CN114534741A - Attapulgite/manganese dioxide/ferroferric oxide nano composite material and preparation method and application thereof - Google Patents
Attapulgite/manganese dioxide/ferroferric oxide nano composite material and preparation method and application thereof Download PDFInfo
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- ferroferric oxide
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- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 title claims abstract description 104
- 229910052625 palygorskite Inorganic materials 0.000 title claims abstract description 74
- 229960000892 attapulgite Drugs 0.000 title claims abstract description 71
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 title claims abstract description 57
- 239000002114 nanocomposite Substances 0.000 title claims abstract description 52
- 239000000463 material Substances 0.000 title claims abstract description 44
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 239000002957 persistent organic pollutant Substances 0.000 claims abstract description 14
- 239000002245 particle Substances 0.000 claims abstract description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 25
- 239000000843 powder Substances 0.000 claims description 19
- 238000010438 heat treatment Methods 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 16
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- 238000001035 drying Methods 0.000 claims description 15
- 239000002244 precipitate Substances 0.000 claims description 13
- 238000003756 stirring Methods 0.000 claims description 12
- 238000005406 washing Methods 0.000 claims description 11
- WAEMQWOKJMHJLA-UHFFFAOYSA-N Manganese(2+) Chemical compound [Mn+2] WAEMQWOKJMHJLA-UHFFFAOYSA-N 0.000 claims description 9
- 239000003638 chemical reducing agent Substances 0.000 claims description 9
- 229910001437 manganese ion Inorganic materials 0.000 claims description 9
- 239000012286 potassium permanganate Substances 0.000 claims description 9
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 8
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 8
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 8
- SURQXAFEQWPFPV-UHFFFAOYSA-L iron(2+) sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Fe+2].[O-]S([O-])(=O)=O SURQXAFEQWPFPV-UHFFFAOYSA-L 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 5
- 238000000227 grinding Methods 0.000 claims description 5
- 239000000047 product Substances 0.000 claims description 5
- 238000005303 weighing Methods 0.000 claims description 5
- 230000000593 degrading effect Effects 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 4
- 229910021380 Manganese Chloride Inorganic materials 0.000 claims description 3
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 claims description 3
- 239000011565 manganese chloride Substances 0.000 claims description 3
- 235000002867 manganese chloride Nutrition 0.000 claims description 3
- 229940099607 manganese chloride Drugs 0.000 claims description 3
- 229940099596 manganese sulfate Drugs 0.000 claims description 3
- 239000011702 manganese sulphate Substances 0.000 claims description 3
- 235000007079 manganese sulphate Nutrition 0.000 claims description 3
- 239000002105 nanoparticle Substances 0.000 claims description 3
- 238000009210 therapy by ultrasound Methods 0.000 claims description 3
- 238000004140 cleaning Methods 0.000 claims description 2
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical group [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 14
- 238000011084 recovery Methods 0.000 abstract description 6
- 238000005516 engineering process Methods 0.000 abstract description 5
- 239000002351 wastewater Substances 0.000 description 24
- YYYARFHFWYKNLF-UHFFFAOYSA-N 4-[(2,4-dimethylphenyl)diazenyl]-3-hydroxynaphthalene-2,7-disulfonic acid Chemical compound CC1=CC(C)=CC=C1N=NC1=C(O)C(S(O)(=O)=O)=CC2=CC(S(O)(=O)=O)=CC=C12 YYYARFHFWYKNLF-UHFFFAOYSA-N 0.000 description 22
- 230000015556 catabolic process Effects 0.000 description 19
- 238000006731 degradation reaction Methods 0.000 description 19
- FHHJDRFHHWUPDG-UHFFFAOYSA-L peroxysulfate(2-) Chemical compound [O-]OS([O-])(=O)=O FHHJDRFHHWUPDG-UHFFFAOYSA-L 0.000 description 19
- 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 17
- 229940012189 methyl orange Drugs 0.000 description 17
- 235000012730 carminic acid Nutrition 0.000 description 16
- 239000003054 catalyst Substances 0.000 description 16
- IQFVPQOLBLOTPF-HKXUKFGYSA-L congo red Chemical compound [Na+].[Na+].C1=CC=CC2=C(N)C(/N=N/C3=CC=C(C=C3)C3=CC=C(C=C3)/N=N/C3=C(C4=CC=CC=C4C(=C3)S([O-])(=O)=O)N)=CC(S([O-])(=O)=O)=C21 IQFVPQOLBLOTPF-HKXUKFGYSA-L 0.000 description 15
- 239000001048 orange dye Substances 0.000 description 12
- 239000000975 dye Substances 0.000 description 11
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 9
- ISPYRSDWRDQNSW-UHFFFAOYSA-L manganese(II) sulfate monohydrate Chemical group O.[Mn+2].[O-]S([O-])(=O)=O ISPYRSDWRDQNSW-UHFFFAOYSA-L 0.000 description 8
- 239000002131 composite material Substances 0.000 description 7
- 238000004042 decolorization Methods 0.000 description 7
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 description 7
- 229940043267 rhodamine b Drugs 0.000 description 7
- 230000000694 effects Effects 0.000 description 5
- 238000001027 hydrothermal synthesis Methods 0.000 description 5
- 238000001556 precipitation Methods 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000000706 filtrate Substances 0.000 description 4
- 238000004064 recycling Methods 0.000 description 4
- 238000002798 spectrophotometry method Methods 0.000 description 4
- 239000002253 acid Substances 0.000 description 3
- 229910044991 metal oxide Inorganic materials 0.000 description 3
- 150000004706 metal oxides Chemical class 0.000 description 3
- 239000012982 microporous membrane Substances 0.000 description 3
- 238000005070 sampling Methods 0.000 description 3
- 238000007789 sealing Methods 0.000 description 3
- 229910002518 CoFe2O4 Inorganic materials 0.000 description 2
- 229910016516 CuFe2O4 Inorganic materials 0.000 description 2
- 230000003213 activating effect Effects 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000000635 electron micrograph Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical compound C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- 239000003242 anti bacterial agent Substances 0.000 description 1
- 229940088710 antibiotic agent Drugs 0.000 description 1
- 239000000987 azo dye Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 1
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 1
- JZGWEIPJUAIDHM-UHFFFAOYSA-N chembl2007771 Chemical compound C1=CC=C2C(N=NC3=C4C(=CC(=CC4=CC=C3O)S(O)(=O)=O)S(O)(=O)=O)=CC=C(S(O)(=O)=O)C2=C1 JZGWEIPJUAIDHM-UHFFFAOYSA-N 0.000 description 1
- 239000002734 clay mineral Substances 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(II,III) oxide Inorganic materials [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- 244000144972 livestock Species 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000000696 magnetic material Substances 0.000 description 1
- 238000007885 magnetic separation Methods 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- CNFDGXZLMLFIJV-UHFFFAOYSA-L manganese(II) chloride tetrahydrate Chemical compound O.O.O.O.[Cl-].[Cl-].[Mn+2] CNFDGXZLMLFIJV-UHFFFAOYSA-L 0.000 description 1
- 229960000907 methylthioninium chloride Drugs 0.000 description 1
- 238000001471 micro-filtration Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000011943 nanocatalyst Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000002073 nanorod Substances 0.000 description 1
- 239000010815 organic waste Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-O oxonium Chemical compound [OH3+] XLYOFNOQVPJJNP-UHFFFAOYSA-O 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 230000029553 photosynthesis Effects 0.000 description 1
- 238000010672 photosynthesis Methods 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000001044 red dye Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 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
- 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
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- 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
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
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- 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
- C02F1/72—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
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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Abstract
The invention discloses an attapulgite/manganese dioxide/ferroferric oxide nano composite material as well as a preparation method and application thereof. The cheap and easily-obtained natural attapulgite is used as the carrier of the nano composite material, so that the manganese dioxide particles can be prevented from agglomerating, and the catalytic activity is improved. The addition of the ferroferric oxide particles enables the nano composite material to be quickly separated from the solution through a magnetic recovery technology with simple operation. The prepared nano composite material has the advantages of high catalytic efficiency, wide pH application range, easy recovery, recyclability, simple preparation process, low cost and the like, and has wide application prospect in the aspect of treating organic pollutants.
Description
Technical Field
The invention relates to the technical field of nano materials, in particular to an attapulgite/manganese dioxide/ferroferric oxide nano composite material, a preparation method thereof and application thereof in degrading organic pollutants.
Background
With the vigorous development of the industries such as textile, paper making, leather, medical treatment, livestock raising and the like, a large amount of generated organic pollutants cause more severe water pollution. The organic wastewater contains a large amount of organic pollutants (such as methylene blue, methyl orange, acid scarlet, phenol, antibiotics and the like), has the characteristics of high chromaticity, strong biotoxicity, difficult degradation and the like, influences the photosynthesis of aquatic plants, and seriously harms the ecological environment and human health. Therefore, the treatment of organic waste water is an urgent problem to be solved.
In recent years, advanced oxidation technologies (such as Fenton or Fenton-like technologies, photocatalytic oxidation, etc.) have received increasing attention due to their excellent degradation properties for organic pollutants. With conventional oxidizing agent H2O2Compared with the Fenton-like reaction in which Peroxymonosulfate (PMS) or Persulfate (PS) participates, the target pollutant can be oxidized more thoroughly, and the applicable pH range is wide. Among them, PMS has many activation modes, such as heating, ultraviolet irradiation, transition metal oxides, and the like. At present, transition metal catalysts, e.g. CuO, CeO2、Fe2O3、Co3O4And MnO2As a PMS catalyst, the catalyst attracts attention because of its advantages such as low energy consumption, low cost, good reactivity, and the like. Among these transition metal catalysts, manganese dioxide has higher cost performance, better catalytic activity and lower toxicity, and is one of the most suitable catalysts for practical use. Wu Guangrui (2018) and other synthetic linear MnO2The method is used for activating PMS to degrade rhodamine B, and 91% of rhodamine B degradation is obtained within 20 minutes. Collufurum (2015) in the presence of alpha-MnO in fibrous catalyst2Research on a PMS heterogeneous catalytic degradation system shows that the degradation efficiency of phenol reaches 100% within 10 minutes. However, manganese dioxide nanoparticles tend to agglomerate, resulting in a significant reduction in their specific surface area, available active sites and catalytic activity. In order to maintain excellent catalytic activity of manganese dioxide, manganese dioxide needs to be supported stablyOn a carrier.
Natural attapulgite (also called palygorskite) is a chain-layered magnesium-containing aluminosilicate nano rod-shaped clay mineral (the crystal diameter is 40 nm), and has the characteristics of unique rod-shaped crystal structure, large specific surface area, developed nano pores and the like. It is reported that attapulgite having excellent dispersibility as a low-cost, environmentally friendly catalyst or catalyst support prevents the agglomeration of manganese dioxide particles. Li and the like (2013) prepare attapulgite loaded Ce1-xMnxO2The catalytic degradation rate of the mesomorphic oxide to methyl orange can reach 98 percent. However, the practical engineering application of the nano-catalyst is limited by the defects of difficult recovery, difficult separation and the like. Many studies have demonstrated that the magnetic material ferroferric oxide can solve these problems. In addition, ferroferric oxide is widely used as an adsorbent or a catalyst for removing organic pollutants, heavy metals, dyes and the like.
Therefore, the attapulgite/manganese dioxide/ferroferric oxide nano composite material is prepared by taking attapulgite as a raw material, adding potassium permanganate, a divalent manganese ion reducing agent and ferroferric oxide and utilizing a hydrothermal method. Solves the problem of poor effect of catalyzing and degrading organic pollutants by using single attapulgite or metal oxide, and provides a new material and a new method for treating the organic pollutants.
Disclosure of Invention
The invention aims to solve the technical problem of providing an attapulgite/manganese dioxide/ferroferric oxide nano composite material and a preparation method thereof, and solves the problems of poor effect and difficult recovery of organic pollutants catalytically degraded by single attapulgite or metal oxides.
In order to solve the problems in the technology, the technical solution of the invention is as follows:
a preparation method of an attapulgite/manganese dioxide/ferroferric oxide nano composite material comprises the following steps: (1) weighing a certain amount of ferrous sulfate heptahydrate, dissolving the ferrous sulfate heptahydrate in water, adding polyvinylpyrrolidone, stirring and heating, then adding a sodium hydroxide solution with the concentration of 3-5 mol/L into the solution, continuously heating and stirring after the solution generates a blue-green precipitate, stopping heating and cooling to room temperature after the blue-green precipitate becomes black, centrifuging, washing and drying to obtain ferroferric oxide powder;
(2) adding potassium permanganate, a divalent manganese ion reducing agent and the ferroferric oxide powder obtained in the step (1) into attapulgite serving as a raw material, adding pure water, oscillating in a water bath oscillator, performing ultrasonic treatment, centrifuging, cleaning, drying, and grinding to more than 200 meshes to obtain the attapulgite/manganese dioxide/ferroferric oxide nano composite material.
Further, in the step (1), the heating temperature is 70-80 ℃, and the time for continuously heating and stirring is 1.5-2 h.
Further, in the step (2), the using amount of potassium permanganate is 40-60% of the mass of the attapulgite.
Furthermore, in the step (2), the dosage of the divalent manganese ion reducing agent is 0.0319-0.0390 mol/L.
Further, in the step (2), the mass ratio of the ferroferric oxide powder to the attapulgite is 1: 3.3-1: 5.
further, in the step (2), the conditions of water bath and drying are as follows: oscillating for 5-6 h in a water bath oscillator at 20-25 ℃ and 200-250 rpm, washing and centrifuging the obtained product, and drying in an oven at 50-60 ℃ for 12-24 h.
Further, in the step (2), the attapulgite is attapulgite powder with the grain size of 200-320 meshes, namely 75-45 μm.
Further, in the step (2), the divalent manganese ion reducing agent is manganese sulfate or manganese chloride.
An attapulgite/manganese dioxide/ferroferric oxide nano composite material is provided, wherein the attapulgite presents a nano rod-shaped structure, and ferroferric oxide nano particles and manganese dioxide particles are attached on the surface of the attapulgite.
Further, the attapulgite/manganese dioxide/ferroferric oxide nano composite material is applied to degradation of organic wastewater.
Compared with the prior art, the invention has the following beneficial effects:
1. the attapulgite is used as a carrier of the nano composite material, can prevent manganese dioxide particles from agglomerating, and ensures that the manganese dioxide has better dispersity and larger specific surface area, and the surface of the material has more active sites, thereby improving the catalytic activity. The addition of the ferroferric oxide particles enables the nano composite material to be quickly separated from the solution through a magnetic recovery technology with simple operation. And in addition, ferroferric oxide can also be used as a catalyst promoter of manganese dioxide, so that the catalytic performance of the manganese dioxide is improved.
2. The attapulgite/manganese dioxide/ferroferric oxide nano composite material is prepared by a hydrothermal method, and the problem of poor effect of catalytic degradation of organic pollutants by single attapulgite or metal oxides is solved.
3. The attapulgite/manganese dioxide/ferroferric oxide nano composite material prepared by a hydrothermal method has the advantages of high degradation efficiency on organic pollutants, wide pH application range, easiness in recovery, recyclability, simple preparation process, low cost and the like, and has wide application prospect in the aspect of treating organic wastewater.
Drawings
FIGS. 1 (a) and (b) are SEM photographs of attapulgite and the attapulgite/manganese dioxide/ferroferric oxide nanocomposite prepared by the method respectively.
FIG. 2 is a curve of the decoloring rate of the attapulgite/manganese dioxide/ferroferric oxide nanocomposite prepared by the invention on acid scarlet (GR), carmine, congo red and methyl orange dye wastewater.
FIG. 3 is a phenol degradation efficiency curve of the attapulgite/manganese dioxide/ferroferric oxide nanocomposite prepared by the method.
FIG. 4 shows the recycling and decoloring efficiency of the attapulgite/manganese dioxide/ferroferric oxide nanocomposite material prepared by the invention on acid scarlet (GR) dye wastewater.
Detailed Description
The invention is described in further detail below with reference to the figures and specific examples.
Example 1
(1) Weighing 0.278 g of ferrous sulfate heptahydrate, dissolving in 100 mL of water, adding 1 g of polyvinylpyrrolidone (PVP), stirring and heating to 80 deg.C, adding 3 mol/L sodium hydroxide solution into the solution, continuing heating and stirring for 2 h after the blue-green precipitate is generated, stopping heating and cooling to room temperature until the precipitate in the solution turns black from blue-green, centrifuging to obtain lower precipitate, washing, drying to obtain ferroferric oxide powder, sealing and storing for use.
(2) Adding 3 g of attapulgite powder into a 150 mL ground conical flask, adding 1.5 g of potassium permanganate, 0.6 g of manganese sulfate monohydrate (in the embodiment, the divalent manganese ion reducing agent is manganese sulfate, specifically manganese sulfate monohydrate, and certainly the divalent manganese ion reducing agent can also be manganese chloride, specifically manganese chloride tetrahydrate) and 0.8 g of ferroferric oxide powder obtained in the step (1), adding 100 mL of pure water, oscillating for 5 hours in a water bath oscillator at 20 ℃ and 200 rpm, performing ultrasonic treatment, centrifuging and washing, drying the obtained product in an oven at 60 ℃ for 12 hours, and grinding to more than 200 meshes to obtain the attapulgite/manganese dioxide/ferroferric oxide nanocomposite.
Respectively selecting 200 mg/L of acid scarlet (GR), carmine, congo red and methyl orange dye wastewater, respectively adding 50 mL into a 100 mL centrifuge tube, adding 2 mL of PMS solution with the concentration of 30 mmol/L into the centrifuge tube, adjusting the pH =5 of the solution, then adding 0.05 g of the nanocomposite material, oscillating the nanocomposite material in a constant-temperature water bath oscillator at 25 ℃ and 250 rpm for 6 h, sampling at a preset time, and measuring the concentrations of the acid scarlet (GR), the carmine, the congo red and the methyl orange dye wastewater by a spectrophotometry method on a filtrate filtered by a 0.45 mu m microporous membrane after precipitation. The decoloring rates of the nano composite material of the example 1 on acid scarlet (GR), carmine, congo red and methyl orange dye wastewater are respectively 100%, 99.67%, 92.99% and 95.45%.
In addition, the preferable proportioning scheme is that the amount of the potassium permanganate is 40-60% of the mass of the attapulgite, the amount of the manganese sulfate monohydrate is 18-22% of the mass of the attapulgite, and the concentration of the manganese sulfate monohydrate is 0.0319-0.0390 mol/L.
Example 2
(1) Weighing 0.278 g of ferrous sulfate heptahydrate, dissolving in 100 mL of water, adding 1 g of polyvinylpyrrolidone (PVP), stirring and heating to 70 deg.C, adding 4 mol/L sodium hydroxide solution, continuing to heat and stir for 2 h after the solution generates blue-green precipitate until the precipitate in the solution turns from blue-green to black, stopping heating and cooling to room temperature, centrifuging to obtain lower precipitate, washing, and drying to obtain ferroferric oxide powder. Sealing and storing for later use.
(2) Adding 3 g of attapulgite powder into a 150 mL ground conical flask, adding 1.2 g of potassium permanganate, 0.54 g of manganese sulfate monohydrate and 0.6 g of ferroferric oxide powder obtained in the step (1), adding 100 mL of pure water, oscillating for 6 h in a water bath oscillator at 20 ℃ and 200 rpm, centrifuging and washing, drying the obtained product in an oven at 50 ℃ for 12 h, and grinding to more than 200 meshes to obtain the attapulgite/manganese dioxide/ferroferric oxide nano composite material. Respectively selecting 200 mg/L of acid scarlet (GR), carmine, congo red and methyl orange dye wastewater, respectively adding 50 mL into a 100 mL centrifuge tube, adding 2 mL of PMS solution with the concentration of 30 mmol/L into the centrifuge tube, adjusting the pH =5 of the solution, then adding 0.05 g of the nanocomposite material, oscillating the nanocomposite material in a constant-temperature water bath oscillator at 25 ℃ and 250 rpm for 6 h, sampling at a preset time, and measuring the concentrations of the acid scarlet (GR), the carmine, the congo red and the methyl orange dye wastewater by a spectrophotometry method on a filtrate filtered by a 0.45 mu m microporous membrane after precipitation. The decolorization rates of the nanocomposites of example 2 for acid carmine (GR), carmine, congo red, and methyl orange dye wastewater were 99.59%, 99.16%, 92.41%, and 96.15%, respectively.
Example 3
(1) Weighing 0.278 g of ferrous sulfate heptahydrate, dissolving in 100 mL of water, adding 1 g of polyvinylpyrrolidone (PVP), stirring and heating to 80 deg.C, adding 5 mol/L sodium hydroxide solution, continuing to heat and stir for 2 h after the blue-green precipitate is generated, stopping heating and cooling to room temperature until the precipitate in the solution turns from blue-green to black, centrifuging to obtain lower precipitate, washing, and drying to obtain ferroferric oxide powder. Sealing and storing for later use.
(2) Adding 3 g of attapulgite powder into a 150 mL ground conical flask, adding 1.8 g of potassium permanganate, 0.66 g of manganese sulfate monohydrate and 0.9 g of ferroferric oxide powder obtained in the step (1), adding 100 mL of pure water, oscillating for 5 h in a water bath oscillator at 20 ℃ and 200 rpm, centrifuging and washing, drying the obtained product in an oven at 60 ℃ for 24 h, and grinding to more than 200 meshes to obtain the attapulgite/manganese dioxide/ferroferric oxide composite material.
Respectively selecting 50 mL of 200 mg/L acid scarlet (GR), carmine, congo red and methyl orange dye wastewater, adding 2 mL of PMS solution with the concentration of 30 mmol/L, adjusting the pH =5 of the solution, then adding 0.05 g of the nanocomposite material, oscillating for 6 h in a constant-temperature water bath oscillator at 25 ℃ and 250 rpm, sampling for a preset time, and measuring the concentrations of the acid scarlet (GR), carmine, congo red and methyl orange dye wastewater by spectrophotometry on a filtrate filtered by a 0.45 mu m microporous membrane after precipitation. The decolorization rates of the nanocomposites of example 3 for acid carmine (GR), carmine, congo red, and methyl orange dye wastewater were 99.66%, 99.95%, 93.94%, and 94.70%, respectively.
Because the natural attapulgite powder is white, the color of the attapulgite/manganese dioxide/ferroferric oxide nano composite material prepared by the invention is obviously changed compared with that of the attapulgite powder, and the color of the obtained nano composite material is black. FIGS. 1 (a) and (b) are SEM photographs of attapulgite and the attapulgite/manganese dioxide/ferroferric oxide nanocomposite prepared by the method respectively. As can be seen from the electron micrograph (a), the natural attapulgite has a nano rod-shaped structure, and the surface of the natural attapulgite is smooth and has no any load. From the electron micrograph (b), it can be seen that the manganese dioxide particles and the ferroferric oxide particles are attached to the surface of the attapulgite. The ferroferric oxide can solve the defect that the attapulgite in a heterogeneous system is difficult to recover, and the effect of catalyzing and degrading organic pollutants is improved. The attapulgite is used as a carrier of the nano composite material, so that the dispersity of manganese dioxide is improved, the manganese dioxide particles are prevented from agglomerating, and the stability of the whole structure is maintained.
Respectively testing the catalytic degradation performance and the recycling performance of the attapulgite/manganese dioxide/ferroferric oxide composite material on organic pollutants such as dye, phenol and the like.
1. Catalytic decoloring performance on dye wastewater
FIG. 2 is a curve of the decoloring efficiency of an attapulgite/manganese dioxide/ferroferric oxide nanocomposite (example 1) on acidic scarlet (GR), carmine, congo red and methyl orange dye wastewater. As can be seen from figure 2, the material reaches the balance of the degradation of 3 dye wastewater of acid scarlet (GR), carmine and methyl orange within 4 hours and reaches the balance of the degradation of Congo red dye wastewater within 6 hours. The decoloring rates of the nano composite material on acid carmine (GR), carmine, congo red and methyl orange dye wastewater can respectively reach 100%, 99.67%, 92.99% and 95.45%. The result shows that the prepared attapulgite/manganese dioxide/ferroferric oxide composite material can realize high-efficiency decolorization on the dye.
In the prior art, Huang et al (2020) prepares nanorod alpha-MnO by a hydrothermal method2And (3) loading palygorskite, and activating PMS to degrade rhodamine B. The results show that under optimal conditions (catalyst dosage 0.10 g/L, PMS = 0.10 g/L, pH (5.5 ± 0.1), temperature 20 ℃), 20 mg/L of rhodamine B was almost completely degraded within 180 minutes. The Luyanximen (2020) adopts magnetic CuFe2O4Palygorskite (CuFe)2O4/Pal) activates PMS to degrade rhodamine B, under the optimal reaction condition (the initial concentration of rhodamine B solution is 10 mg/L, the concentration of PMS is 0.1 g/L, the initial pH value is 3, CuFe2O4The dosage of Pal is 0.3 g/L), and the degradation efficiency of rhodamine B after 120 min reaction is 99.99%. The plum-shaped hydronium etc. (2021) adopts a two-step hydrothermal method to prepare MnO2/CoFe2O4Magnetic composite catalyst, the result shows that in MnO2/CoFe2O4The adding amount of the composite material is 0.3 g/L, the concentration of PMS is 1.25 mmol/L, and the decolorization rate of an acid scarlet 3R solution with the initial concentration of 50 mg/L after 10 min of reaction is 93.5% under the condition of pH 3. Compared with the materials, the composite material prepared by the invention has the advantages of wide pH application range, good decolorization effect and the like.
2. Degradation property of p-phenol
60 mL of 10 mg/L phenol solution was selected, 1 mL of PMS solution with a concentration of 40 mmol/L was added thereto, the pH =5 of the solution was adjusted, then 0.05 g of the nanocomposite of the present invention was added, the mixture was shaken in a constant temperature water bath shaker at 25 ℃ and 250 rpm for 5 hours, a sample was taken at a predetermined time, and the phenol concentration was measured spectrophotometrically with respect to the filtrate after filtration through a 0.45 μm microfiltration membrane after precipitation. FIG. 3 is a phenol degradation efficiency curve of the attapulgite/manganese dioxide/ferroferric oxide nanocomposite (example 1) prepared by the method. As can be seen from figure 3, the nano composite material catalyzes PMS to degrade phenol, the balance is achieved within 2 h, and the degradation efficiency can reach 97.89%. The result shows that the prepared attapulgite/manganese dioxide/ferroferric oxide nano composite material can be used as a PMS catalyst to realize the high-efficiency removal of phenol.
3. Nanocomposite recycling performance
Taking 50 mL of acid scarlet (GR) dye wastewater with the concentration of 200 mg/L, adding 2 mL of PMS solution with the concentration of 30 mmol/L, adjusting the pH to be =5, then adding the nanocomposite material, oscillating for 6 h in a constant-temperature water bath oscillator at 25 ℃ and 250 rpm, filtering by using a 0.45 mu m microporous filter membrane after precipitation, and measuring the concentration of the acid scarlet (GR) dye wastewater by a spectrophotometry method. And performing magnetic separation (collecting the attapulgite/manganese dioxide/ferroferric oxide nano composite material, washing and drying), and then performing catalytic degradation on the acid scarlet (GR) dye wastewater. FIG. 4 shows the cyclic decoloring efficiency of the attapulgite/manganese dioxide/ferroferric oxide nanocomposite prepared by the method (example 1) on acid scarlet (GR) dye wastewater. As can be seen from FIG. 4, the decolorization rate of the nanocomposite after 5 times of catalytic degradation on acid scarlet (GR) dye wastewater by circulation is 90.74%. The result shows that the attapulgite/manganese dioxide/ferroferric oxide nano composite material obtained by the invention has good recycling performance.
Panliang et al (2020) preparation of Fe3O4the/RGO magnetic composite material is used as a catalyst to degrade methyl orange, and the catalyst obtains 70.2% of methyl orange removal efficiency after 5 times of circulation. The magnetic ternary material CoFeNi-LDH is successfully prepared by a chemical coprecipitation method in the step of Schneider et al (2017), PMS is activated, and azo dye is degradedAnd (5) taking Congo red as a raw material. After the catalyst is subjected to cyclic regeneration for 3 times, the Congo red decolorization rate is 88%. Compared with the materials, the invention has good reusability and is easy to recycle.
The above-mentioned embodiments are only preferred embodiments of the present invention, and do not limit the technical scope of the present invention, so that the changes and modifications made by the claims and the specification of the present invention should fall within the scope of the present invention.
Claims (10)
1. A preparation method of an attapulgite/manganese dioxide/ferroferric oxide nano composite material is characterized by comprising the following steps: the method comprises the following steps: (1) weighing a certain amount of ferrous sulfate heptahydrate, dissolving the ferrous sulfate heptahydrate in water, adding polyvinylpyrrolidone, stirring and heating, then adding a sodium hydroxide solution with the concentration of 3-5 mol/L into the solution, continuously heating and stirring after the solution generates a blue-green precipitate, stopping heating and cooling to room temperature after the blue-green precipitate becomes black, centrifuging, washing and drying to obtain ferroferric oxide powder; (2) adding potassium permanganate, a divalent manganese ion reducing agent and the ferroferric oxide powder obtained in the step (1) into attapulgite serving as a raw material, adding pure water, oscillating in a water bath oscillator, performing ultrasonic treatment, centrifuging, cleaning, drying, and grinding to more than 200 meshes to obtain the attapulgite/manganese dioxide/ferroferric oxide nano composite material.
2. A preparation method of an attapulgite/manganese dioxide/ferroferric oxide nano composite material is characterized by comprising the following steps: in the step (1), the heating temperature is 70-80 ℃, and the time for continuously heating and stirring is 1.5-2 h.
3. The method of claim 1, wherein: in the step (2), the using amount of the potassium permanganate is 40-60% of the mass of the attapulgite.
4. The method of claim 1, wherein: in the step (2), the dosage of the divalent manganese ion reducing agent is 0.0319-0.0390 mol/L.
5. The method of claim 1, wherein: in the step (2), the mass ratio of the ferroferric oxide powder to the attapulgite is 1: 3.3-1: 5.
6. the method of claim 1, wherein: in the step (2), the conditions of the water bath and the drying are as follows: oscillating for 5-6 h in a water bath oscillator at 20-25 ℃ and 200-250 rpm, washing and centrifuging the obtained product, and drying in an oven at 50-60 ℃ for 12-24 h.
7. The method of claim 1, wherein: in the step (2), the attapulgite is attapulgite powder with the grain diameter of 200-320 meshes, namely 75-45 μm.
8. The method of claim 1, wherein: in the step (2), the divalent manganese ion reducing agent is manganese sulfate or manganese chloride.
9. An attapulgite/manganese dioxide/ferroferric oxide nanocomposite prepared by the method of claim 1, which is characterized in that: the attapulgite has a nano rod-shaped structure, and ferroferric oxide nano particles and manganese dioxide particles are attached to the surface of the attapulgite.
10. The application of the attapulgite/manganese dioxide/ferroferric oxide nanocomposite material according to claim 8 in degrading organic pollutants.
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