CN114471707B - Hydrogel sphere containing catalyst, preparation method thereof and application thereof in photocatalytic treatment of organic pollutants - Google Patents
Hydrogel sphere containing catalyst, preparation method thereof and application thereof in photocatalytic treatment of organic pollutants Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 137
- 239000000017 hydrogel Substances 0.000 title claims abstract description 89
- 230000001699 photocatalysis Effects 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 239000002957 persistent organic pollutant Substances 0.000 title claims abstract description 18
- 108010010803 Gelatin Proteins 0.000 claims abstract description 47
- 239000008273 gelatin Substances 0.000 claims abstract description 47
- 229920000159 gelatin Polymers 0.000 claims abstract description 47
- 235000019322 gelatine Nutrition 0.000 claims abstract description 47
- 235000011852 gelatine desserts Nutrition 0.000 claims abstract description 47
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 40
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 40
- 229920001661 Chitosan Polymers 0.000 claims abstract description 38
- SXRSQZLOMIGNAQ-UHFFFAOYSA-N Glutaraldehyde Chemical compound O=CCCCC=O SXRSQZLOMIGNAQ-UHFFFAOYSA-N 0.000 claims abstract description 34
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 claims abstract description 30
- 235000010413 sodium alginate Nutrition 0.000 claims abstract description 30
- 229940005550 sodium alginate Drugs 0.000 claims abstract description 30
- 239000000661 sodium alginate Substances 0.000 claims abstract description 30
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000000203 mixture Substances 0.000 claims abstract description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000002156 mixing Methods 0.000 claims abstract description 7
- 238000010438 heat treatment Methods 0.000 claims abstract description 5
- 238000000034 method Methods 0.000 claims description 32
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 claims description 26
- 239000008188 pellet Substances 0.000 claims description 22
- 235000010265 sodium sulphite Nutrition 0.000 claims description 13
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- 229910002492 Ce(NO3)3·6H2O Inorganic materials 0.000 claims description 7
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical group [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 claims description 6
- 239000000356 contaminant Substances 0.000 claims description 5
- 239000011258 core-shell material Substances 0.000 claims description 5
- 239000011541 reaction mixture Substances 0.000 claims description 4
- 238000004090 dissolution Methods 0.000 claims description 3
- 230000015556 catabolic process Effects 0.000 abstract description 11
- 238000006731 degradation reaction Methods 0.000 abstract description 11
- 238000013033 photocatalytic degradation reaction Methods 0.000 abstract description 7
- 238000010521 absorption reaction Methods 0.000 abstract description 6
- 238000007146 photocatalysis Methods 0.000 abstract description 3
- 238000004064 recycling Methods 0.000 abstract description 3
- 238000011084 recovery Methods 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 53
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- 229910052760 oxygen Inorganic materials 0.000 description 6
- 238000001354 calcination Methods 0.000 description 5
- 229910052777 Praseodymium Inorganic materials 0.000 description 4
- 238000009303 advanced oxidation process reaction Methods 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 239000003344 environmental pollutant Substances 0.000 description 4
- 230000031700 light absorption Effects 0.000 description 4
- 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 4
- 229940012189 methyl orange Drugs 0.000 description 4
- 230000003287 optical effect Effects 0.000 description 4
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- 231100000719 pollutant Toxicity 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 229910052724 xenon Inorganic materials 0.000 description 4
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 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 2
- 238000002835 absorbance Methods 0.000 description 2
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- 125000003118 aryl group Chemical group 0.000 description 2
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- 230000003139 buffering effect Effects 0.000 description 2
- 239000012295 chemical reaction liquid Substances 0.000 description 2
- ZXJXZNDDNMQXFV-UHFFFAOYSA-M crystal violet Chemical compound [Cl-].C1=CC(N(C)C)=CC=C1[C+](C=1C=CC(=CC=1)N(C)C)C1=CC=C(N(C)C)C=C1 ZXJXZNDDNMQXFV-UHFFFAOYSA-M 0.000 description 2
- 230000000593 degrading effect Effects 0.000 description 2
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- 229960000907 methylthioninium chloride Drugs 0.000 description 2
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- 230000001590 oxidative effect Effects 0.000 description 2
- 239000011941 photocatalyst Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000002035 prolonged effect Effects 0.000 description 2
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- 230000001105 regulatory effect Effects 0.000 description 2
- 238000005070 sampling Methods 0.000 description 2
- 238000010008 shearing Methods 0.000 description 2
- 239000011734 sodium Substances 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
- 238000012360 testing method Methods 0.000 description 2
- 238000002211 ultraviolet spectrum Methods 0.000 description 2
- 229910052684 Cerium Inorganic materials 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 229910002828 Pr(NO3)3·6H2O Inorganic materials 0.000 description 1
- 241000907663 Siproeta stelenes Species 0.000 description 1
- OUUQCZGPVNCOIJ-UHFFFAOYSA-M Superoxide Chemical compound [O-][O] OUUQCZGPVNCOIJ-UHFFFAOYSA-M 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 229910000420 cerium oxide Inorganic materials 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 229910052747 lanthanoid Inorganic materials 0.000 description 1
- 150000002602 lanthanoids Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229940107698 malachite green Drugs 0.000 description 1
- FDZZZRQASAIRJF-UHFFFAOYSA-M malachite green Chemical compound [Cl-].C1=CC(N(C)C)=CC=C1C(C=1C=CC=CC=1)=C1C=CC(=[N+](C)C)C=C1 FDZZZRQASAIRJF-UHFFFAOYSA-M 0.000 description 1
- 238000013507 mapping Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000000643 oven drying Methods 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 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 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000009284 supercritical water oxidation Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 238000003911 water pollution Methods 0.000 description 1
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
- B01J31/069—Hybrid organic-inorganic polymers, e.g. silica derivatized with organic groups
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
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- B01J35/20—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/51—Spheres
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
- C02F1/32—Treatment of water, waste water, or sewage by irradiation with ultraviolet light
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
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- C—CHEMISTRY; METALLURGY
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- C02F2305/10—Photocatalysts
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Abstract
The invention discloses a hydrogel ball containing a catalyst, a preparation method thereof and application of the hydrogel ball in photocatalytic treatment of organic pollutants, and belongs to the technical field of photocatalysis. Comprises adding chitosan into acetic acid solution to obtain chitosan solution; adding sodium alginate into ultra-light water, and then adding glutaraldehyde solution to obtain sodium alginate glutaraldehyde solution; adding gelatin, graphene and a catalyst into ultra-light water, and heating and dissolving to obtain a graphene gelatin solution serving as a catalyst; and mixing the chitosan solution with the catalyst graphene gelatin solution, dropwise adding the mixture into the sodium alginate glutaraldehyde solution, and after the mixture is molded, obtaining the catalyst-containing hydrogel spheres. The invention is applied to photocatalytic degradation of organic matters, solves the problems of low degradation efficiency, narrow applicable pH range, difficult recovery and poor anti-interference capability of a system of the existing catalyst, and has the characteristics of widening the applicable pH range, increasing the anti-interference capability of the system, improving the absorption capability of the catalyst to visible light and increasing the recycling of the catalyst.
Description
Technical Field
The invention belongs to the technical field of photocatalysis, and particularly relates to a hydrogel ball containing a catalyst, a preparation method thereof and application of the hydrogel ball in photocatalysis treatment of organic pollutants.
Background
Advanced oxidation techniques (Advanced Oxidation Process, AOPs) mainly use oxidants to generate highly reactive hydroxyl radicals (oh·) that are extremely oxidizing and are capable of degrading organic contaminants in water by radical chain reactions. Compared with the traditional treatment method, the AOPs can greatly improve the reaction rate and thoroughly oxidize and decompose pollutants. However, this method also has many disadvantages such as the demanding reaction pH range (3.5-4.5), excessive quenching reaction, and oxidant H 2 O 2 Is liquid and is not easy to store and transport. In order to solve the problems, AOPs such as a photocatalytic oxidation method, an ozone oxidation method, an electrocatalytic oxidation method, a wet air oxidation method, a supercritical water oxidation method and the like are developed successively, and a great contribution is made to solving the problem of water pollution. Among them, the photocatalytic oxidation method is favored because of its advantages of normal temperature and pressure, low energy consumption, simple operation, etc. However, the conventional photocatalyst can only absorb ultraviolet light but cannot utilize visible light, and the use of ultraviolet light consumes a large amount of energy, which is unfavorable for saving resources.
CeO with fluorite structure 2 And compounds thereof have been attracting attention because of their wide application as catalysts, oxygen sensors, ultraviolet blockers, polishing powders, and the like. Studies by Fallah et al show that CeO 2 Can be photoactivated under near ultraviolet-visible light irradiation, but CeO 2 The forbidden bandwidth of (2) is 3.2eV, so that the ultraviolet light absorption spectrum has strong absorption in the ultraviolet light region, and the absorption intensity in the visible light region is relatively low. To improve CeO 2 Photocatalytic activity under visible or solar irradiation, typically at CeO 2 Other metal oxides such as Fe, cu, etc. are doped in the middle, but the effect is not good. Praseodymium (Pr) and Ce are lanthanoid elements and have adjacent atomic numbers and similar atomic radii, so Pr is expected to replace Ce to enter CeO 2 Without altering CeO in the crystal lattice of (C) 2 Is a crystal form of (a). In addition, since Pr has special f and d orbitals, pr doping can provide intermediate energy level to drive CeO 2 The forbidden bandwidth of the light source is reduced to 2.2eV, and the visible light absorption capacity of the light source is greatly improved. Hao et al prepared Pr doped CeO 2 And H 2 O 2 Together used for degrading rhodamine under sunlight irradiation. In this study, pr (Ce, prO) -doped mesoporous cerium oxide with an ordered two-dimensional hexagonal structure was successfully synthesized. The result shows that the mesoporous Ce-Pr-O has good visible light absorption capability and a large number of oxygen vacancies. H due to formation of oxygen vacancies 2 O 2 Greatly increasing the adsorption capacity of (C), which is more beneficial to H 2 O 2 The decomposition produces OH, which can further promote the degradation of pollutants.
However, the catalyst still has the problems of low degradation efficiency on organic pollutants, narrow applicable pH range, difficult recovery, poor anti-interference capability of a system and the like.
Disclosure of Invention
Aiming at the defects existing in the prior art, the invention aims to solve the problems that the existing catalyst has lower degradation efficiency on organic pollutants, has narrow applicable pH range, is not easy to recycle and has poor anti-interference capability of a system, and provides a catalyst-containing hydrogel ball which has the advantages of widening the applicable pH range, increasing the anti-interference capability of the system, further improving the absorption capability of the catalyst on visible light and increasing the recycling capability of the catalyst, a preparation method thereof and application thereof in the aspect of photocatalytic treatment on the organic pollutants.
In order to solve the technical problems, the invention adopts the following technical scheme:
in one aspect, the invention provides a method for preparing a hydrogel sphere containing a catalyst, which comprises
Preparing a chitosan solution, wherein the chitosan solution is obtained by adding chitosan into an acetic acid solution;
preparing a sodium alginate glutaraldehyde solution, which comprises the steps of adding sodium alginate into ultra-light water, and then adding the glutaraldehyde solution to obtain the sodium alginate glutaraldehyde solution;
preparing a catalyst graphene gelatin solution, adding gelatin, graphene and a catalyst into ultra-light water, and heating for dissolution to obtain the catalyst graphene gelatin solution;
mixing the chitosan solution with the catalyst graphene gelatin solution, dropwise adding the mixture into the sodium alginate glutaraldehyde solution, and after the mixture is molded, obtaining the catalyst-containing hydrogel spheres;
the catalyst is Pr-CeO with cubic fluorite structure 2 。
Preferably, the mass concentration of chitosan in the chitosan solution is 1%; the mass fraction of gelatin in the graphene gelatin solution is 5% -15%, and the dosage of the catalyst is 0.1g/L-1g/L; the volume fraction of glutaraldehyde in the sodium alginate glutaraldehyde solution is 0.25% -1%.
Preferably, after the chitosan solution and the graphene gelatin solution are mixed, the volume ratio of the gelatin to the chitosan is 5:1-10:1.
Preferably, the catalyst is prepared by the following method:
0.18-0.1M Ce (NO 3 ) 3 ·6H 2 O and 0-0.02M Pr (NO) 3 ) 3 ·6H 2 The mixture of O was mixed with 11.5M NaOH, and after the reaction mixture was reacted at 180℃for 24 hours, it was cooled, centrifuged, washed and dried to obtain the catalyst.
The invention also provides a catalyst-containing hydrogel ball prepared by the preparation method of the catalyst-containing hydrogel ball in any one of the technical schemes.
Preferably, the hydrogel ball containing the catalyst is of a core-shell structure, a layer of sodium alginate shell is wrapped outside a gelatin chitosan spherical framework, graphene is uniformly distributed in the core, and the catalyst is uniformly distributed on the graphene.
The invention also provides application of the catalyst-containing hydrogel sphere in photocatalytic treatment of organic pollutants, wherein the catalyst-containing hydrogel sphere is prepared by any one of the technical schemes.
Preferably, visible light, sodium sulfite and the catalyst-containing hydrogel spheres are utilized to photo-catalytically treat organic pollutants.
Preferably, the concentration of the sodium sulfite is 5g/L.
Preferably, the power of the visible light is 30mW, and the dosage of the hydrogel ball containing the catalyst is 50 particles.
Compared with the prior art, the invention has the beneficial effects that:
the hydrogel ball containing the catalyst provided by the invention has the advantages that the hydrogel is used for wrapping the catalyst, so that the catalyst is convenient to recycle, the catalyst is protected, the catalyst is prevented from being damaged by too violent reaction when the catalyst reacts with pollutants, the service life of the catalyst is reduced, the hydrogel is wrapped for playing a buffering role, and the service life of the catalyst can be prolonged;
the invention also provides application of the hydrogel ball containing the catalyst in the aspect of photocatalytic treatment of organic pollutants, and the hydrogel ball containing the catalyst has the characteristics of wide applicable pH range, strong anti-interference capability of a system and strong absorption capability of visible light.
Drawings
FIG. 1 is a diagram showing the reaction mechanism of a catalyst-containing hydrogel sphere according to an embodiment of the present invention in the photocatalytic treatment of organic pollutants;
FIG. 2 is a graph showing the effect of photocatalytic degradation of methylene blue by the catalyst-containing hydrogel spheres according to example 1 of the present invention;
FIG. 3 is a graph showing the effect of photocatalytic degradation of methyl violet by the catalyst-containing hydrogel pellets according to example 1 of the present invention;
FIG. 4 is a graph showing the effect of photocatalytic degradation of methyl orange by the catalyst-containing hydrogel pellets according to example 1 of the present invention;
FIG. 5 is a graph showing the effect of photocatalytic degradation of malachite green by the catalyst-containing hydrogel pellets according to example 1 of the present invention;
FIG. 6 is a graph showing the effect of photocatalytic degradation of methyl orange by the catalyst-containing hydrogel pellets according to example 2 of the present invention;
fig. 7 is a graph showing the effect of photocatalytic degradation of methyl orange by the catalyst-containing hydrogel pellets according to example 3 of the present invention.
Detailed Description
The following detailed description of the technical solutions in the specific embodiments of the present invention will be given with reference to the accompanying drawings. It is apparent that the described embodiments are only some specific implementations, but not all implementations, of the general technical solution of the present invention. All other embodiments, which are obtained by those skilled in the art based on the general inventive concept, fall within the scope of the present invention.
In one aspect, the invention provides a method for preparing a hydrogel sphere containing a catalyst, which comprises
Preparing a chitosan solution, wherein the chitosan solution is obtained by adding chitosan into an acetic acid solution;
preparing a sodium alginate glutaraldehyde solution, which comprises the steps of adding sodium alginate into ultra-light water, and then adding the glutaraldehyde solution to obtain the sodium alginate glutaraldehyde solution;
preparing a catalyst graphene gelatin solution, adding gelatin, graphene and a catalyst into ultra-light water, and heating for dissolution to obtain the catalyst graphene gelatin solution;
mixing the chitosan solution with the catalyst graphene gelatin solution, dropwise adding the mixture into the sodium alginate glutaraldehyde solution, and after the mixture is molded, obtaining the catalyst-containing hydrogel spheres;
the catalyst is Pr-CeO with cubic fluorite structure 2 。
The technical proposalThe prepared hydrogel ball presents a core-shell structure, namely, a layer of sodium alginate shell is wrapped outside a gelatin chitosan spherical framework, and the shell can help the hydrogel ball to buffer solution shearing force and collision force with a cup wall in the stirring process, so that the hydrogel ball cannot be damaged. In addition, graphene is further added into the hydrogel, the three-dimensional network structure of the graphene can enable the microstructure of the hydrogel to be more three-dimensional, the mechanical strength of the hydrogel pellets can be further improved, and the catalyst can be attached to the graphene sheet, so that the hydrogel has better dispersion degree and cannot be aggregated. The technical proposal specifically limits that the catalyst is Pr-CeO with cubic fluorite structure 2 The catalyst with the cubic fluorite structure has more stable property and has more recyclable value.
In a preferred embodiment, the mass concentration of chitosan in the chitosan solution is 1%; the mass fraction of gelatin in the graphene gelatin solution is 5% -15%, and the dosage of the catalyst is 0.1g/L-1g/L; the volume fraction of glutaraldehyde in the sodium alginate glutaraldehyde solution is 0.25% -1%. The technical proposal specifically limits the dosage of each raw material, because the dosage of each raw material affects the structure of the hydrogel sphere, the mechanical strength of the hydrogel sphere and the catalytic activity of the catalyst. It is understood that the mass fraction of gelatin in the graphene gelatin solution of the catalyst can be 7%, 9%, 11%, 13% and any point value in the range thereof, the catalyst can be used in an amount of 0.2g/L, 0.3g/L, 0.4g/L, 0.5g/L, 0.6g/L, 0.7g/L, 0.8g/L, 0.9g/L and any point value in the range thereof, and the volume fraction of glutaraldehyde in the glutaraldehyde solution of the sodium alginate can be 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9% and any point value in the range thereof. Preferably, the mass fraction of gelatin in the graphene gelatin solution is 10%, the dosage of the catalyst is 1g/L, the volume fraction of glutaraldehyde in the sodium alginate glutaraldehyde solution is 0.5%, and the dosage ratio of gelatin to chitosan is 10:1.
In a preferred embodiment, after the chitosan solution and the graphene gelatin solution are mixed, the volume ratio of the gelatin to the chitosan is 5:1-10:1. The technical scheme specifically limits the dosage ratio of gelatin to chitosan, because the optimal mechanical strength and the optimal degradation effect can be considered in the ratio. It will be appreciated that the ratio may also be any point value ratio within the 6:1, 7:1, 8:1, 9:1 and ranges thereof.
In a preferred embodiment, the catalyst is prepared by the following method:
0.18-0.1M Ce (NO 3 ) 3 ·6H 2 O and 0-0.02M Pr (NO) 3 ) 3 ·6H 2 The mixture of O was mixed with 11.5M NaOH, and after the reaction mixture was reacted at 180℃for 24 hours, it was cooled, centrifuged, washed and dried to obtain the catalyst. Further, the method also comprises a calcination step, specifically, the flow rate is 60mL/min at 600 ℃ and 5% O 2 Calcining for 1h in He atmosphere to obtain the catalyst. Preferably, ce (NO 3 ) 3 ·6H 2 O concentration of 0.094M, pr (NO 3 ) 3 ·6H 2 The concentration of O was 0.01M. Ce (NO 3 ) 3 ·6H 2 O and Pr (NO) 3 ) 3 ·6H 2 The adding proportion of O can influence the crystal form of the product, and the too high Pr (NO 3 ) 3 ·6H 2 O can change the crystal form of the product, a part of the product becomes nano rod-shaped when the product is added in an amount of 20%, and in addition, the preparation of the calcined sample is closely related to the reaction time, the temperature and the gas composition and the flow rate. The catalyst prepared by the method is found out by TEM characterization result to be 10 percent Pr-CeO 2 The perfect cube structure is presented, and the mapping result shows that Pr and Ce are uniformly doped together, which indicates that Pr is substituted for Ce to enter CeO 2 In the crystal lattice of (a) and does not change CeO 2 The original crystal form. After calcination at 600 ℃,10% Pr-CeO 2 The face of the O600 cube became a saw-tooth structure, which provided more active sites, and according to the crystal plane analysis, as shown in Table 1, transformation of {100} crystal plane to {110} crystal plane occurred after calcination, and {110} crystal plane had higher activity.
TABLE 1 Crystal face analysis results of catalysts with different Pr doping amounts
The invention also provides a catalyst-containing hydrogel ball prepared by the preparation method of the catalyst-containing hydrogel ball in any one of the technical schemes. Preferably, the hydrogel ball containing the catalyst is of a core-shell structure, a layer of sodium alginate shell is wrapped outside a gelatin chitosan spherical framework, graphene is uniformly distributed in the core, and the catalyst is uniformly distributed on the graphene. It should be noted that the hydrogel prepared by the technology is not a conventional simple hydrogel, and has a core-shell structure, namely, a spherical gelatin chitosan skeleton is coated with a layer of sodium alginate shell, and the shell can help hydrogel pellets to buffer solution shearing force and collision force with a cup wall in the stirring process, so that the hydrogel pellets cannot be damaged. In addition, graphene is further added into the hydrogel, the three-dimensional network structure of the graphene can enable the microstructure of the hydrogel to be more three-dimensional, the mechanical strength of the hydrogel pellets can be further improved, and the catalyst can be attached to the graphene sheet, so that the hydrogel has better dispersion degree and cannot be aggregated.
The invention also provides application of the catalyst-containing hydrogel sphere in photocatalytic treatment of organic pollutants, wherein the catalyst-containing hydrogel sphere is prepared by any one of the technical schemes. During application, the hydrogel is used for wrapping the catalyst, so that the catalyst is convenient to recycle, the catalyst is protected, the violent reaction of the catalyst and pollutants is avoided, the catalyst is damaged by the violent reaction, the service life of the catalyst is reduced, the hydrogel is wrapped for buffering, and the service life of the catalyst can be prolonged.
In a preferred embodiment, visible light, sodium sulfite and the catalyst-containing hydrogel spheres are utilized to photo-catalytically treat organic contaminants. In this system, pr-CeO 2 After irradiation by visible light, electrons are transited from valence band to conduction band through intermediate energy level, the electrons of the conduction band react with dissolved oxygen to generate superoxide anion, and holes of the valence band activate sodium sulfite to lead the sodium sulfite to be finalGenerating SO4 ] – Superoxide anion and SO4 ] – Together with organic pollutants, the organic pollutants are thoroughly decomposed, and the reaction mechanism diagram is shown in figure 1. The active species generated by the combination of the catalyst and sodium sulfite is SO4 · – ，SO4· – Has a higher redox potential (2.5-3.1V) than hydroxyl radicals, and a longer lifetime t 1/2 =30-40 μs, better selectivity (easy reaction with aromatic organics with unsaturated bonds and pi electrons) and stronger anti-interference ability. When the sodium sulfite is used, the dosage of the sodium sulfite needs to be controlled, the lower sodium sulfite has poor effect, and the excessive sodium sulfite can compete with organic pollutants for active free radicals to reduce degradation efficiency. Optionally, the concentration of the sodium sulfite is 5g/L.
In a preferred embodiment, the power of the visible light is 30mW, and the amount of the catalyst-containing hydrogel spheres is 50. Specifically, 50 Pr-CeO particles are used 2 The hydrogel pellets were mixed with 50mL of 40mg/L methyl orange solution, followed by 5g/L Na 2 SO 3 Stirring under 30mW of visible light irradiation, sampling at intervals, detecting ultraviolet spectrum, and observing absorbance change at 464 nm. The visible light source is provided by a xenon lamp provided with a 420nm optical filter, and the current and the height of the xenon lamp are regulated by an optical power meter, so that the light intensity of the light irradiated to the reaction liquid level is ensured to be 30mW/cm 2 . The photocatalyst used by the method has good visible light absorption performance, and the level almost consistent with the ultraviolet absorption capacity can be achieved only by 10% Pr doping amount; the active species produced was SO4 · – ，SO4· – Has higher oxidation-reduction potential, longer service life and better selectivity (easy reaction with aromatic organic matters with unsaturated bonds and pi electrons) than hydroxyl free radicals and stronger anti-interference capability; the pH value range is wide (pH value is 4-10), and the degradation efficiency on organic pollutants such as methyl orange is good; the anti-interference capability is strong, and common anions in the wastewater can not inhibit the degradation effect of the system; the hydrogel pellets are convenient to recycle and have good recycling capability.
In order to more clearly describe the catalyst-containing hydrogel spheres, the preparation method thereof and the application thereof in the photocatalytic treatment of organic pollutants provided in the embodiments of the present invention in detail, the following description will be made with reference to specific embodiments.
Example 1
1. Preparation of the catalyst
Will be 0.094M Ce (NO 3 ) 3 ·6H 2 O and 0.01M Pr (NO) 3 ) 3 ·6H 2 Mixing the mixture of O with 11.5M NaOH, reacting the reaction mixture at 180deg.C for 24 hr, cooling the mixture to room temperature, centrifuging, washing with deionized water and absolute ethanol, and oven drying the sample at 80deg.C for 24 hr, 600deg.C at a flow rate of 60mL/min at 5% O 2 Calcining for 1 hour in He atmosphere to obtain a catalyst;
2. preparation of catalyst-containing hydrogel spheres
Preparing a chitosan solution, diluting 0.25mL of acetic acid solution to 25mL to obtain an acetic acid solution with a volume fraction of 1%, and adding 0.25g of chitosan to obtain a 1% chitosan solution;
preparing sodium alginate glutaraldehyde solution, adding 0.25g of sodium alginate into 25mL of the solution, and adding 0.5mL of the solution of 25% glutaraldehyde to obtain sodium alginate glutaraldehyde solution;
preparing a catalyst graphene gelatin solution, mixing 2.5g gelatin with 0.025g graphene and 0.025g Pr-CeO 2 Adding the graphene and the gelatin into 25mLDDW together, and heating and dissolving to obtain a catalyst graphene gelatin solution;
mixing a chitosan solution and a catalyst graphene gelatin solution according to a volume ratio of 1:10, dropwise adding the mixture into a sodium alginate glutaraldehyde solution, and after the mixture is molded, obtaining a catalyst-containing hydrogel sphere;
wherein the mass fraction of gelatin in the graphene gelatin solution is 10%, the dosage of the catalyst is 1g/L, the volume fraction of glutaraldehyde in the sodium alginate glutaraldehyde solution is 0.5%, and the dosage ratio of gelatin to chitosan is 10:1.
Example 2
The procedure for preparing the catalyst was as in example 1, except that Ce (NO 3 ) 3 ·6H 2 The concentration of O was 0.095M,Pr(NO 3 ) 3 ·6H 2 the concentration of O is 0.005M;
the procedure for the preparation of the catalyst-containing hydrogels was as in example 1.
Example 3
The procedure for preparing the catalyst was as in example 1, except that Ce (NO 3 ) 3 ·6H 2 O concentration is 0.085M, pr (NO 3 ) 3 ·6H 2 The concentration of O is 0.015M;
the procedure for the preparation of the catalyst-containing hydrogels was as in example 1.
Example 4
The procedure for the preparation of the catalyst was as in example 1;
the procedure for the preparation of the catalyst-containing hydrogels was as in example 1, except that the mass fraction of gelatin was changed to 2.5%, the volume fraction of glutaraldehyde was 0.25%, and the gelatin to chitosan ratio was 2.5:1.
Example 5
The procedure for the preparation of the catalyst was as in example 1,
the procedure for the preparation of the catalyst-containing hydrogel was as in example 1, except that the mass fraction of gelatin was changed to 5% and the volume fraction of glutaraldehyde was 0.25%
Example 6
The procedure for the preparation of the catalyst was as in example 1,
the procedure for the preparation of the catalyst-containing hydrogels was as in example 1, except that the glutaraldehyde volume fraction was 0.25%
Performance testing
Observations of the catalyst-containing hydrogel spheres prepared in examples 1 to 6 show that the catalyst-containing hydrogel spheres prepared in examples 1 to 3 have good mechanical strength and the hydrogel spheres prepared in examples 4 to 6 have poor mechanical strength; further, the catalyst-containing hydrogel spheres prepared in examples 1 to 3 were subjected to a photocatalytic test, as follows:
the catalyst-containing hydrogel pellets prepared in example 1 were subjected to a photocatalytic experiment, in particular: 50 Pr-CeO particles each 2 The hydrogel pellets are respectively mixed with 50mL of 40mg/L methyl orange solution, methylene blue and malachite greenMixing with methyl violet, and adding 5g/L Na 2 SO 3 Stirring under 30mW of visible light irradiation, sampling at intervals, detecting ultraviolet spectrum, and observing absorbance change at 464 nm. The visible light source is provided by a xenon lamp provided with a 420nm optical filter, and the current and the height of the xenon lamp are regulated by an optical power meter, so that the light intensity of the light irradiated to the reaction liquid level is ensured to be 30mW/cm 2 The degradation effect is shown in figures 2-5.
The photocatalytic experiment was performed on the catalyst-containing hydrogel pellets prepared in example 2, and the degradation effect is shown in fig. 6.
The photocatalytic experiment was performed on the catalyst-containing hydrogel pellets prepared in example 3, and the degradation effect is shown in fig. 7.
Claims (9)
1. A preparation method of a hydrogel ball containing a catalyst is characterized by comprising the following steps of
Preparing a chitosan solution, wherein the chitosan solution is obtained by adding chitosan into an acetic acid solution;
preparing a sodium alginate glutaraldehyde solution, which comprises the steps of adding sodium alginate into ultra-light water, and then adding the glutaraldehyde solution to obtain the sodium alginate glutaraldehyde solution;
preparing a catalyst graphene gelatin solution, adding gelatin, graphene and a catalyst into ultra-light water, and heating for dissolution to obtain the catalyst graphene gelatin solution;
mixing the chitosan solution with the catalyst graphene gelatin solution, dropwise adding the mixture into the sodium alginate glutaraldehyde solution, and after the mixture is molded, obtaining the catalyst-containing hydrogel spheres;
the catalyst is Pr-CeO with cubic fluorite structure 2 。
2. The method for preparing the catalyst-containing hydrogel spheres according to claim 1, wherein the mass concentration of chitosan in the chitosan solution is 1%; the mass fraction of gelatin in the graphene gelatin solution is 5% -15%, and the dosage of the catalyst is 0.1g/L-1g/L; the volume fraction of glutaraldehyde in the sodium alginate glutaraldehyde solution is 0.25% -1%.
3. The method for preparing the hydrogel sphere containing the catalyst according to claim 1, wherein the catalyst is prepared by the following method:
0.18-0.1M Ce (NO 3 ) 3 ·6H 2 O and 0-0.02M Pr (NO) 3 ) 3 ·6H 2 The mixture of O was mixed with 11.5M NaOH, and after the reaction mixture was reacted at 180℃for 24h, it was cooled, centrifuged, washed and dried to obtain the catalyst.
4. A catalyst-containing hydrogel pellet prepared by the method of any one of claims 1 to 3.
5. The catalyst-containing hydrogel sphere according to claim 4, wherein the catalyst-containing hydrogel sphere is of a core-shell structure, a layer of sodium alginate shell is wrapped outside a gelatin chitosan spherical framework, graphene is uniformly distributed in a core, and the catalyst is uniformly distributed on the graphene.
6. Use of catalyst-containing hydrogel spheres for the photocatalytic treatment of organic pollutants, characterized in that the catalyst-containing hydrogel spheres are according to any of claims 4 to 5.
7. The use of the catalyst-containing hydrogel pellets according to claim 6 for the photocatalytic treatment of organic contaminants using visible light, sodium sulfite and the catalyst-containing hydrogel pellets.
8. The use of the catalyst-containing hydrogel pellets according to claim 7 for the photocatalytic treatment of organic contaminants, wherein the concentration of sodium sulfite is 5g/L.
9. The use of the catalyst-containing hydrogel pellets according to claim 7 for photocatalytic treatment of organic contaminants, wherein the visible light power is 30mW and the catalyst-containing hydrogel pellets are used in an amount of 50 pellets.
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