CN111151242A - Preparation method of cerium-manganese metal ion modified aluminate photocatalyst - Google Patents
Preparation method of cerium-manganese metal ion modified aluminate photocatalyst Download PDFInfo
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- CN111151242A CN111151242A CN202010047639.0A CN202010047639A CN111151242A CN 111151242 A CN111151242 A CN 111151242A CN 202010047639 A CN202010047639 A CN 202010047639A CN 111151242 A CN111151242 A CN 111151242A
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- 239000011941 photocatalyst Substances 0.000 title claims abstract description 70
- 150000004645 aluminates Chemical class 0.000 title claims abstract description 29
- YOSLGHBNHHKHST-UHFFFAOYSA-N cerium manganese Chemical compound [Mn].[Mn].[Mn].[Mn].[Mn].[Ce] YOSLGHBNHHKHST-UHFFFAOYSA-N 0.000 title claims abstract description 23
- 229910021645 metal ion Inorganic materials 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims abstract description 18
- 150000000703 Cerium Chemical class 0.000 claims abstract description 18
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 18
- 150000002696 manganese Chemical class 0.000 claims abstract description 16
- ZIUHHBKFKCYYJD-UHFFFAOYSA-N n,n'-methylenebisacrylamide Chemical compound C=CC(=O)NCNC(=O)C=C ZIUHHBKFKCYYJD-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000005245 sintering Methods 0.000 claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 12
- 238000001035 drying Methods 0.000 claims abstract description 8
- 239000002738 chelating agent Substances 0.000 claims abstract description 7
- 229910052684 Cerium Inorganic materials 0.000 claims abstract description 6
- 238000001816 cooling Methods 0.000 claims abstract description 3
- 238000005303 weighing Methods 0.000 claims description 32
- 239000003153 chemical reaction reagent Substances 0.000 claims description 20
- 239000011572 manganese Substances 0.000 claims description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- 239000008367 deionised water Substances 0.000 claims description 10
- 229910021641 deionized water Inorganic materials 0.000 claims description 10
- 150000004676 glycans Chemical class 0.000 claims description 10
- 238000000227 grinding Methods 0.000 claims description 10
- 229920001282 polysaccharide Polymers 0.000 claims description 10
- 239000005017 polysaccharide Substances 0.000 claims description 10
- 239000006228 supernatant Substances 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 238000012719 thermal polymerization Methods 0.000 claims description 9
- 150000003839 salts Chemical class 0.000 claims description 8
- 239000000843 powder Substances 0.000 claims description 5
- -1 cerium ions Chemical class 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- 150000007522 mineralic acids Chemical class 0.000 claims description 4
- 150000002500 ions Chemical class 0.000 claims description 3
- 229910052748 manganese Inorganic materials 0.000 claims description 3
- URDCARMUOSMFFI-UHFFFAOYSA-N 2-[2-[bis(carboxymethyl)amino]ethyl-(2-hydroxyethyl)amino]acetic acid Chemical class OCCN(CC(O)=O)CCN(CC(O)=O)CC(O)=O URDCARMUOSMFFI-UHFFFAOYSA-N 0.000 claims description 2
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical class OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 2
- 239000004593 Epoxy Substances 0.000 claims description 2
- QPCDCPDFJACHGM-UHFFFAOYSA-N N,N-bis{2-[bis(carboxymethyl)amino]ethyl}glycine Chemical class OC(=O)CN(CC(O)=O)CCN(CC(=O)O)CCN(CC(O)=O)CC(O)=O QPCDCPDFJACHGM-UHFFFAOYSA-N 0.000 claims description 2
- 150000001412 amines Chemical class 0.000 claims description 2
- 229910052788 barium Inorganic materials 0.000 claims description 2
- 229910052793 cadmium Inorganic materials 0.000 claims description 2
- 229910052791 calcium Inorganic materials 0.000 claims description 2
- 238000005352 clarification Methods 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 239000012535 impurity Substances 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 229910052749 magnesium Inorganic materials 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 229910052758 niobium Inorganic materials 0.000 claims description 2
- 229910052697 platinum Inorganic materials 0.000 claims description 2
- 230000000379 polymerizing effect Effects 0.000 claims description 2
- 229910052703 rhodium Inorganic materials 0.000 claims description 2
- 229910052707 ruthenium Inorganic materials 0.000 claims description 2
- 229910052712 strontium Inorganic materials 0.000 claims description 2
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 229910052726 zirconium Inorganic materials 0.000 claims description 2
- 239000007787 solid Substances 0.000 claims 1
- 230000001699 photocatalysis Effects 0.000 abstract description 6
- 230000015572 biosynthetic process Effects 0.000 abstract description 3
- 238000003786 synthesis reaction Methods 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 2
- 229910001437 manganese ion Inorganic materials 0.000 abstract 2
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 abstract 1
- 239000011258 core-shell material Substances 0.000 abstract 1
- 150000007524 organic acids Chemical class 0.000 abstract 1
- VYLVYHXQOHJDJL-UHFFFAOYSA-K cerium trichloride Chemical compound Cl[Ce](Cl)Cl VYLVYHXQOHJDJL-UHFFFAOYSA-K 0.000 description 43
- 229940099596 manganese sulfate Drugs 0.000 description 26
- 235000007079 manganese sulphate Nutrition 0.000 description 26
- 239000011702 manganese sulphate Substances 0.000 description 26
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 26
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 24
- 239000011248 coating agent Substances 0.000 description 21
- 238000000576 coating method Methods 0.000 description 21
- MCPLVIGCWWTHFH-UHFFFAOYSA-L methyl blue Chemical compound [Na+].[Na+].C1=CC(S(=O)(=O)[O-])=CC=C1NC1=CC=C(C(=C2C=CC(C=C2)=[NH+]C=2C=CC(=CC=2)S([O-])(=O)=O)C=2C=CC(NC=3C=CC(=CC=3)S([O-])(=O)=O)=CC=2)C=C1 MCPLVIGCWWTHFH-UHFFFAOYSA-L 0.000 description 15
- 239000000203 mixture Substances 0.000 description 15
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 15
- 229910020068 MgAl Inorganic materials 0.000 description 11
- 229910016010 BaAl2 Inorganic materials 0.000 description 10
- 229910052596 spinel Inorganic materials 0.000 description 9
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 8
- 229910026161 MgAl2O4 Inorganic materials 0.000 description 8
- 239000008103 glucose Substances 0.000 description 8
- 238000003760 magnetic stirring Methods 0.000 description 8
- 238000009210 therapy by ultrasound Methods 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 239000000463 material Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 4
- 229910003303 NiAl2O4 Inorganic materials 0.000 description 3
- 238000013459 approach Methods 0.000 description 2
- 230000000593 degrading effect Effects 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 229910015999 BaAl Inorganic materials 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- RZUBARUFLYGOGC-MTHOTQAESA-L acid fuchsin Chemical compound [Na+].[Na+].[O-]S(=O)(=O)C1=C(N)C(C)=CC(C(=C\2C=C(C(=[NH2+])C=C/2)S([O-])(=O)=O)\C=2C=C(C(N)=CC=2)S([O-])(=O)=O)=C1 RZUBARUFLYGOGC-MTHOTQAESA-L 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 150000001875 compounds Chemical group 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 239000012776 electronic material Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 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
- CEQFOVLGLXCDCX-WUKNDPDISA-N methyl red Chemical compound C1=CC(N(C)C)=CC=C1\N=N\C1=CC=CC=C1C(O)=O CEQFOVLGLXCDCX-WUKNDPDISA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 229920002401 polyacrylamide Polymers 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
- 229940043267 rhodamine b Drugs 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000001308 synthesis method 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
- B01J35/396—Distribution of the active metal ingredient
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/32—Manganese, technetium or rhenium
- B01J23/34—Manganese
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- 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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Abstract
The invention discloses a preparation method of a cerium-manganese metal ion modified aluminate photocatalyst, which takes aluminate as a raw material, cerium salt and manganese salt as modified metal ions, organic acid as a chelating agent to complex cerium or manganese ions, and a proper amount of acrylamide and methylene bisacrylamide are added to carry out polymerization reaction and finally form gel. The method is characterized in that the cerium manganese metal ion modified aluminate photocatalyst with controllable photocatalytic activity and a core-shell structure is prepared by a two-step polymerization mode through the processes of drying, sintering, cooling and the like, and changing the polymerization conditions, the cerium manganese ion ratio, the acrylamide and methylene bisacrylamide ratio, the sintering temperature, the synthesis sequence and the like.
Description
Technical Field
The invention relates to the technical field of preparation of inorganic composite metal oxide materials, in particular to a preparation method of a cerium-manganese metal ion modified aluminate photocatalyst.
Background
Spinel type MAl2O4The aluminate is a very important semiconductor photocatalyst, and has a unique crystal structure and energy band structure, so that the aluminate has extremely high photocatalytic activity in the field of photocatalysis, particularly in the aspect of degrading various organic pollutants. MAl2O4The material is rich, environment friendly, high in chemical stability, low in cost and easy to prepare, and is an important candidate photocatalytic material for industrial application of photocatalytic technology. However, MAl2O4The band gap of the photocatalyst is wide, about 3.9eV, and only ultraviolet light with the wavelength less than 320nm can be absorbed, so that the utilization rate of sunlight is low.
Currently, there are three main approaches to obtaining high efficiency semiconductor photocatalysts:
(1) the separation of photo-generated electron-hole pairs is improved, and the utilization rate of photons is increased;
(2) the spectral response range is expanded, and sunlight is fully utilized;
(3) the surface activity of the photocatalyst is improved.
Therefore, the above approach may be considered to enhance MAl2O4Photocatalytic activity of (1).
Comprehensively considering the three ways, and adopting a mode of compounding Ce and Mn ions to enhance MAL2O4Charge transfer and separation efficiency. MAl synthesized by irradiation-assisted polyacrylamide gel method2O4Ce Mn photocatalyst [ Wang, et al, journal of electronic Materials,2019,48(10): 6675-6685-]The method successfully synthesizes the photocatalyst and improves MAL2O4Photocatalytic activity of (1). However, MAl2O4MAl prepared by this method, which is easily hydrolyzed when used as a photocatalyst2O4MAl in Ce: Mn photocatalyst2O4Exists in a compound form, and does not solve the problem of easy hydrolysis. Thus, the synthesis method is improved to synthesize the MAL with a multi-layer coating structure2O4Ce: Mn photocatalyst is a major challenge.
Disclosure of Invention
In order to solve the technical problems, the technical scheme provided by the invention is as follows: a preparation method of a cerium manganese metal ion modified aluminate photocatalyst comprises the following steps:
step 1: weighing 0.1-2g of MAL2O4Putting aluminate into a beaker, adding M which is one of Mg, Ca, Sr, Ba, Mn, Fe, Co, Ni, Cu, Zn, Nb, Zr, Cd, Ga, Pd, Ru, Rh and Pt, adding a certain amount of alcohol for ultrasonic dispersion for 0.5-3 hours, standing for clarification, and pouring out supernatant.
Step 2: adding 20-40mL of deionized water into the beaker in the step (1), weighing 6.5235g of cerium salt, and slowly adding the cerium salt into the solution; then weighing a certain amount of organic chelating agent, wherein the molar ratio of the chelating agent to cerium ions is 15: 1-1: 5; after the polysaccharide is completely dissolved, 0-100g of polysaccharide is weighed and used as a collapsing agent for preventing collapse and added into the solution; then, adding an acrylamide monomer and methylene bisacrylamide, wherein the molar ratio of the acrylamide monomer to cerium ions is 1: 5-5: 1, and the mass ratio of the methylene bisacrylamide to acrylamide is 0: 1-1: 10, and continuously adding the acrylamide monomer and the methylene bisacrylamide after the former reagent is completely dissolved;
and step 3: after the reagent in the step (2) is completely dissolved, polymerizing by adopting different polymerization modes to obtain gel; transferring the obtained gel into a drying oven, and drying at the constant temperature of 80-200 ℃ for 24-120 hours to obtain dry gel; after cooling to room temperature, taking out the dry gel, grinding the dry gel into powder, and sintering part of the powder at 400-1400 ℃ for 2-72 hours to obtain MAL2O4Ce photocatalyst, noted as sample A.
And 4, step 4: weighing 0.1-3 g of the sample A in the step (3), repeating the steps 1-3, and keeping the other steps consistent except that the cerium salt weighed in the step (2) is modified into manganese salt; drying and sintering to obtain MAL2O4Ce is Mn photocatalyst, noteSample B was obtained.
Preferably, the inorganic chelating agent in the step (2) is one of NTA series, EDTA series, DTPA series, amine series, HEDTA series, or epoxy curing agent series, and cannot introduce new metal impurity ions.
Preferably, the polymerization mode in the step (3) is thermal polymerization, ultraviolet polymerization or irradiation polymerization.
Preferably, the cerium salt in step (2) is one of salts composed of inorganic acid or organic acid radical, the polysaccharide is one of homogeneous polysaccharide or heterogeneous polysaccharide, and the manganese salt in step (4) is one of salts composed of inorganic acid or organic acid radical.
Preferably, the MAL2O4The molar ratio of Ce to Ce salt is 0: 1-9: 1; the molar ratio of the Ce salt to the manganese salt can be 0: 1-9: 1.
Preferably, the MAL synthesized in said step (4)2O4The Ce-Mn photocatalyst forms a multi-layer coated structure.
The invention has the beneficial effects that:
1. the invention synthesizes MAl with a multilayer coating structure by taking aluminate as a core and cerium salt and manganese salt as outer coating materials2O4Ce is Mn photocatalyst, which effectively solves the problem that aluminate is easy to hydrolyze when used as photocatalyst.
2. The invention has wide raw material selection range, and the polymerization mode can be selected according to the self condition of a laboratory, thereby realizing the economical use of resources. The morphology and photocatalytic activity of the powder sample can be controlled and synthesized by adjusting experimental parameters, large-scale production can be realized, the repeatability is good, and the method can be used for degrading organic pollution dyes such as methyl blue, methyl orange, rhodamine B, methyl red, acid fuchsin and the like.
Drawings
FIG. 1 is a MAl with a multilayer coating structure prepared by the method for preparing a cerium manganese metal ion modified aluminate photocatalyst2O4A preparation flow chart of the Ce-Mn photocatalyst is provided.
FIG. 2 shows a cerium manganese metal ion modified aluminate photocatalyst of the present inventionPreparation method of 0.1MAL of multilayer coating structure2O40.8Ce:0.1Mn photocatalyst.
FIG. 3 is 0.1MAL of multi-layer coating structure of preparation method of cerium manganese metal ion modified aluminate photocatalyst2O40.8Ce to 0.1 Mn.
FIGS. 1-3 are intended to be illustrative, and are presented in the form of schematic illustrations only, rather than in physical illustrations, and should not be construed as limiting the present invention; to better illustrate the embodiments of the present invention, some parts of the drawings may be omitted, enlarged or reduced, and do not represent the size of an actual product; it will be understood by those skilled in the art that certain well-known structures in the drawings and descriptions thereof may be omitted.
Detailed Description
The embodiments of the present invention are described below with reference to specific embodiments, and other advantages and effects of the present invention will be easily understood by those skilled in the art from the disclosure of the present specification. The invention is capable of other and different embodiments and of being practiced or of being carried out in various ways, and its several details are capable of modification in various respects, all without departing from the spirit and scope of the present invention. It should be noted that the drawings provided in the following embodiments are only for illustrating the basic idea of the present invention in a schematic way, and the features in the following embodiments and examples may be combined with each other without conflict.
Wherein the showings are for the purpose of illustrating the invention only and not for the purpose of limiting the same, and in which there is shown by way of illustration only and not in the drawings in which there is no intention to limit the invention thereto; to better illustrate the embodiments of the present invention, some parts of the drawings may be omitted, enlarged or reduced, and do not represent the size of an actual product; it will be understood by those skilled in the art that certain well-known structures in the drawings and descriptions thereof may be omitted.
The first embodiment is as follows:
a preparation method of a cerium manganese metal ion modified aluminate photocatalyst comprises the following steps:
step 1: taking a beaker with the scale of 100mL,adding a cerium salt (cerium chloride) and manganese salt (manganese sulfate) in a molar ratio of 0.1: 0.9 of MgAl2O4Adding 20mL of alcohol into the mixture, and performing ultrasonic treatment in an ultrasonic instrument for half an hour, wherein the molar ratio of cerium chloride to manganese sulfate is 0.8: 0.1; subsequently, it was taken out, left to stand for 12 hours, and the supernatant was poured off.
Step 2: adding 20mL of deionized water into the beaker, weighing 0.8 part of cerium chloride, and adding the cerium chloride into the beaker for magnetic stirring; after the mixture was completely dissolved, 4.728g of citric acid, 20g of glucose, 9.5959g of acrylamide and 1.9192g of methylenebisacrylamide were added, and each reagent was added until the last reagent was completely dissolved.
And step 3: under the condition of thermal polymerization at 80 ℃, a gel was obtained. The obtained gel was dried at a constant temperature of 120 ℃ for about 24 hours to obtain a black xerogel. Grinding part of the black xerogel, and sintering the ground black xerogel for 5 hours at 700 ℃ in a box-type furnace to obtain MgAl2O4Ce photocatalyst.
And 4, step 4: MgAl obtained in the step 32O4Repeating the steps 1-3 by the Ce photocatalyst, and only changing the weighing of 0.8 part of cerium chloride in the step 2 into the weighing of 0.1 part of manganese sulfate to obtain 0.1MgAl with a multilayer coating structure2O40.8Ce to 0.1Mn photocatalyst, the photocatalytic degradation percentage of which reaches 95.3 percent after the methyl blue is illuminated for 3.5 hours.
Example two:
a preparation method of a cerium manganese metal ion modified aluminate photocatalyst comprises the following steps:
step 1: taking a beaker with the scale of 100mL, adding a cerium salt (cerium chloride) and manganese salt (manganese sulfate) in a molar ratio of 0.1: 0.9 BaAl2O4Adding 20mL of alcohol into the mixture, and performing ultrasonic treatment in an ultrasonic instrument for half an hour, wherein the molar ratio of cerium chloride to manganese sulfate is 0.8: 0.1; subsequently, it was taken out, left to stand for 12 hours, and the supernatant was poured off.
Step 2: adding 20mL of deionized water into the beaker, weighing 0.8 part of cerium chloride, and adding the cerium chloride into the beaker for magnetic stirring; after the mixture was completely dissolved, 4.728g of citric acid, 20g of glucose, 9.5959g of acrylamide and 1.9192g of methylenebisacrylamide were added, and each reagent was added until the last reagent was completely dissolved.
And step 3: under the condition of thermal polymerization at 80 ℃, a gel was obtained. The obtained gel was dried at a constant temperature of 120 ℃ for about 24 hours to obtain a black xerogel. Grinding part of the black xerogel, and sintering the ground black xerogel for 5 hours at 700 ℃ in a box-type furnace to obtain BaAl2O4Ce photocatalyst.
And 4, step 4: BaAl obtained in the step 32O4Repeating the steps 1-3 by the Ce photocatalyst, and only changing the weighing of 0.8 part of cerium chloride in the step 2 into the weighing of 0.1 part of manganese sulfate to obtain 0.1BaAl with a multilayer coating structure2O40.8Ce to 0.1Mn photocatalyst, the photocatalytic degradation percentage of which reaches 82.6 percent after the methyl blue is illuminated for 3.5 hours.
Comparative example one and example two: changing MgAl in step 12O4Is BaAl2O4After synthesis, 0.1BaAl with multilayer coating structure is obtained2O40.8Ce:0.9Mn luminescent material, its XRD phase structure mainly uses BaAl2O4The phase is main, and the photocatalytic degradation percentage reaches 82.6 percent after the methyl blue is illuminated for 3.5 hours.
Example three:
a preparation method of a cerium manganese metal ion modified aluminate photocatalyst comprises the following steps:
step 1: taking a beaker with the scale of 100mL, adding a cerium salt (cerium chloride) and manganese salt (manganese sulfate) in a molar ratio of 0.1: 0.9 of MgAl2O4Adding 20mL of alcohol into the mixture, and performing ultrasonic treatment in an ultrasonic instrument for half an hour, wherein the molar ratio of cerium chloride to manganese sulfate is 0.8: 0.1; subsequently, it was taken out, left to stand for 12 hours, and the supernatant was poured off.
Step 2: adding 20mL of deionized water into the beaker, weighing 0.8 part of cerium chloride, and adding the cerium chloride into the beaker for magnetic stirring; after the mixture was completely dissolved, 4.728g of citric acid, 20g of glucose, 9.5959g of acrylamide and 1.9192g of methylenebisacrylamide were added, and each reagent was added until the last reagent was completely dissolved.
And step 3: a gel was obtained under conditions of radiation polymerization at 80 ℃. The obtained gel was dried at a constant temperature of 120 ℃ for about 24 hours to obtain a black xerogel. Grinding part of the black xerogel, and sintering the ground black xerogel for 5 hours at 700 ℃ in a box-type furnace to obtain MgAl2O4Ce photocatalyst.
And 4, step 4: MgAl obtained in the step 32O4Repeating the steps 1-3 by the Ce photocatalyst, and only changing the weighing of 0.8 part of cerium chloride in the step 2 into the weighing of 0.1 part of manganese sulfate to obtain 0.1MgAl with a multilayer coating structure2O40.8Ce to 0.1Mn photocatalyst, the photocatalytic degradation percentage of which reaches 92 percent after 2.5 hours of irradiation of methyl blue.
Comparative example one and example three: changing the mode of thermal polymerization into irradiation polymerization in the step 3, and obtaining the 0.1MgAl with a multilayer coating structure after sintering2O40.8Ce to 0.1Mn photocatalyst, the photocatalytic degradation percentage of which reaches 92 percent after 2.5 hours of irradiation of methyl blue.
Example four:
a preparation method of a cerium manganese metal ion modified aluminate photocatalyst comprises the following steps:
step 1: taking a beaker with the scale of 100mL, adding a cerium salt (cerium chloride) and manganese salt (manganese sulfate) in a molar ratio of 0.1: 0.9 of MgAl2O4Adding 20mL of alcohol into the mixture, and performing ultrasonic treatment in an ultrasonic instrument for half an hour, wherein the molar ratio of cerium chloride to manganese sulfate is 0.8: 0.1; subsequently, it was taken out, left to stand for 12 hours, and the supernatant was poured off.
Step 2: adding 20mL of deionized water into the beaker, weighing 0.8 part of cerium chloride, and adding the cerium chloride into the beaker for magnetic stirring; after the mixture was completely dissolved, 4.728g of citric acid, 20g of glucose, 9.5959g of acrylamide and 1.9192g of methylenebisacrylamide were added, and each reagent was added until the last reagent was completely dissolved.
And step 3: under the condition of ultraviolet photopolymerization at 80 ℃, gel is obtained. Drying the obtained gel at constant temperature of 120 deg.C24 hours, a black xerogel was obtained. Grinding part of the black xerogel, and sintering the ground black xerogel for 5 hours at 700 ℃ in a box-type furnace to obtain MgAl2O4Ce photocatalyst.
And 4, step 4: MgAl obtained in the step 32O4Repeating the steps 1-3 by the Ce photocatalyst, and only changing the weighing of 0.8 part of cerium chloride in the step 2 into the weighing of 0.1 part of manganese sulfate to obtain 0.1MgAl with a multilayer coating structure2O40.8Ce to 0.1Mn photocatalyst, the photocatalytic degradation percentage of which reaches 91 percent after the methyl blue is irradiated for 3 hours.
Comparative example one and example four: changing the mode of thermal polymerization into ultraviolet polymerization in the step 3, and obtaining the 0.1MgAl with a multilayer coating structure after sintering2O40.8Ce to 0.1Mn photocatalyst, the photocatalytic degradation percentage of which reaches 91 percent after the methyl blue is irradiated for 3 hours.
Example five:
a preparation method of a cerium manganese metal ion modified aluminate photocatalyst comprises the following steps:
step 1: taking a beaker with the scale of 100mL, adding a cerium salt (cerium chloride) and manganese salt (manganese sulfate) in a molar ratio of 0.1: 0.9 of MgAl2O4Wherein the molar ratio of cerium chloride to manganese sulfate is 0.1:0.8, adding 20mL of alcohol, and performing ultrasonic treatment in an ultrasonic instrument for half an hour; subsequently, it was taken out, left to stand for 12 hours, and the supernatant was poured off.
Step 2: adding 20mL of deionized water into the beaker, weighing 0.8 part of cerium chloride, and adding the cerium chloride into the beaker for magnetic stirring; after the mixture was completely dissolved, 4.728g of citric acid, 20g of glucose, 9.5959g of acrylamide and 1.9192g of methylenebisacrylamide were added, and each reagent was added until the last reagent was completely dissolved.
And step 3: under the condition of thermal polymerization at 80 ℃, a gel was obtained. The obtained gel was dried at a constant temperature of 120 ℃ for about 24 hours to obtain a black xerogel. Grinding part of the black xerogel, and sintering the ground black xerogel for 5 hours at 700 ℃ in a box-type furnace to obtain MgAl2O4Ce photocatalyst.
And 4, step 4: MgAl obtained in the step 32O4Repeating the steps 1-3 by the Ce photocatalyst, and only changing the weighing of 0.8 part of cerium chloride in the step 2 into the weighing of 0.1 part of manganese sulfate to obtain 0.1MgAl with a multilayer coating structure2O40.8Ce to 0.1Mn photocatalyst, the photocatalytic degradation percentage of which reaches 95.3 percent after the methyl blue is illuminated for 3.5 hours.
Comparative example one and example five: changing the molar ratio of cerium chloride to manganese sulfate in the step 1 to 0.8:0.1 to 0.1:0.8, and obtaining the 0.1MgAl with the multilayer coating structure after preparation2O40.1Ce to 0.8Mn photocatalyst, the photocatalytic degradation percentage of which reaches 67.2 percent after the methyl blue is illuminated for 3.5 hours.
Example six:
a preparation method of a cerium manganese metal ion modified aluminate photocatalyst comprises the following steps:
step 1: taking a beaker with the scale of 100mL, adding a cerium salt (cerium chloride) and manganese salt (manganese sulfate) in a molar ratio of 0.1: 0.9 BaAl2O4Adding 20mL of alcohol into the mixture, and performing ultrasonic treatment in an ultrasonic instrument for half an hour, wherein the molar ratio of cerium chloride to manganese sulfate is 0.1: 0.8; subsequently, it was taken out, left to stand for 12 hours, and the supernatant was poured off.
Step 2: adding 20mL of deionized water into the beaker, weighing 0.8 part of cerium chloride, and adding the cerium chloride into the beaker for magnetic stirring; after the mixture was completely dissolved, 4.728g of citric acid, 20g of glucose, 9.5959g of acrylamide and 1.9192g of methylenebisacrylamide were added, and each reagent was added until the last reagent was completely dissolved.
And step 3: under the condition of thermal polymerization at 80 ℃, a gel was obtained. The obtained gel was dried at a constant temperature of 120 ℃ for about 24 hours to obtain a black xerogel. Grinding part of the black xerogel, and sintering the ground black xerogel for 5 hours at 700 ℃ in a box-type furnace to obtain BaAl2O4Ce photocatalyst.
And 4, step 4: MgAl obtained in the step 32O4Repeating the steps 1-3 by the Ce photocatalyst, wherein the weighing of 0.8 part of cerium chloride in the step 2 is only changed into the weighing of 0.1 partManganese sulfate to obtain 0.1BaAl with multilayer coating structure2O40.1Ce to 0.8Mn photocatalyst, the photocatalytic degradation percentage of which reaches 58.7 percent after the methyl blue is illuminated for 3.5 hours.
Comparative example one to example six: changing MgAl in step 12O4Is BaAl2O4And the molar ratio of cerium chloride to manganese sulfate is changed to 0.8:0.1 and 0.1:0.8, so that 0.1BaAl with a multilayer coating structure is obtained after preparation2O40.1Ce to 0.8Mn photocatalyst, the photocatalytic degradation percentage of which reaches 58.7 percent after the methyl blue is illuminated for 3.5 hours.
Example seven:
a preparation method of a cerium manganese metal ion modified aluminate photocatalyst comprises the following steps:
step 1: taking a beaker with the scale of 100mL, adding a cerium salt (cerium chloride) and manganese salt (manganese sulfate) in a molar ratio of 0.1: 0.9 BaAl2O4Adding 20mL of alcohol into the mixture, and performing ultrasonic treatment in an ultrasonic instrument for half an hour, wherein the molar ratio of cerium chloride to manganese sulfate is 0.1: 0.8; subsequently, it was taken out, left to stand for 12 hours, and the supernatant was poured off.
Step 2: adding 20mL of deionized water into the beaker, weighing 0.8 part of cerium chloride, and adding the cerium chloride into the beaker for magnetic stirring; after the mixture was completely dissolved, 4.728g of citric acid, 20g of glucose, 9.5959g of acrylamide and 1.9192g of methylenebisacrylamide were added, and each reagent was added until the last reagent was completely dissolved.
And step 3: a gel was obtained under conditions of radiation polymerization at 80 ℃. The obtained gel was dried at a constant temperature of 120 ℃ for about 24 hours to obtain a black xerogel. Grinding part of the black xerogel, and sintering the ground black xerogel for 5 hours at 700 ℃ in a box-type furnace to obtain BaAl2O4Ce photocatalyst.
And 4, step 4: MgAl obtained in the step 32O4Repeating the steps 1-3 by the Ce photocatalyst, and only changing the weighing of 0.8 part of cerium chloride in the step 2 into the weighing of 0.1 part of manganese sulfate to obtain 0.1BaAl with a multilayer coating structure2O4:0.1Ce:0.8The photocatalytic degradation percentage of the Mn photocatalyst reaches 65.8 percent after methyl blue is illuminated for 3.5 hours.
Comparative example one and example seven: changing MgAl in step 12O4Is BaAl2O4Changing the molar ratio of cerium chloride to manganese sulfate to be 0.8:0.1 to be 0.1:0.8 and changing the polymerization mode to be irradiation polymerization, and obtaining 0.1BaAl with a multilayer coating structure after preparation2O40.1Ce to 0.8Mn photocatalyst, the photocatalytic degradation percentage of which reaches 65.8 percent after the methyl blue is illuminated for 3.5 hours.
Example eight:
a preparation method of a cerium manganese metal ion modified aluminate photocatalyst comprises the following steps:
step 1: taking a beaker with the scale of 100mL, adding a cerium salt (cerium chloride) and manganese salt (manganese sulfate) in a molar ratio of 0.1: 0.9 NiAl2O4Adding 20mL of alcohol into the mixture, and performing ultrasonic treatment in an ultrasonic instrument for half an hour, wherein the molar ratio of cerium chloride to manganese sulfate is 0.8: 0.1; subsequently, it was taken out, left to stand for 12 hours, and the supernatant was poured off.
Step 2: adding 20mL of deionized water into the beaker, weighing 0.8 part of cerium chloride, and adding the cerium chloride into the beaker for magnetic stirring; after the mixture was completely dissolved, 4.728g of citric acid, 20g of glucose, 9.5959g of acrylamide and 1.9192g of methylenebisacrylamide were added, and each reagent was added until the last reagent was completely dissolved.
And step 3: under the condition of thermal polymerization at 80 ℃, a gel was obtained. The obtained gel was dried at a constant temperature of 120 ℃ for about 24 hours to obtain a black xerogel. Grinding part of the black xerogel, and sintering the ground black xerogel for 5 hours at 700 ℃ in a box-type furnace to obtain NiAl2O4Ce photocatalyst.
And 4, step 4: MgAl obtained in the step 32O4Repeating the steps 1-3 by the Ce photocatalyst, and only changing the weighing of 0.8 part of cerium chloride in the step 2 into the weighing of 0.1 part of manganese sulfate to obtain 0.1NiAl with a multilayer coating structure2O40.8Ce to 0.9Mn photocatalyst, the photocatalytic degradation percentage of which is in the light armorThe bluish color reached 93.5% after 3.5 hours.
Comparative example one and example eight: changing MgAl in step 12O4Is NiAl2O4After synthesis, 0.1NiAl with multilayer coating structure is obtained2O40.8Ce to 0.9Mn luminescent material, the photocatalytic degradation percentage of which reaches 93.5 percent after the methyl blue is illuminated for 3.5 hours.
Although the present invention has been described in detail with reference to the preferred embodiments, it will be understood by those skilled in the art that various changes may be made and equivalents may be substituted without departing from the spirit and scope of the invention as defined in the appended claims.
Claims (6)
1. A preparation method of a cerium manganese metal ion modified aluminate photocatalyst is characterized by comprising the following steps:
step 1: weighing 0.1-2g of MAL2O4Putting aluminate into a beaker, adding M which is one of Mg, Ca, Sr, Ba, Mn, Fe, Co, Ni, Cu, Zn, Nb, Zr, Cd, Ga, Pd, Ru, Rh and Pt, adding a certain amount of alcohol for ultrasonic dispersion for 0.5-3 hours, standing for clarification, and pouring out supernatant.
Step 2: adding 20-40mL of deionized water into the beaker in the step (1), weighing 6.5235g of cerium salt, and slowly adding the cerium salt into the solution; then weighing a certain amount of organic chelating agent, wherein the molar ratio of the chelating agent to cerium ions is 15: 1-1: 5; after the polysaccharide is completely dissolved, 0-100g of polysaccharide is weighed and used as a collapsing agent for preventing collapse and added into the solution; then, adding an acrylamide monomer and methylene bisacrylamide, wherein the molar ratio of the acrylamide monomer to cerium ions is 1: 5-5: 1, and the mass ratio of the methylene bisacrylamide to acrylamide is 0: 1-1: 10, and continuously adding the acrylamide monomer and the methylene bisacrylamide after the former reagent is completely dissolved;
and step 3: after the reagent in the step (2) is completely dissolved, polymerizing by adopting different polymerization modes to obtain gel; transferring the obtained gel to a drying oven for drying at constant temperature of 80-200 ℃ to 24EXerogel is obtained after 120 hours; after cooling to room temperature, taking out the dry gel, grinding the dry gel into powder, and sintering part of the powder at 400-1400 ℃ for 2-72 hours to obtain MAL2O4Ce photocatalyst, noted as sample A;
and 4, step 4: weighing 0.1-3 g of the sample A in the step (3), repeating the steps 1-3, and keeping the other steps consistent except that the cerium salt weighed in the step (2) is modified into manganese salt; drying and sintering to obtain MAL2O4Ce is Mn photocatalyst and is marked as sample B.
2. The method for preparing cerium manganese metal ion modified aluminate photocatalyst according to claim 1, wherein the inorganic chelating agent in the step (2) is one of NTA series, EDTA series, DTPA series, solid amine series, HEDTA series or epoxy curing agent series, and new metal impurity ions cannot be introduced.
3. The method for preparing cerium manganese metal ion modified aluminate photocatalyst according to claim 1, wherein the polymerization manner in the step (3) is thermal polymerization, ultraviolet polymerization or irradiation polymerization.
4. The method as claimed in claim 1, wherein the cerium salt in step (2) is one of salts of inorganic acid or organic acid radical, the polysaccharide is one of homogeneous polysaccharide or heterogeneous polysaccharide, and the manganese salt in step (4) is one of salts of inorganic acid or organic acid radical.
5. The method of claim 1, wherein the MAl is a cerium manganese metal ion modified aluminate photocatalyst2O4The molar ratio of Ce to Ce salt is 0: 1-9: 1; the molar ratio of the Ce salt to the manganese salt can be 0: 1-9: 1.
6. The cerium manganese metal ion modified aluminate according to claim 1The preparation method of the photocatalyst is characterized in that the MAl synthesized in the step (4)2O4The Ce-Mn photocatalyst forms a multi-layer coated structure.
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