CN112264096A - Magnetic Fenton-like catalyst based on chitosan and preparation method and application thereof - Google Patents
Magnetic Fenton-like catalyst based on chitosan and preparation method and application thereof Download PDFInfo
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- 229920001661 Chitosan Polymers 0.000 title claims abstract description 79
- 239000003054 catalyst Substances 0.000 title claims abstract description 51
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims abstract description 50
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 39
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 39
- 239000000243 solution Substances 0.000 claims abstract description 38
- 239000004005 microsphere Substances 0.000 claims abstract description 25
- 239000003513 alkali Substances 0.000 claims abstract description 24
- 239000002131 composite material Substances 0.000 claims abstract description 20
- 239000012266 salt solution Substances 0.000 claims abstract description 19
- 239000011324 bead Substances 0.000 claims abstract description 16
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims abstract description 14
- 238000004108 freeze drying Methods 0.000 claims abstract description 13
- 238000005406 washing Methods 0.000 claims abstract description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 13
- 230000032683 aging Effects 0.000 claims abstract description 12
- 150000002696 manganese Chemical class 0.000 claims abstract description 12
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims abstract description 11
- 230000010355 oscillation Effects 0.000 claims abstract description 11
- 239000001632 sodium acetate Substances 0.000 claims abstract description 11
- 235000017281 sodium acetate Nutrition 0.000 claims abstract description 11
- 239000011259 mixed solution Substances 0.000 claims abstract description 9
- 230000007935 neutral effect Effects 0.000 claims abstract description 9
- 150000003839 salts Chemical class 0.000 claims abstract description 7
- 238000006731 degradation reaction Methods 0.000 claims description 28
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 20
- CXKWCBBOMKCUKX-UHFFFAOYSA-M methylene blue Chemical compound [Cl-].C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 CXKWCBBOMKCUKX-UHFFFAOYSA-M 0.000 claims description 19
- 229960000907 methylthioninium chloride Drugs 0.000 claims description 19
- 230000015556 catabolic process Effects 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 13
- 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 claims description 12
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims description 9
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical group OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 7
- 229910002651 NO3 Inorganic materials 0.000 claims description 7
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 7
- 238000011065 in-situ storage Methods 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- 229910021380 Manganese Chloride Inorganic materials 0.000 claims description 5
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 claims description 5
- 150000002505 iron Chemical class 0.000 claims description 5
- 239000011565 manganese chloride Substances 0.000 claims description 5
- 235000002867 manganese chloride Nutrition 0.000 claims description 5
- 229940099607 manganese chloride Drugs 0.000 claims description 5
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims description 5
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 4
- 229960002089 ferrous chloride Drugs 0.000 claims description 4
- 239000011790 ferrous sulphate Substances 0.000 claims description 4
- 235000003891 ferrous sulphate Nutrition 0.000 claims description 4
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 claims description 4
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 4
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 claims description 4
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 4
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 4
- 229940099596 manganese sulfate Drugs 0.000 claims description 4
- 239000011702 manganese sulphate Substances 0.000 claims description 4
- 235000007079 manganese sulphate Nutrition 0.000 claims description 4
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims description 4
- 239000007800 oxidant agent Substances 0.000 claims description 3
- 239000012670 alkaline solution Substances 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 claims 1
- 229910052751 metal Inorganic materials 0.000 abstract description 8
- 239000002184 metal Substances 0.000 abstract description 8
- 238000005054 agglomeration Methods 0.000 abstract description 4
- 230000002776 aggregation Effects 0.000 abstract description 4
- 239000002923 metal particle Substances 0.000 abstract description 3
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 52
- 238000006243 chemical reaction Methods 0.000 description 8
- 239000008367 deionised water Substances 0.000 description 7
- 229910021641 deionized water Inorganic materials 0.000 description 7
- 238000005303 weighing Methods 0.000 description 7
- 238000004458 analytical method Methods 0.000 description 5
- 239000000975 dye Substances 0.000 description 5
- 238000003760 magnetic stirring Methods 0.000 description 5
- 238000001035 drying Methods 0.000 description 4
- 238000007710 freezing Methods 0.000 description 4
- 230000008014 freezing Effects 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 238000002159 adsorption--desorption isotherm Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000000975 co-precipitation Methods 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000001027 hydrothermal synthesis Methods 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 239000011325 microbead Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000010525 oxidative degradation reaction Methods 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
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- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 229910001448 ferrous ion Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 1
- 238000010335 hydrothermal treatment Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- DALUDRGQOYMVLD-UHFFFAOYSA-N iron manganese Chemical class [Mn].[Fe] DALUDRGQOYMVLD-UHFFFAOYSA-N 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 239000006249 magnetic particle Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000012286 potassium permanganate Substances 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 238000009987 spinning Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
- B01J31/069—Hybrid organic-inorganic polymers, e.g. silica derivatized with organic groups
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/28—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of the platinum group metals, iron group metals or copper
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- B01J35/33—
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- B01J35/50—
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/722—Oxidation by peroxides
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/40—Organic compounds containing sulfur
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Abstract
The invention provides a magnetic Fenton catalyst based on chitosan and a preparation method and application thereof, wherein the chitosan is dissolved in an acetic acid solution, a manganese salt, a ferric salt and a ferrous salt are added and stirred to obtain a uniformly dispersed salt solution A, and sodium hydroxide and sodium acetate are dissolved in water to form an alkali solution B; dropwise adding the salt solution A into the alkali solution B at a constant speed, and after dropwise adding, placing the obtained mixed solution into a constant-temperature oscillator for oscillation aging to obtain CH-Mn-Fe gel beads; washing the CH-Mn-Fe gel beads to be neutral, and freeze-drying to obtain the magnetic microsphere MnO with the porous structure2‑Fe3O4a/CH composite catalyst. Avoids the agglomeration of metal particles, inhibits the metal loss, is extremely easy to recover and has simple preparation process.
Description
Technical Field
The invention relates to the technical field of magnetic catalyst preparation, in particular to MnO2-Fe3O4A chitosan composite magnetic microsphere and a one-step in-situ preparation method and application thereof.
Background
The dye is widely applied to the industries of synthesis, spinning, cosmetics, printing and the like, and the problem of serious environmental pollution is caused by the discharge of a large amount of industrial dye wastewater. Methylene blue is one of the most common dyes and has been shown to cause a variety of human diseases. Therefore, the removal of methylene blue from water is of great importance. There are many methods for removing dyes from water, and among them, advanced oxidative degradation technology has attracted much attention because of its advantages such as simplicity and high efficiency. The fenton method is a classical advanced oxidative degradation technique: namely hydrogen peroxide (H)2O2) And ferrous ion (Fe)2+) The mixtures of (a) oxidize many organic compounds, such as carboxylic acids, alcohols and esters, to harmless chemicals. However, the application of the traditional Fenton method is limited by the defects that the applicable pH range (2-4) is narrow, the catalyst is not easy to separate and recycle from the wastewater after the reaction, a large amount of iron mud is generated, secondary pollution is caused, and the like. In order to solve the above problems, efforts have been made to develop heterogeneous fenton-like systems: using metal oxides instead of Fe2+As a reaction catalyst. The use of a heterogeneous fenton-like system has the following advantages: (1) the application range is wide, and the degradation rate is high; (2) the catalyst is easy to separate and recycle, and secondary pollution is avoided.
The electron transfer is an important process of a heterogeneous Fenton-like catalytic system, so that the nano manganese dioxide (MnO) with multiple oxidation states2) And nano ferroferric oxide (Fe)3O4) Is an ideal heterogeneous Fenton-like catalyst. However, the direct use of these nano metal catalysts causes the following problems: (1) agglomeration phenomenon. The effective active area of the catalyst is reduced and thus the catalytic efficiency is reduced. (2) The metal runs off. The leaching of metal ions leads to the reduction of active components and simultaneously brings secondary pollution to water. (3) Recovery is difficult. Powdered nano metal has higher hydrophilicity, and needs to be centrifuged or filtered in a laboratory to be recycled, so that the actual application cost is increased. These problems above limit the nano-MnO to a great extent2And Fe3O4Industrial application of (1).
Nano MnO2And nano Fe3O4The synergistic effect of (A) contributes to the improvement of the degradation efficiency, and at present most of MnO is2-Fe3O4The preparation method of the composite catalyst is a two-step hydrothermal method, and ferrous sulfate (FeSO) is firstly used4) Raw materials are synthesized into nano Fe by a hydrothermal method3O4Then potassium permanganate (KMnO) is added4) With nano Fe3O4MnO is obtained after mixed hydrothermal treatment2-Fe3O4Composite catalyst (Chemical Engineering Journal,2019,357 (337-347)). The preparation method has complicated steps, and the obtained composite catalyst has nanometer MnO due to the unsaturation and instability of the surface of the nanometer particles2And Fe3O4The particles are easy to aggregate and are not beneficial to activating H2O2。
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a magnetic Fenton-like catalyst based on chitosan, a one-step in-situ preparation method and application thereof, which avoid metal particle agglomeration, inhibit metal loss, are easy to recover and have a simple preparation process.
The invention is realized by the following technical scheme:
a preparation method of a magnetic Fenton-like catalyst based on chitosan comprises the following steps:
dissolving chitosan in an acetic acid solution, adding manganese salt, ferric salt and ferrous salt, stirring to obtain a uniformly dispersed salt solution A, and dissolving sodium hydroxide and sodium acetate in water to form an alkali solution B; dropwise adding the salt solution A into the alkali solution B at a constant speed, and after dropwise adding, placing the obtained mixed solution into a constant-temperature oscillator for oscillation aging to obtain CH-Mn-Fe gel beads; washing the CH-Mn-Fe gel beads to be neutral, and freeze-drying to obtain the magnetic microsphere MnO with the porous structure2-Fe3O4a/CH composite catalyst.
Preferably, the mass volume ratio of the chitosan to the acetic acid is 1 g: (0.1-1) mL, and the concentration of the acetic acid solution is 0.25-2.5 wt%.
Preferably, the manganese salt is one of manganese nitrate, manganese sulfate and manganese chloride; the ferrous salt is one of ferrous nitrate, ferrous sulfate and ferrous chloride; the iron salt is one of ferric nitrate, ferric sulfate and ferric chloride.
Preferably, the mass molar ratio of the chitosan to the manganese salt is 1 g: (0.001-0.02) mol, wherein the molar ratio of manganese salt to iron salt is 1: (0.1-10), and the molar ratio of the ferric salt to the ferrous salt is 2: 1.
Preferably, the concentration of sodium hydroxide in the alkali solution B is 0.1-2M, and the molar ratio of sodium hydroxide to sodium acetate is 1: 1.
Preferably, the dropping speed of the saline solution A dropwise adding the alkali solution B at constant speed is 3-10 mL/min.
Preferably, the temperature of the constant temperature oscillator is 20-80 ℃, the oscillation aging time is 3-24 h, and the freeze drying time is 6-24 h.
Magnetic microsphere MnO obtained by adopting the preparation method2-Fe3O4a/CH composite catalyst.
The magnetic microsphere MnO2-Fe3O4The application of the/CH composite catalyst in catalyzing methylene blue heterogeneous Fenton degradation reaction.
Preferably, the oxidant for the heterogeneous Fenton-like degradation reaction of methylene blue is H2O2，H2O2The dosage is 0.1-2M, MnO2-Fe3O4The dosage of the/CH composite catalyst is 0.5-5 g/L, and the degradation time is 30-120 min.
Compared with the prior art, the invention has the following beneficial technical effects:
the process of the invention is based on ferromanganese salts and OH-Coprecipitated oxidation (Fe)2++2Fe3++8OH-→Fe3O4+4H2O,2Mn2++4OH-+O2→2MnO2+2H2O) and Chitosan (CH) is subjected to polymerization crosslinking by alkali, the two reaction processes are coupled, and the nano MnO is subjected to next step under the alkali condition2And nano Fe3O4Immobilized in a chitosan network structure to obtain macroscopic magnetic microspheres MnO2-Fe3O4and/CH. abundant-NH on the carbon chain of chitosan2and-OH function with Mn2+And Fe3+And through interaction, the metal oxide is uniformly dispersed in situ in a network structure generated by chitosan crosslinking, so that the agglomeration of metal particles is avoided. At the same time, the active metaland-NH2The coordination of (2) inhibits metal loss and improves the stability of the catalyst. Obtained macroscopic magnetic microsphere MnO2-Fe3O4the/CH is millimeter-scale magnetic particles and is easy to recover. MnO2And Fe3O4The metal synergistic effect exists between the two, and the transmission of electrons in Fenton-like reaction is promoted, so that MnO is2-Fe3O4The catalytic activity of/CH for Fenton degradation of methylene blue is obviously higher than that of a single metal catalyst (MnO)2/CH or Fe3O4/CH). The invention is prepared in one step, the preparation process is mild, the process is simple, the operation is easy, and the cost of the chitosan serving as the raw material is lower.
Drawings
FIG. 1 one-step in-situ preparation of magnetic microsphere MnO2-Fe3O4Flow diagram of/CH.
FIG. 2 magnetic microsphere MnO2-Fe3O4a/CH: (A) before freeze-drying, (B) after freeze-drying.
FIG. 3MnO2/CH、Fe3O4[ CH ] and MnO2-Fe3O4XRD diffractogram of/CH sample.
FIG. 4MnO2-Fe3O4Of the/CH samples: (A) n is a radical of2Adsorption-desorption isotherms, and (B) size distribution curves.
FIG. 5 is a comparison of the images before and after Fenton-like degradation of methylene blue solution.
Detailed Description
The present invention will now be described in further detail with reference to specific examples, which are intended to be illustrative, but not limiting, of the invention.
The method of the invention is to form nano particles in situ in a polymer matrix through alkaline coprecipitation of manganese salt, ferric salt and ferrous salt, and form magnetic chitosan gel microbeads through joint aging. No MnO has been found yet by searching domestic and foreign documents2-Fe3O4The coprecipitation process is coupled with the alkali polymerization process of the chitosan, and MnO is synthesized in situ by one step2-Fe3O4A preparation method of a/CH composite catalyst.
As shown in fig. 1, the preparation method of the invention specifically comprises the following steps:
(1) weighing 1g of chitosan, fully dissolving the chitosan in 40mL of 0.25-2.5 wt% acetic acid solution, sequentially adding 0.001-0.02 mol of manganese salt, 0.0001-0.2 mol of ferric salt and 0.00005-0.1 mol of ferrous salt, and fully dissolving to obtain a salt solution A. Weighing 0.01-0.2 mol of sodium hydroxide and 0.01-0.2 mol of sodium acetate, and dissolving in 100mL of deionized water to form an alkali solution B. And dropwise adding the salt solution A into the alkali liquor B at a constant speed of 3-10 mL/min. After the dropwise addition is finished, the obtained mixed solution is placed in a constant-temperature oscillator at the temperature of 20-80 ℃ for oscillation and aging for 3-24 hours, and the composite gel microbeads are obtained. Washing the gel microspheres with deionized water to be neutral, and freeze-drying for 6-24 h to obtain magnetic microspheres MnO with a porous structure2-Fe3O4a/CH composite catalyst.
The manganese salt is one of manganese nitrate, manganese sulfate and manganese chloride; the ferrous salt is one of ferrous nitrate, ferrous sulfate and ferrous chloride; the iron salt is one of ferric nitrate, ferric sulfate and ferric chloride.
Magnetic microsphere MnO as described above2-Fe3O4the/CH is used for catalyzing the Fenton-like degradation of methylene blue heterogeneous phase and comprises the following steps: firstly, magnetic microspheres MnO are added2-Fe3O4Mixing the/CH with the dye solution, and adding hydrogen peroxide to carry out Fenton-like degradation reaction. Wherein the concentration of methylene blue is 10-500 mg/L, and the oxidant H2O2The dosage is 0.1-2M, and the magnetic microspheres MnO2-Fe3O4The dosage of/CH is 0.5-5 g/L, and the degradation time is 30-120 min.
Example 1
Weighing 1g of chitosan, fully dissolving the chitosan in 40mL of 0.25 wt% acetic acid solution, sequentially adding 0.001mol of manganese nitrate, 0.2mol of ferric nitrate and 0.1mol of ferrous nitrate, and keeping magnetic stirring until the chitosan is fully dissolved to obtain a uniformly dispersed salt solution A. 0.01mol of sodium hydroxide and 0.01mol of sodium acetate are weighed out and dissolved in 100mL of deionized water to form an alkali solution B. Dropwise adding the salt solution A into the alkali solution B at a constant speed of 3mL/min, after dropwise adding, placing the obtained mixed solution into a constant temperature oscillator at 20 ℃ for oscillation aging for 3h,CH-Mn-Fe gel beads were obtained as shown in FIG. 2 (A). Washing the CH-Mn-Fe gel beads to be neutral, and freeze-drying for 6h to obtain the magnetic microsphere MnO with the porous structure2-Fe3O4The particle diameter of the/CH composite catalyst is 2-4mm as shown in FIG. 2 (B).
By wide angle XRD (FIG. 3), MnO2-Fe3O4the/CH corresponds to MnO at 2 θ of 19.2 °, 36.9 ° and 50.2 °, respectively2The (111), (311) and (331) faces (JCPDS No. 44-0992); fe corresponds to 30.2 °, 35.6 °, 43.3 °, 57.1 ° and 62.8 ° for 2 θ, respectively3O4The (220), (311), (400), (511) and (440) faces (JCPDS No. 19-0629). This indicates MnO2-Fe3O4Successful preparation of the/CH composite catalyst. In addition, MnO2-Fe3O4N of/CH2The adsorption-desorption isotherm (fig. 4(a)) is type IV of the hysteresis cycle of H3, which clearly indicates the presence of mesopores. Pore size distribution curve (FIG. 4(B)) shows MnO2-Fe3O4the/CH is distributed in micro/meso/macro pores, and the size is mainly between 20 and 100 nm.
100mL of 10 mg/L methylene blue solution were measured in an Erlenmeyer flask, and 0.01mol of H were added2O2And 0.5g of magnetic microsphere MnO prepared above2-Fe3O4and/CH, stirring and reacting for 30min at room temperature. The degradation rate of methylene blue is 75.5 percent by the analysis of an ultraviolet visible light spectrophotometer. After the reaction is finished, the catalyst is separated by a magnet (figure 5), the catalyst is fully washed, then is frozen and dried overnight, the cycle test is carried out under the same condition, and the degradation rate can still reach 69.4 percent after three continuous degradation reactions. The catalyst proved to have good stability.
Example 2
Weighing 1g of chitosan, fully dissolving the chitosan in 40mL of 1.0 wt% acetic acid solution, sequentially adding 0.005mol of manganese sulfate, 0.025mol of ferric nitrate and 0.0125mol of ferrous nitrate, and keeping magnetic stirring until the chitosan is fully dissolved to obtain a uniformly dispersed salt solution A. 0.05mol of sodium hydroxide and 0.05mol of sodium acetate are weighed out and dissolved in 100mL of deionized water to form an alkali solution B. Dropwise adding the salt solution A into the alkali solution B at a constant speed of 5mL/min to obtain a solutionThe mixed solution is placed in a constant temperature oscillator at 40 ℃ for oscillation and aging for 8 hours to obtain CH-Mn-Fe gel beads. Washing the CH-Mn-Fe gel beads to be neutral, and freeze-drying for 12h to obtain the magnetic microsphere MnO with the porous structure2-Fe3O4a/CH composite catalyst.
100mL of 50 mg/L methylene blue solution were measured in an Erlenmeyer flask, and 0.05mol of H were added2O2And 2.0g of magnetic microsphere MnO prepared as described above2-Fe3O4and/CH, stirring and reacting for 60min at room temperature. The degradation rate of methylene blue is 90.7 percent by the analysis of an ultraviolet visible light spectrophotometer. After the reaction is finished, separating the catalyst by using a magnet, fully washing, freezing and drying overnight, carrying out a cycle test under the same condition, and carrying out three continuous degradation reactions until the degradation rate still reaches 87.2%. The catalyst proved to have good stability.
Embodiment 3
Weighing 1g of chitosan, fully dissolving the chitosan in 40mL of 2.0 wt% acetic acid solution, sequentially adding 0.01mol of manganese chloride, 0.02mol of ferric chloride and 0.01mol of ferrous chloride, and keeping magnetic stirring until the chitosan is fully dissolved to obtain a uniformly dispersed salt solution A. 0.1mol of sodium hydroxide and 0.1mol of sodium acetate are weighed out and dissolved in 100mL of deionized water to form an alkali solution B. Dropwise adding the salt solution A into the alkali solution B at a constant speed of 7mL/min, and after dropwise adding, placing the obtained mixed solution into a constant-temperature oscillator at 50 ℃ for oscillation aging for 12h to obtain CH-Mn-Fe gel beads. Washing the CH-Mn-Fe gel beads to be neutral, and freeze-drying for 16h to obtain the magnetic microsphere MnO with the porous structure2-Fe3O4a/CH composite catalyst.
100mL of a 100 mg/L methylene blue solution was measured in an Erlenmeyer flask, and 0.1mol of H was added2O2And 3.0g of magnetic microsphere MnO prepared as described above2-Fe3O4and/CH, stirring and reacting for 80min at room temperature. The degradation rate of methylene blue is 100% by the analysis of an ultraviolet-visible light spectrophotometer. After the reaction is finished, separating the catalyst by using a magnet, fully washing, freezing and drying overnight, carrying out a cycle test under the same condition, and carrying out three continuous degradation reactions until the degradation rate still reaches 98.2%. The catalyst proved to have good stability.
Example 4
Weighing 1g of chitosan, fully dissolving the chitosan in 40mL of 4.0 wt% acetic acid solution, sequentially adding 0.015mol of manganese nitrate, 0.015mol of ferric nitrate and 0.0075mol of ferrous nitrate, and keeping magnetic stirring until the chitosan is fully dissolved to obtain a uniformly dispersed salt solution A. 0.15mol of sodium hydroxide and 0.15mol of sodium acetate are weighed out and dissolved in 100mL of deionized water to form the alkali solution B. Dropwise adding the salt solution A into the alkali solution B at a constant speed of 9mL/min, and after dropwise adding, placing the obtained mixed solution into a constant-temperature oscillator at 70 ℃ for oscillation aging for 18h to obtain CH-Mn-Fe gel beads. Washing the CH-Mn-Fe gel beads to be neutral, and freeze-drying for 20h to obtain the magnetic microsphere MnO with the porous structure2-Fe3O4a/CH composite catalyst.
100mL of 250 mg/L methylene blue solution was measured in an Erlenmeyer flask, and 0.15mol of H was added2O2And 3.0g of magnetic microsphere MnO prepared as described above2-Fe3O4and/CH, stirring and reacting for 100min at room temperature. The degradation rate of methylene blue is 98.3 percent by the analysis of an ultraviolet visible light spectrophotometer. After the reaction is finished, separating the catalyst by using a magnet, fully washing, freezing and drying overnight, carrying out a cycle test under the same condition, and carrying out three continuous degradation reactions until the degradation rate still reaches 95.6%. The catalyst proved to have good stability.
Example 5
Weighing 1g of chitosan, fully dissolving the chitosan in 40mL of 5.0 wt% acetic acid solution, sequentially adding 0.01mol of manganese chloride, 0.0001mol of ferric sulfate and 0.00005mol of ferrous nitrate, and keeping magnetic stirring until the chitosan is fully dissolved to obtain a uniformly dispersed salt solution A. 0.2mol of sodium hydroxide and 0.2mol of sodium acetate are weighed out and dissolved in 100mL of deionized water to form the alkali solution B. Dropwise adding the salt solution A into the alkali solution B at a constant speed of 10mL/min, and after dropwise adding, placing the obtained mixed solution into a constant-temperature oscillator at 80 ℃ for oscillation aging for 24h to obtain CH-Mn-Fe gel beads. Washing the CH-Mn-Fe gel beads to be neutral, and freeze-drying for 24h to obtain the magnetic microsphere MnO with the porous structure2-Fe3O4a/CH composite catalyst.
Measuring 100mL500 mg/LMethylene blue solution is put into a conical flask, and 0.2mol of H is added2O2And 5.0g of magnetic microsphere MnO prepared above2-Fe3O4and/CH, stirring and reacting for 120min at room temperature. The degradation rate of methylene blue is 95.8 percent by the analysis of an ultraviolet visible light spectrophotometer. After the reaction is finished, separating the catalyst by using a magnet, fully washing, freezing and drying overnight, carrying out a cycle test under the same condition, and carrying out three continuous degradation reactions until the degradation rate still reaches 92.4%. The catalyst proved to have good stability.
Claims (10)
1. A preparation method of a magnetic Fenton-like catalyst based on chitosan is characterized by comprising the following steps:
dissolving chitosan in an acetic acid solution, adding manganese salt, ferric salt and ferrous salt, stirring to obtain a uniformly dispersed salt solution A, and dissolving sodium hydroxide and sodium acetate in water to form an alkali solution B; dropwise adding the salt solution A into the alkali solution B at a constant speed, and after dropwise adding, placing the obtained mixed solution into a constant-temperature oscillator for oscillation aging to obtain CH-Mn-Fe gel beads; washing the CH-Mn-Fe gel beads to be neutral, and freeze-drying to obtain the magnetic microsphere MnO with the porous structure2-Fe3O4a/CH composite catalyst.
2. The method of preparing a chitosan-based magnetic fenton-like catalyst according to claim 1, wherein the mass volume ratio of chitosan to acetic acid is 1 g: (0.1-1) mL, and the concentration of the acetic acid solution is 0.25-2.5 wt%.
3. The method of preparing a chitosan-based magnetic fenton-like catalyst according to claim 1, wherein the manganese salt is one of manganese nitrate, manganese sulfate and manganese chloride; the ferrous salt is one of ferrous nitrate, ferrous sulfate and ferrous chloride; the iron salt is one of ferric nitrate, ferric sulfate and ferric chloride.
4. The method for preparing a chitosan-based magnetic fenton-like catalyst according to claim 1, wherein the mass molar ratio of chitosan to manganese salt is 1 g: (0.001-0.02) mol, wherein the molar ratio of manganese salt to iron salt is 1: (0.1-10), and the molar ratio of the ferric salt to the ferrous salt is 2: 1.
5. The method for preparing a magnetic fenton-like catalyst based on chitosan according to claim 1, wherein the concentration of sodium hydroxide in the alkali solution B is 0.1-2M, and the molar ratio of sodium hydroxide to sodium acetate is 1: 1.
6. The preparation method of the chitosan-based magnetic Fenton-like catalyst according to claim 1, wherein the dropping speed of the alkaline solution B dropwise added into the salt solution A at a constant speed is 3-10 mL/min.
7. The one-step in-situ preparation method of the chitosan-based magnetic Fenton-like catalyst according to claim 1, wherein the temperature of the constant temperature oscillator is 20-80 ℃, the oscillation aging time is 3-24 h, and the freeze drying time is 6-24 h.
8. A chitosan-based magnetic Fenton-like catalyst obtained by the production method according to any one of claims 1 to 7.
9. Use of the chitosan-based magnetic Fenton-like catalyst of claim 8 in catalyzing methylene blue heterogeneous Fenton-like degradation reactions.
10. The use according to claim 9, wherein the oxidizing agent for the heterogeneous Fenton-like degradation reaction of methylene blue is H2O2，H2O2The dosage is 0.1-2M, MnO2-Fe3O4The dosage of the/CH composite catalyst is 0.5-5 g/L, and the degradation time is 30-120 min.
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