the distance between molecular chains is far, and an intramolecular cross-linking structure, namely the porous microgel, is formed; in the process of crosslinking in polymer molecules, synchronously synthesized nano cerium oxide is wrapped in a three-dimensional network of hydrogel microspheres or adsorbed on the surfaces of the hydrogel microspheres through mutual entanglement of molecular chains and adsorption of the hydrogel microspheres, so that microgel of high-load nano cerium oxide is formed; meanwhile, the high molecular polymer in the solution is also used as a surfactant in the system, so that the nano cerium oxide generated in the reaction is stabilized and uniformly dispersed, the agglomeration of the nano cerium oxide is avoided, and the nano cerium oxide is uniformly distributed on the pores and/or the surface of the hydrogel microsphere.
Therefore, the preparation method provided by the application forms a nanoscale porous structure due to the intramolecular crosslinking effect of polyvinylpyrrolidone, has better cerium oxide dispersion effect, has no agglomeration and precipitation phenomenon, increases the cerium oxide loading rate through physical adsorption effect, and improves the cerium oxide catalytic efficiency; the cerium oxide hydrogel microsphere prepared by the method does not need to be added with additives and post-treatment auxiliary agents, has high biological safety, simple preparation process and low cost, and can realize large-scale production.
Drawings
FIG. 1 shows PVP-CeO prepared in example 1 of the present invention 2 Transmission electron microscope pictures of hydrogel microspheres;
FIG. 2 shows PVP-CeO prepared according to the invention 2 Hydrodynamic radius curves of hydrogel microspheres at different PVP concentrations;
FIG. 3 shows PVP-CeO prepared according to the invention 2 Hydrodynamic radius curves of hydrogel microspheres at different dose rates;
FIG. 4 shows PVP-CeO prepared according to the invention 2 Ultraviolet light absorption spectrogram of hydrogel microsphere under different cerium acetate concentrations;
FIG. 5 shows PVP-CeO prepared in example 2 of the present invention 2 The effect diagram of the hydrogel microspheres in actually degrading methyl orange;
FIG. 6 is a graph showing the degradation of methyl orange under various conditions;
FIG. 7 is a graph showing the comparison of the morphologies of hydrogels formed in examples 3, 9, and 10.
Detailed Description
For a further understanding of the present invention, preferred embodiments of the invention are described below in conjunction with the examples, but it should be understood that these descriptions are merely intended to illustrate further features and advantages of the invention, and are not limiting of the claims of the invention.
In view of the problem that cerium oxide nano particles are easy to agglomerate and further influence catalytic efficiency in the prior art, the application provides a cerium oxide hydrogel microsphere and a preparation method thereof. Specifically, the embodiment of the invention discloses a cerium oxide hydrogel microsphere, which consists of porous three-dimensional network hydrogel microsphere formed by high molecular polymer polyvinylpyrrolidone and nano cerium oxide, wherein the nano cerium oxide is distributed on the pores and/or the surface of the hydrogel microsphere.
The application provides a cerium oxide hydrogel microsphere, wherein polyvinylpyrrolidone forms a porous hydrogel microsphere with a three-dimensional network structure, nano cerium oxide is distributed in pores of the hydrogel microsphere, and/or nano cerium oxide is distributed on the surface of the hydrogel microsphere.
In the application, the radius of the cerium oxide hydrogel microsphere is 20-60 nm, and the specific surface area is 100-140 m 2 And/g. The load rate of the nano cerium oxide in the hydrogel microsphere is more than 60 percent.
Further, the application also provides a preparation method of the cerium oxide hydrogel microsphere, which comprises the following steps:
mixing polyvinylpyrrolidone, cerium salt and water to obtain a mixed solution; the concentration of polyvinylpyrrolidone in the mixed solution is 1-5 g/L;
and (3) carrying out high-energy ray irradiation on the mixed solution to obtain the cerium oxide hydrogel microsphere.
In the preparation process of the cerium oxide hydrogel microsphere, firstly, polyvinylpyrrolidone, cerium salt and water are mixed to obtain a mixed solution; in the mixed solution, the concentration of polyvinylpyrrolidone is 1-5 g/L, the concentration of cerium salt is 5-30 mmol/L, specifically, the concentration of polyvinylpyrrolidone is 1g/L, 2g/L, 3g/L, 4g/L or 5g/L, and the concentration of cerium salt is 6mmol/L, 10mmol/L, 12mmol/L, 14mmol/L, 18mmol/L, 20mmol/L, 22mmol/L, 24mmol/L or 28mmol/L. In the present application, the cerium salt is selected from one or both of cerium nitrate and cerium acetate.
And then carrying out high-energy ray irradiation on the mixed solution, filtering the cerium oxide hydrogel microsphere obtained by the reaction, and freeze-drying to obtain the cerium oxide hydrogel microsphere. In the process, polyvinylpyrrolidone is internally crosslinked under the irradiation of high-energy rays, and cerium ions form nano cerium oxide. The high-energy ray irradiation adopts electron beam irradiation, the energy of the electron beam is 1-10 MeV, and the dose is 30-50 kGy; specifically, the energy of the electron beam is 2-7 MeV, and the dose is 32-45 kGy. The filtering specifically adopts a filter with the aperture of 10-120 nm for filtering. The freeze-drying is a freeze-drying well known to those skilled in the art, and the specific means for carrying out the method is not particularly limited.
Furthermore, the application also provides application of the cerium oxide hydrogel microsphere as a catalyst for a photocatalytic oxidation technology; specifically, the cerium oxide hydrogel microsphere provided by the application can be used for degrading methyl orange, photodegradable organic pollutants and the like.
In order to further understand the present invention, the following examples are provided to illustrate the cerium oxide hydrogel microsphere, the preparation method thereof and the application thereof in detail, and the scope of the present invention is not limited by the following examples.
Example 1
Dissolving 2g of polyvinylpyrrolidone in 1L of purified water, stirring to dissolve completely, adding 10mmol of cerium acetate, and stirring to dissolve completely;
carrying out high-dose-rate electron beam irradiation on the solution which is uniformly dissolved, wherein the energy of the electron beam is 2MeV, the beam current is 500 mu A, and the accumulated irradiation dose is 20KGy;
filtering the cerium oxide hydrogel microsphere obtained by the reaction through a filter with the aperture of 10nm, and freeze-drying to obtain PVP-CeO 2 Hydrogel microsphere powder.
Example 2
With PVP-CeO of example 1 2 The preparation method of the hydrogel microsphere powder is the same, and the difference is that: the concentration of polyvinylpyrrolidone was 3g/L.
Example 3
With PVP-CeO of example 1 2 The preparation method of the hydrogel microsphere powder is the same, and the difference is that: the concentration of polyvinylpyrrolidone was 4g/L.
Example 4
With PVP-CeO of example 1 2 The preparation method of the hydrogel microsphere powder is the same, and the difference is that: the beam current of the electron beam irradiation was 400. Mu.A.
Example 5
With PVP-CeO of example 1 2 The preparation method of the hydrogel microsphere powder is the same, and the difference is that: the beam current of the electron beam irradiation was 300. Mu.A.
Example 6
With PVP-CeO of example 1 2 The preparation method of the hydrogel microsphere powder is the same, and the difference is that: the beam current of the electron beam irradiation was 200. Mu.A.
Example 7
With PVP-CeO of example 1 2 The preparation method of the hydrogel microsphere powder is the same, and the difference is that: the concentration of cerium acetate was 16mM.
Example 8
With PVP-CeO of example 1 2 The preparation method of the hydrogel microsphere powder is the same, and the difference is that: the concentration of cerium acetate was 24mM.
Comparative example
The same preparation method of PVP-CeO2 hydrogel microsphere powder of example 1 is different only in that: the cerium acetate was replaced with commercially available 10nm CeO 2 And (3) particles.
Example 9
With PVP-CeO of example 1 2 The preparation method of the hydrogel microsphere powder is the same, and the difference is that: the concentration of polyvinylpyrrolidone was 6g/L.
Example 10
With PVP-CeO of example 1 2 The preparation method of the hydrogel microsphere powder is the same, and the difference is that: the concentration of polyvinylpyrrolidone was 10g/L.
The test methods of the above examples and comparative examples are as follows:
1) And (3) microscopic morphology analysis of cerium oxide hydrogel microspheres: dynamic light scattering method for measuring hydrodynamic diameter (R h ) Observing microscopic morphology by a transmission electron microscope;
2) Determination of specific surface area of cerium oxide hydrogel microspheres: a BET specific surface area measurement method is adopted;
3) Testing an ultraviolet absorption spectrum of the cerium oxide hydrogel microsphere;
4) Efficiency of catalytic degradation of methyl orange by cerium oxide hydrogel microspheres: preparing 0.1L of 10mg/L methyl orange solution, adding 0.1g of cerium oxide hydrogel microspheres prepared in example 1, and fully stirring under a dark condition to obtain a uniform solution; starting an ultraviolet lamp, simulating a photocatalytic reaction, taking 10ml of the solution every 10 minutes for 60 minutes, centrifuging to remove the cerium oxide hydrogel microspheres, testing the absorbance of the methyl orange solution by a spectrophotometer, calculating the residual concentration of the methyl orange in the solution, and further calculating the degradation rate of the methyl orange, namely the catalytic efficiency of the cerium oxide hydrogel microspheres.
The test results were as follows:
FIG. 1 shows PVP-CeO prepared in example 1 2 As can be seen from the transmission electron microscope photograph of the hydrogel microsphere in FIG. 1, PVP-CeO is prepared 2 The hydrodynamics radius of the hydrogel microsphere is 28.8+/-4.18 nm.
FIG. 2 PVP-CeO 2 As can be seen from fig. 2, the particle size of the cerium oxide hydrogel microspheres gradually increases with increasing concentration of polyvinylpyrrolidone due to increasing concentration of polymer such that the molecular chains are close to each other, resulting in an increased probability of intermolecular crosslinking.
FIG. 3 PVP-CeO 2 As can be seen from fig. 3, the hydrodynamic radius curve of the hydrogel microsphere under different irradiation doses is reduced, the hydrodynamic radius of the formed hydrogel microsphere is increased, the distribution is widened, and the high dose rate is more favorable for forming the hydrogel microsphere with compact crosslinking as the irradiation dose rate is reduced.
FIG. 4 PVP-CeO 2 Ultraviolet light absorption patterns of hydrogel microspheres under different cerium acetate concentrations, a is example 8, b is example 7, and c is example 1; as can be seen from fig. 4, as the addition amount of cerium acetate increases, the content of nano cerium oxide increases accordingly, and the ultraviolet absorbance of the prepared cerium oxide hydrogel microsphere is higher. Table 1 shows the oxidation of examples 1 to 8Hydrodynamic radius of cerium hydrogel microsphere, specific surface area test data and load rate data of nano cerium oxide. Table 1 hydrodynamic radii and specific surface area test data sheets for examples 1 to 8 and comparative ceria hydrogel microspheres
| Sequence number | R h (nm) | Specific surface area (m) 2 /g) | Nanometer cerium oxide loading rate |
| Example 1 | 28.8±4.18nm | 137 | 62.3％ |
| Example 2 | 37.6±3.11nm | 123 | 67.5％ |
| Example 3 | 48.8±3.18nm | 121 | 70.2％ |
| Example 4 | 37.7±3.12nm | 108 | 67.2％ |
| Example 5 | 39.1±3.77nm | 117 | 64.2％ |
| Example 6 | 51.5±4.29nm | 122 | 60.3％ |
| Example 7 | 31.6±4.98nm | 127 | 63.4％ |
| Example 8 | 35.7±3.97nm | 129 | 63.9％ |
| Comparative example 1 | 11.3±2.19nm | 88 | 38.6％ |
As can be seen from the table, the 10nm nano cerium oxide particles purchased had a hydrodynamic radius of 11.3nm and a specific surface area of 88m 2 And/g, the hydrogel microsphere is coated in the hydrogel microsphere, the loading rate is only 38.6%, and the main reason is that the hydrogel microsphere has aggregation behavior after dissolution, cerium oxide is insoluble in water, the hydrogel microsphere has a coating effect on the hydrogel microsphere completely by physical coating, and the coating efficiency is low in the process, so that the loading rate is low. The hydrodynamics radius of the hydrogel microspheres in examples 1-8 is larger than that of the comparative example, and the specific surface area is also larger than that of the comparative example; for solid ballsIn other words, the larger the particle diameter, the smaller the specific surface area, and therefore, the increase in specific surface area of the microparticles in examples 1 to 8 is attributable to the formation of hydrogel microspheres, the three-dimensional network structure inside which greatly increases the specific surface area thereof.
From the above data, the major influencing factors of the hydrodynamic radius of the ceria hydrogel microspheres are: 1) The smaller the concentration of the high molecular polymer, the greater the tendency of forming intramolecular cross-links than intermolecular cross-links, and the smaller the hydrodynamic radius of the formed hydrogel microsphere; 2) The higher the dose rate of the high-energy ray irradiation, the more the number of initial chain free radicals are formed, the higher the intramolecular crosslinking degree is, the more compact the crosslinking structure is formed, and the smaller the hydrodynamic radius is.
FIG. 5 shows PVP-CeO prepared in example 1 2 As can be clearly seen from fig. 5, the effect of the hydrogel microspheres on actually degrading methyl orange shows that under the degradation effect of the cerium oxide hydrogel microspheres, the color of the methyl orange is obviously changed, i.e. the degradation effect of the methyl orange is obvious.
FIG. 6 shows the degradation curves of methyl orange under different conditions, curve a shows the degradation curve of methyl orange in the presence of UV light alone, and curve b shows the coating of commercially available 10nm CeO in the comparative example 2 The degradation curve of the hydrogel microsphere of the particle to methyl orange and curve c are PVP-CeO prepared in example 2 2 Degradation curve for methyl orange; as can be seen from FIG. 6, the prepared cerium oxide hydrogel microsphere has the effect of degrading methyl orange by photocatalysis, more than 99% of methyl orange can be removed only in 40min, and the comparative example is wrapped with commercial 10nm CeO 2 The catalytic efficiency of the hydrogel microsphere of the particle is obviously lower than that of the hydrogel microsphere for in-situ synthesis of cerium oxide, and the main reason is that the cerium oxide is more uniformly distributed and the catalytic efficiency is higher by utilizing cerium salt to synthesize the cerium oxide nano hydrogel microsphere in the polymer in-situ.
FIG. 7 is a graph showing the comparison of the morphology of the hydrogels formed in examples 3, 9 and 10, wherein the hydrogel microspheres formed are homogeneous solutions with blue opalescence (example 3) when the concentration of polyvinylpyrrolidone is 5g/L; when the polyvinylpyrrolidone concentration reached 6g/L, the hydrogel formed was similar to a gel (example 9); continuing to increase the concentration, a sheetlike hydrogel was formed (example 10).
The above description of the embodiments is only for aiding in the understanding of the method of the present invention and its core ideas. It should be noted that it will be apparent to those skilled in the art that various modifications and adaptations of the invention can be made without departing from the principles of the invention and these modifications and adaptations are intended to be within the scope of the invention as defined in the following claims.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (10)
1. The cerium oxide hydrogel microsphere consists of porous three-dimensional network hydrogel microsphere formed by high molecular polymer polyvinylpyrrolidone and nano cerium oxide, wherein the nano cerium oxide is distributed on the pores and/or the surface of the hydrogel microsphere.
2. The cerium oxide hydrogel microsphere according to claim 1, wherein the radius of the cerium oxide hydrogel microsphere is 20 to 60nm and the specific surface area is 100 to 140m 2 /g。
3. A preparation method of cerium oxide hydrogel microspheres, which comprises the following steps:
mixing polyvinylpyrrolidone, cerium salt and water to obtain a mixed solution; the concentration of polyvinylpyrrolidone in the mixed solution is 1-5 g/L;
and (3) carrying out high-energy ray irradiation on the mixed solution to obtain the cerium oxide hydrogel microsphere.
4. A production method according to claim 3, characterized in that the high-energy ray irradiation further comprises:
and filtering the microspheres obtained by high-energy ray irradiation, and freeze-drying.
5. The method according to claim 3 or 4, wherein the concentration of the cerium salt is 5 to 30mmol/L.
6. The method according to claim 3 or 4, wherein the cerium salt is one or both of cerium nitrate and cerium acetate.
7. The method according to claim 3 or 4, wherein the high-energy ray is an electron beam.
8. The method according to claim 3 or 4, wherein the energy of the electron beam irradiated is 1 to 10MeV, and the dose is 30 to 50kGy.
9. The method according to claim 4, wherein the filtration is performed by using a filter having a pore size of 10 to 120 nm.
10. Use of the ceria hydrogel microsphere according to any one of claims 1 to 2 or the ceria hydrogel microsphere prepared by the preparation method according to any one of claims 3 to 9 as a catalyst for photocatalytic oxidation technology.
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