CN111569899A - MnFe2O4-TiO2-preparation method of graphene aerogel - Google Patents
MnFe2O4-TiO2-preparation method of graphene aerogel Download PDFInfo
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- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 74
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 63
- 239000004964 aerogel Substances 0.000 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 239000000243 solution Substances 0.000 claims abstract description 37
- 238000009210 therapy by ultrasound Methods 0.000 claims abstract description 32
- 238000006243 chemical reaction Methods 0.000 claims abstract description 29
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000007864 aqueous solution Substances 0.000 claims abstract description 21
- 239000006185 dispersion Substances 0.000 claims abstract description 16
- 239000007788 liquid Substances 0.000 claims abstract description 15
- 238000004108 freeze drying Methods 0.000 claims abstract description 14
- 238000002791 soaking Methods 0.000 claims abstract description 13
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229920002873 Polyethylenimine Polymers 0.000 claims abstract description 11
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 11
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000000034 method Methods 0.000 claims abstract description 11
- 229910010446 TiO2-a Inorganic materials 0.000 claims abstract description 5
- 235000019441 ethanol Nutrition 0.000 claims abstract description 4
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims abstract 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 30
- SZQUEWJRBJDHSM-UHFFFAOYSA-N iron(3+);trinitrate;nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O SZQUEWJRBJDHSM-UHFFFAOYSA-N 0.000 claims description 10
- ALIMWUQMDCBYFM-UHFFFAOYSA-N manganese(2+);dinitrate;tetrahydrate Chemical compound O.O.O.O.[Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ALIMWUQMDCBYFM-UHFFFAOYSA-N 0.000 claims description 8
- 239000003638 chemical reducing agent Substances 0.000 claims description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 6
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 4
- 239000000463 material Substances 0.000 claims description 3
- 229960005070 ascorbic acid Drugs 0.000 claims description 2
- 235000010323 ascorbic acid Nutrition 0.000 claims description 2
- 239000011668 ascorbic acid Substances 0.000 claims description 2
- 229960004106 citric acid Drugs 0.000 claims description 2
- 235000015165 citric acid Nutrition 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 239000011782 vitamin Substances 0.000 claims description 2
- 229940088594 vitamin Drugs 0.000 claims description 2
- 229930003231 vitamin Natural products 0.000 claims description 2
- 235000013343 vitamin Nutrition 0.000 claims description 2
- XPJDHWXQFHGQAR-UHFFFAOYSA-N iron tetrahydrate Chemical compound O.O.O.O.[Fe] XPJDHWXQFHGQAR-UHFFFAOYSA-N 0.000 claims 1
- QZRHHEURPZONJU-UHFFFAOYSA-N iron(2+) dinitrate nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QZRHHEURPZONJU-UHFFFAOYSA-N 0.000 claims 1
- 239000003054 catalyst Substances 0.000 abstract description 5
- 238000001027 hydrothermal synthesis Methods 0.000 abstract description 3
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 abstract 2
- 238000002156 mixing Methods 0.000 abstract 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 abstract 1
- 238000001338 self-assembly Methods 0.000 abstract 1
- 229910021642 ultra pure water Inorganic materials 0.000 description 10
- 239000012498 ultrapure water Substances 0.000 description 10
- 238000006731 degradation reaction Methods 0.000 description 7
- 230000015556 catabolic process Effects 0.000 description 6
- LQJVOKWHGUAUHK-UHFFFAOYSA-L disodium 5-amino-4-hydroxy-3-phenyldiazenylnaphthalene-2,7-disulfonate Chemical compound [Na+].[Na+].OC1=C2C(N)=CC(S([O-])(=O)=O)=CC2=CC(S([O-])(=O)=O)=C1N=NC1=CC=CC=C1 LQJVOKWHGUAUHK-UHFFFAOYSA-L 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 229910017163 MnFe2O4 Inorganic materials 0.000 description 5
- 239000004408 titanium dioxide Substances 0.000 description 5
- 239000002131 composite material Substances 0.000 description 4
- 230000001699 photocatalysis Effects 0.000 description 3
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- FHHJDRFHHWUPDG-UHFFFAOYSA-L peroxysulfate(2-) Chemical compound [O-]OS([O-])(=O)=O FHHJDRFHHWUPDG-UHFFFAOYSA-L 0.000 description 2
- 230000027756 respiratory electron transport chain Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000002371 ultraviolet--visible spectrum Methods 0.000 description 2
- 229910052724 xenon Inorganic materials 0.000 description 2
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical group [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000005345 coagulation Methods 0.000 description 1
- 230000015271 coagulation Effects 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 239000011943 nanocatalyst Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 239000011941 photocatalyst Substances 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000004626 scanning electron microscopy Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 150000003722 vitamin derivatives Chemical class 0.000 description 1
- 238000003911 water pollution Methods 0.000 description 1
Images
Classifications
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/889—Manganese, technetium or rhenium
- B01J23/8892—Manganese
-
- 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
- B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
- B01J13/0091—Preparation of aerogels, e.g. xerogels
-
- B01J35/23—
Abstract
The invention discloses MnFe2O4‑TiO2-a method for preparing a graphene aerogel, the method comprising the steps of: (1) mixing the graphene oxide aqueous solution with absolute ethyl alcohol, then carrying out ultrasonic treatment, firstly adding ferric nitrate and manganese nitrate solution for ultrasonic treatment, then adding polyethyleneimine for ultrasonic treatment, and finally adding tetrabutyl titanate for ultrasonic treatment to form a good dispersion liquid; (2) transferring the dispersion liquid to a high-temperature high-pressure reaction kettle for reaction; (3) taking out the sample after the reaction is finished, soaking the sample in ammonia water (10 v/v%), soaking the sample in 20% ethanol before freeze drying to prepare MnFe2O4‑TiO2-graphene aerogels. According to the invention, the aerogel is synthesized by a one-step hydrothermal method, the addition of polyethyleneimine promotes the reduction of graphene oxide, so that the aerogel is easier to complete self-assembly, and the amino is introduced to enhance the mechanical strength of the aerogel. The aerogel preparation method of the invention is simple and convenient,the catalyst is easy to recover, secondary pollution is reduced, and the utilization rate of visible light is enhanced.
Description
Technical Field
The invention relates to a method for synthesizing MnFe in one step2O4-TiO2A preparation method of graphene aerogel, belonging to the field of catalyst preparation.
Background
With the development of industry, more and more refractory organics are generated and accumulated. The traditional methods such as adsorption and coagulation only carry out physical separation on organic matters, degradation on organic matters difficult to degrade is not finished, and an efficient method is needed for treating the increasingly serious water pollution problem.
The photocatalysis technology has the characteristics of no selectivity on organic matters, capability of thoroughly degrading the organic matters, utilization of solar energy and the like, and has attracted more and more attention. However, the photocatalytic technology also faces the problems of longer degradation period and lower efficiency, so that the selection of a composite system to improve the efficiency and the development of an efficient catalyst have important significance.
Titanium dioxide, as a good semiconductor photocatalyst, has the advantages of low cost, good chemical stability and no toxicity. However, TiO2The forbidden band width of the nano TiO is 3.2ev, the energy required by electrons from a valence band to a conduction band is higher, only the ultraviolet part of sunlight can be received, the utilization rate of solar energy is low, photoelectron hole pairs are easy to recombine, and in addition, nano TiO is used for preparing the nano TiO material2Are prone to agglomeration and are difficult to recycle. Numerous studies show that the transition metals Fe, Mn, Cu, Co and Ni can reduce the recombination of photoelectron hole pairs and can improve the visible light absorption. In addition, studies indicate that graphene doped TiO2The electron transfer capability can be improved, and the utilization rate of visible light can be improved. However, nano graphene TiO2The specific surface area of the catalyst is not greatly improved and it is difficult to recover it. The preparation of graphene having a three-dimensional structure is one of effective approaches to solve the above problems. Compared with two-dimensional graphene, the three-dimensional graphene not only has excellent physical and chemical properties of graphene, but also has a larger specific surface area and can provide more active point sites, and more importantly, the three-dimensional stoneThe ink alkene is convenient to be recycled.
Chinese patent 201810516300.3 provides a preparation method of graphene titanium dioxide composite nano material, and the prepared composite nano catalyst has higher photocatalytic efficiency than pure titanium dioxide catalyst, but has the defect of difficult recycling. Thus exploring and preparing MnFe2O4-TiO2Graphene aerogels are very essential.
Disclosure of Invention
The invention aims to provide MnFe with simple preparation, high mechanical strength and good catalytic effect2O4-TiO2-graphene aerogels.
The invention is realized by the following technical scheme:
1. MnFe2O4-TiO2-a method for preparing a graphene aerogel, characterized in that it comprises the following specific steps:
(1) preparing a graphene oxide aqueous solution by using an ultrasonic crusher;
(2) and (3) carrying out ultrasonic treatment on the graphene oxide aqueous solution and absolute ethyl alcohol for 30min, and then adding the ferric nitrate nonahydrate and the manganese nitrate tetrahydrate aqueous solution for ultrasonic treatment for 30min to form a solution A.
(3) Adding a reducing agent into the solution A, performing ultrasonic treatment for 30min, and finally adding a tetrabutyl titanate solution, and performing ultrasonic treatment for 30min to form a good dispersion liquid;
(4) transferring the dispersion liquid to a high-temperature high-pressure reaction kettle for reaction;
(5) after the reaction is finished, taking out the sample after the reaction kettle is cooled to room temperature, and soaking the sample in ammonia water (10 v/v%);
(6) soaking the sample in 20% ethanol before freeze drying, and freeze drying to obtain MnFe2O4-TiO2-graphene aerogels.
2. In the step (1), the power of the ultrasonic crusher is 135-315W, and the ultrasonic crushing time is 2-3 h.
3. In the step (2), the concentration of the graphene oxide aqueous solution is 3-6 mg/mL, the volume ratio of the graphene oxide aqueous solution to absolute ethyl alcohol is 1:1, the molar ratio of ferric nitrate nonahydrate to manganese nitrate tetrahydrate is 2:1, and the concentration of the ferric nitrate nonahydrate is 24.7-123.8 mmol/L.
4. The reducing agent in the step (3) is ascorbic acid, citric acid, vitamin or polyethyleneimine, and the mass ratio of the reducing agent to the graphene oxide is 1-10: 1. The mass ratio of tetrabutyl titanate to graphene oxide is 1.25-6.25: 1.
5. In the step (4), the reaction temperature is 160-200 ℃, and the reaction time is 12-24 h.
6. In the step (5), the soaking time in ammonia water (10 v/v%) is 3-6 h.
7. In the step (6), the temperature of freeze drying is-56-43 ℃, the time of freeze drying is 24-48 h, and MnFe is prepared2O4-TiO2-graphene aerogels.
The beneficial technical effects of the invention are as follows:
(1) by adding polyethyleneimine, amino groups are formed in one-step hydrothermal synthesis, compared with a method of soaking in ammonia water after hydrothermal reaction, the method is more convenient and faster, and the mechanical strength of the aerogel is improved.
(2)MnFe2O4The octahedral ligand provides more active sites and generates more radicals. Graphene and MnFe2O4The introduction of (2) enables the light source absorbed by the titanium dioxide to be transferred from ultraviolet light to visible light.
(3) The three-dimensional graphene aerogel has a large specific surface area and can adsorb more titanium dioxide and MnFe in unit volume2O4Moreover, the electron transfer capability can be improved, the catalytic efficiency is accelerated, and more importantly, the macroscopic three-dimensional structure is convenient to recycle.
Drawings
FIG. 1 shows MnFe in example 1 of the present invention2O4-TiO2-scanning electron micrographs of graphene aerogel.
FIG. 2 shows MnFe in example 3 of the present invention2O4-TiO2-x-ray diffraction pattern of graphene aerogel.
FIG. 3 shows MnFe in example 1 of the present invention2O4-TiO2-graphene aerogelAnd (5) a degradation effect diagram of the glue under different light sources.
FIG. 4 is a graph showing the change of the UV-visible spectrum during the degradation of acid Red B in example 1 according to the present invention.
Detailed Description
The invention is further described below with reference to the following examples:
example 1
(1) Placing 0.4g of graphene oxide in 100mL of ultrapure water, and crushing for 2h at the power of 270W by using an ultrasonic crusher to prepare a 4mg/mL graphene oxide aqueous solution;
(2) adding 12.5mL (1) of graphene oxide aqueous solution and 12.5mL of absolute ethyl alcohol into a beaker, carrying out ultrasonic treatment for 30min, dissolving 0.0913g of ferric nitrate nonahydrate and 0.0285g of manganese nitrate tetrahydrate in 5mL of ultrapure water, pouring into the beaker, and carrying out ultrasonic treatment for 30min to form a solution A;
(3) measuring 1mL of polyethyleneimine water solution (40mg/mL), adding the polyethyleneimine water solution into the solution A for 30min by ultrasonic treatment, adjusting the pH to 10.5, adding 0.19mL of tetrabutyl titanate into 5mL of absolute ethyl alcohol, adding the tetrabutyl titanate into the solution, and performing ultrasonic treatment for 30min to form a good dispersion liquid;
(4) transferring the dispersion liquid to a 50mL high-temperature high-pressure reaction kettle, and reacting for 24h at 180 ℃ in an oven;
(5) after the reaction is finished, taking out a sample after the reaction kettle is cooled to room temperature, and soaking the sample in ammonia water (10 v/v%) for 4 hours;
(6) freeze drying the sample at-43 deg.C for 24h to obtain MnFe2O4-TiO2-graphene aerogels.
As shown in FIG. 1, the MnFe obtained in the above example2O4-TiO2-scanning electron microscopy of graphene aerogels, composite material having an interconnected three-dimensional porous microstructure, and TiO2And MnFe2O4The particles are attached to the surface of the randomly oriented folded graphene or are wrapped by the graphene.
As shown in FIG. 3, the MnFe obtained in the above example is used2O4-TiO2Graph of degradation effect of graphene aerogels under different light sources, with acid red to simulate pollutants, testing MnFe2O4-TiO2-catalytic effect of graphene aerogel. In the figure, an ultraviolet light source is a 365nm ultraviolet lamp, simulated sunlight is a xenon lamp, visible light is obtained by adding a 420nm optical filter to the xenon lamp, and the added peroxymonosulfate is n (pms): n (acid red B) ═ 7:1, the degradation rates for acid red B under uv, simulated sunlight and visible light conditions were 91.7%, 87.7% and 79.7%, it can be seen that the effect was better under uv and simulated sunlight conditions, and that this material also had good effect under visible light conditions.
As shown in FIG. 4, the MnFe obtained in the above example is used2O4-TiO2An ultraviolet-visible spectrum change diagram of the graphene aerogel on the degradation process of acid red B, wherein a 365nm ultraviolet light source is utilized, and the added peroxymonosulfate is n (pms): n (acid red B) ═ 7:1, and as the reaction proceeded, the characteristic peak of acid red B at 515nm decreased, indicating that the naphthalene ring and azo bond of acid red B were oxidized.
Example 2
(1) Placing 0.4g of graphene oxide in 100mL of ultrapure water, and crushing for 2h at the power of 270W by using an ultrasonic crusher to prepare a 4mg/mL graphene oxide aqueous solution;
(2) adding 12.5mL (1) of graphene oxide aqueous solution and 12.5mL of absolute ethyl alcohol into a beaker, carrying out ultrasonic treatment for 30min, dissolving 0.0913g of ferric nitrate nonahydrate and 0.0285g of manganese nitrate tetrahydrate in 5mL of ultrapure water, pouring into the beaker, and carrying out ultrasonic treatment for 30min to form a solution A;
(3) measuring 1mL of polyethyleneimine water solution (30mg/mL), adding the solution A into the solution A for 30min by ultrasonic treatment, adjusting the pH value to 10, adding 0.125mL of tetrabutyl titanate into 5mL of absolute ethyl alcohol, adding the solution into the solution, and performing ultrasonic treatment for 30min to form a good dispersion liquid;
(4) transferring the dispersion liquid to a 50mL high-temperature high-pressure reaction kettle, and reacting for 24h at 180 ℃ in an oven;
(5) after the reaction is finished, taking out a sample after the reaction kettle is cooled to room temperature, and soaking the sample in ammonia water (10 v/v%) for 3 hours;
(6) freeze drying the sample at-43 deg.C for 24h to obtain MnFe2O4-TiO2-graphene aerogels.
Example 3
(1) Placing 0.4g of graphene oxide in 100mL of ultrapure water, and crushing for 2h at the power of 270W by using an ultrasonic crusher to prepare a 4mg/mL graphene oxide aqueous solution;
(2) adding 12.5mL (1) of graphene oxide aqueous solution and 12.5mL of absolute ethyl alcohol into a beaker, carrying out ultrasonic treatment for 20min, dissolving 0.0913g of ferric nitrate nonahydrate and 0.0285g of manganese nitrate tetrahydrate in 5mL of ultrapure water, pouring into the beaker, and carrying out ultrasonic treatment for 50min to form a solution A;
(3) measuring 1mL of polyethyleneimine water solution (30mg/mL), adding the solution A into the solution A for 30min by ultrasonic treatment, adjusting the pH value to 10, adding 0.19mL of tetrabutyl titanate into 5mL of absolute ethyl alcohol, adding the solution into the solution, and performing ultrasonic treatment for 30min to form a good dispersion liquid;
(4) transferring the dispersion liquid to a 50mL high-temperature high-pressure reaction kettle, and reacting for 24h at 180 ℃ in an oven;
(5) after the reaction is finished, taking out a sample after the reaction kettle is cooled to room temperature, and soaking the sample in ammonia water (10 v/v%) for 3 hours;
(6) freeze drying the sample at-43 deg.C for 24h to obtain MnFe2O4-TiO2-graphene aerogels.
As shown in FIG. 2, for MnFe obtained in the above example2O4-TiO2X-ray diffraction patterns of the graphene aerogels, from which it can be seen that the diffraction peaks in both patterns are associated with anatase-phase TiO2(JCPDS 21-1272) is well matched, MnFe2O4-TiO2Diffraction peaks in rGO also with MnFe2O4(JCPDS 10-0319) match well. Diffraction peaks at 25.4 °, 38.1 °, 47.9 °, 54.7 °, 62.7 °, 69.4 °, and 75 ° of 2 θ correspond to TiO2The (101), (004), (200), (211), (204), (220), and (215) lattice planes of (a); diffraction peaks at 2 θ of 18 °, 29.7 °, 34.8 °, 36.6 °, and 41.6 ° correspond to MnFe2O4The (111), (220), (200), (311), (222), and (400) lattice planes of (b).
Example 4
(1) Placing 0.4g of graphene oxide in 100mL of ultrapure water, and crushing for 2h at the power of 270W by using an ultrasonic crusher to prepare a 4mg/mL graphene oxide aqueous solution;
(2) adding 12.5mL (1) of graphene oxide aqueous solution and 12.5mL of absolute ethyl alcohol into a beaker, carrying out ultrasonic treatment for 30min, dissolving 0.0913g of ferric nitrate nonahydrate and 0.0285g of manganese nitrate tetrahydrate in 5mL of ultrapure water, pouring into the beaker, and carrying out ultrasonic treatment for 30min to form a solution A;
(3) measuring 1mL of polyethyleneimine water solution (30mg/mL), adding the solution A into the solution A for 30min by ultrasonic treatment, adjusting the pH value to 10, adding 0.25mL of tetrabutyl titanate into 5mL of absolute ethyl alcohol, adding the solution into the solution, and performing ultrasonic treatment for 30min to form a good dispersion solution;
(4) transferring the dispersion liquid to a 50mL high-temperature high-pressure reaction kettle, and reacting for 24h at 180 ℃ in an oven;
(5) after the reaction is finished, taking out a sample after the reaction kettle is cooled to room temperature, and soaking the sample in ammonia water (10 v/v%) for 3 hours;
(6) freeze drying the sample at-43 deg.C for 24h to obtain MnFe2O4-TiO2-graphene aerogels.
Example 5
(1) Placing 0.4g of graphene oxide in 100mL of ultrapure water, and crushing for 2h at the power of 270W by using an ultrasonic crusher to prepare a 4mg/mL graphene oxide aqueous solution;
(2) adding 12.5mL (1) of graphene oxide aqueous solution and 12.5mL of absolute ethyl alcohol into a beaker, carrying out ultrasonic treatment for 30min, dissolving 0.0913g of ferric nitrate nonahydrate and 0.0285g of manganese nitrate tetrahydrate in 5mL of ultrapure water, pouring into the beaker, and carrying out ultrasonic treatment for 30min to form a solution A;
(3) measuring 1mL of polyethyleneimine water solution (30mg/mL), adding the solution A into the solution A for 30min by ultrasonic treatment, adjusting the pH value to 10, adding 0.31mL of tetrabutyl titanate into 5mL of absolute ethyl alcohol, adding the solution into the solution, and performing ultrasonic treatment for 30min to form a good dispersion liquid;
(4) transferring the dispersion liquid to a 50mL high-temperature high-pressure reaction kettle, and reacting for 24h at 180 ℃ in an oven;
(5) after the reaction is finished, taking out a sample after the reaction kettle is cooled to room temperature, and soaking the sample in ammonia water (10 v/v%) for 3 hours;
(6) freeze drying the sample at-43 deg.C for 24h to obtain MnFe2O4-TiO2-grapheneAn aerogel.
Claims (9)
1. MnFe2O4-TiO2-a method for preparing a graphene aerogel, characterized in that it comprises the following specific steps:
(1) preparing a graphene oxide aqueous solution by using an ultrasonic cell crusher;
(2) carrying out ultrasonic treatment on the graphene oxide aqueous solution and absolute ethyl alcohol for 20-60 min, and then adding ferric nitrate nonahydrate and manganese nitrate tetrahydrate aqueous solution for ultrasonic treatment for 20-60 min to form a solution A;
(3) adding a reducing agent into the solution A, performing ultrasonic treatment for 20-60 min, and finally adding a tetrabutyl titanate alcohol solution, and performing ultrasonic treatment for 20-60 min to form a good dispersion liquid;
(4) transferring the dispersion liquid to a high-temperature high-pressure reaction kettle for reaction;
(5) after the reaction is finished, taking out a sample after the reaction kettle is cooled to room temperature, and soaking the sample in ammonia water with the volume percentage of 5-10 v/v%;
(6) soaking the sample in 10-20% ethanol before freeze drying, and freeze drying to obtain MnFe2O4-TiO2-graphene aerogels.
2. MnFe of claim 12O4-TiO2The preparation method of the graphene aerogel is characterized in that in the step (1), the power of an ultrasonic cell crusher is 135-315W, and the crushing time is 2-3 h.
3. MnFe of claim 12O4-TiO2The preparation method of the graphene aerogel is characterized in that in the step (2), the concentration of the graphene oxide aqueous solution is 3-6 mg/mL, and the volume ratio of the graphene oxide aqueous solution to the absolute ethyl alcohol is 1: 1.
4. MnFe of claim 12O4-TiO2A method for preparing a graphene aerogel, characterized in that, in the step (2), iron nitrate nonahydrate and iron tetrahydrate are addedThe molar ratio of the hydrated manganese nitrate is 2:1, and the concentration of the ferric nitrate nonahydrate is 24.7-123.8 mmol/L.
5. MnFe of claim 12O4-TiO2-a method for preparing graphene aerogel, characterized in that, in step (3), the reducing agent is selected from the following: ascorbic acid, citric acid, vitamins and polyethyleneimine, wherein the mass ratio of the reducing agent to the graphene oxide is (1-10): 1.
6. MnFe of claim 12O4-TiO2The preparation method of the graphene aerogel is characterized in that in the step (3), the mass ratio of tetrabutyl titanate to graphene oxide is 1.25-6.25: 1.
7. MnFe of claim 12O4-TiO2The preparation method of the graphene aerogel is characterized in that in the step (4), the reaction temperature is 160-200 ℃, and the reaction time is 12-24 hours.
8. MnFe of claim 12O4-TiO2The preparation method of the graphene aerogel is characterized in that in the step (5), the graphene aerogel is soaked in ammonia water with the volume percentage of 5-10 v/v% for 3-6 hours.
9. MnFe of claim 12O4-TiO2The preparation method of the graphene aerogel is characterized in that in the step (6), the temperature of freeze drying is-56-43 ℃, the time of freeze drying is 24-48 h, and MnFe is prepared2O4-TiO2-a graphene aerogel material.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116328794A (en) * | 2023-04-19 | 2023-06-27 | 苏州科技大学 | Preparation method and application of high-efficiency catalytic oxidation heterojunction material |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003210990A (en) * | 2002-01-28 | 2003-07-29 | Toda Kogyo Corp | Catalyst for treating organic compound |
| CN102319563A (en) * | 2011-05-30 | 2012-01-18 | 湖南大学 | Magnetic nanometer composite photocatalyst and application |
| CN102887508A (en) * | 2012-09-28 | 2013-01-23 | 上海理工大学 | Method for preparing high-strength graphite oxide aerogel |
| CN103030208A (en) * | 2013-01-08 | 2013-04-10 | 哈尔滨工业大学 | Application of spinel ferrite catalyst and method for urging persulfate to generate free radicals to catalytically degrade organic matters |
| CN105110316A (en) * | 2015-08-05 | 2015-12-02 | 哈尔滨工业大学 | Graphene-carbon nanofiber composite aerogel preparation method |
| CN105833882A (en) * | 2016-04-05 | 2016-08-10 | 山东大学 | Performance enhanced Fenton catalyst and application thereof |
| CN105854860A (en) * | 2016-03-22 | 2016-08-17 | 江苏大学 | Preparation method for titanium dioxide/graphene aerogel with high specific surface area |
| CN107539980A (en) * | 2017-09-07 | 2018-01-05 | 马鞍山中粮生物化学有限公司 | A kind of novel graphite alkene aerogel material and preparation method thereof |
| CN111203159A (en) * | 2020-01-16 | 2020-05-29 | 苏州科技大学 | Preparation method and application of curcumin-titanium dioxide-three-dimensional graphene composite aerogel |
-
2020
- 2020-06-03 CN CN202010495333.1A patent/CN111569899A/en active Pending
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003210990A (en) * | 2002-01-28 | 2003-07-29 | Toda Kogyo Corp | Catalyst for treating organic compound |
| CN102319563A (en) * | 2011-05-30 | 2012-01-18 | 湖南大学 | Magnetic nanometer composite photocatalyst and application |
| CN102887508A (en) * | 2012-09-28 | 2013-01-23 | 上海理工大学 | Method for preparing high-strength graphite oxide aerogel |
| CN103030208A (en) * | 2013-01-08 | 2013-04-10 | 哈尔滨工业大学 | Application of spinel ferrite catalyst and method for urging persulfate to generate free radicals to catalytically degrade organic matters |
| CN105110316A (en) * | 2015-08-05 | 2015-12-02 | 哈尔滨工业大学 | Graphene-carbon nanofiber composite aerogel preparation method |
| CN105854860A (en) * | 2016-03-22 | 2016-08-17 | 江苏大学 | Preparation method for titanium dioxide/graphene aerogel with high specific surface area |
| CN105833882A (en) * | 2016-04-05 | 2016-08-10 | 山东大学 | Performance enhanced Fenton catalyst and application thereof |
| CN107539980A (en) * | 2017-09-07 | 2018-01-05 | 马鞍山中粮生物化学有限公司 | A kind of novel graphite alkene aerogel material and preparation method thereof |
| CN111203159A (en) * | 2020-01-16 | 2020-05-29 | 苏州科技大学 | Preparation method and application of curcumin-titanium dioxide-three-dimensional graphene composite aerogel |
Non-Patent Citations (5)
| Title |
|---|
| JING-JIEZHANG ET AL.,: "Three-dimensional Fe2O3–TiO2–graphene aerogel nanocomposites with enhanced adsorption and visible light-driven photocatalytic performance in the removal of RhB dyes", 《JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY》 * |
| XUEWANG ET AL.,: "3D self-assembly polyethyleneimine modified graphene oxide hydrogel for the extraction of uranium from aqueous solution", 《APPLIED SURFACE SCIENCE》 * |
| YUWEI SUN ET AL.,: "Fabrication of a magnetic ternary ZnFe2O4/TiO2/RGO Z-scheme system with efficient photocatalytic activity and easy recyclability", 《RSC ADVANCES》 * |
| 付乌有等: "锐钛矿型TiO_2/MnFe_2O_4核壳结构复合纳米颗粒的制备及其光催化特性", 《复合材料学报》 * |
| 何光裕等: "ZnO/氧化石墨烯复合材料的制备及其可见光催化性能", 《高校化学工程学报》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116328794A (en) * | 2023-04-19 | 2023-06-27 | 苏州科技大学 | Preparation method and application of high-efficiency catalytic oxidation heterojunction material |
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