WO2022042530A1 - Mn2o 3@n-dopted porous carbon hybrid fenton-like material, preparation method therefor and application thereof - Google Patents
Mn2o 3@n-dopted porous carbon hybrid fenton-like material, preparation method therefor and application thereof Download PDFInfo
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- WO2022042530A1 WO2022042530A1 PCT/CN2021/114260 CN2021114260W WO2022042530A1 WO 2022042530 A1 WO2022042530 A1 WO 2022042530A1 CN 2021114260 W CN2021114260 W CN 2021114260W WO 2022042530 A1 WO2022042530 A1 WO 2022042530A1
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- fenton
- porous carbon
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- doped porous
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 71
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 71
- 239000000463 material Substances 0.000 title claims abstract description 69
- 238000002360 preparation method Methods 0.000 title claims abstract description 40
- 239000011572 manganese Substances 0.000 claims abstract description 168
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims abstract description 76
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 64
- 238000001354 calcination Methods 0.000 claims abstract description 61
- 239000013239 manganese-based metal-organic framework Substances 0.000 claims abstract description 56
- QMKYBPDZANOJGF-UHFFFAOYSA-N benzene-1,3,5-tricarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(C(O)=O)=C1 QMKYBPDZANOJGF-UHFFFAOYSA-N 0.000 claims abstract description 40
- 238000006243 chemical reaction Methods 0.000 claims abstract description 30
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical compound N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 claims abstract description 21
- 238000003756 stirring Methods 0.000 claims abstract description 18
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 17
- YMKHJSXMVZVZNU-UHFFFAOYSA-N manganese(2+);dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YMKHJSXMVZVZNU-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000011343 solid material Substances 0.000 claims abstract description 16
- 239000000203 mixture Substances 0.000 claims abstract description 15
- 238000004140 cleaning Methods 0.000 claims abstract description 3
- 238000001035 drying Methods 0.000 claims abstract description 3
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims description 41
- 230000003197 catalytic effect Effects 0.000 claims description 36
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 34
- 239000007787 solid Substances 0.000 claims description 31
- 238000000034 method Methods 0.000 claims description 16
- 239000011259 mixed solution Substances 0.000 claims description 15
- 238000010438 heat treatment Methods 0.000 claims description 14
- 238000003760 magnetic stirring Methods 0.000 claims description 14
- 239000002957 persistent organic pollutant Substances 0.000 claims description 13
- 229940106691 bisphenol a Drugs 0.000 claims description 6
- 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 claims description 6
- 229940012189 methyl orange Drugs 0.000 claims description 6
- 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 claims description 6
- 229940043267 rhodamine b Drugs 0.000 claims description 6
- -1 polytetrafluoroethylene Polymers 0.000 claims description 5
- 230000035484 reaction time Effects 0.000 claims description 5
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 abstract description 32
- GEYXPJBPASPPLI-UHFFFAOYSA-N manganese(III) oxide Inorganic materials O=[Mn]O[Mn]=O GEYXPJBPASPPLI-UHFFFAOYSA-N 0.000 abstract description 11
- 239000002105 nanoparticle Substances 0.000 abstract description 5
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 abstract description 3
- 239000011258 core-shell material Substances 0.000 abstract description 3
- 239000003344 environmental pollutant Substances 0.000 abstract description 3
- 231100000719 pollutant Toxicity 0.000 abstract description 3
- 230000007935 neutral effect Effects 0.000 abstract 1
- 231100001234 toxic pollutant Toxicity 0.000 abstract 1
- 239000000126 substance Substances 0.000 description 21
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 20
- 150000003254 radicals Chemical class 0.000 description 19
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 10
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- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 6
- 230000001590 oxidative effect Effects 0.000 description 6
- 239000011148 porous material Substances 0.000 description 6
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- 229910016978 MnOx Inorganic materials 0.000 description 5
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
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- 230000006798 recombination Effects 0.000 description 4
- 238000005215 recombination Methods 0.000 description 4
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 3
- 229910018648 Mn—N Inorganic materials 0.000 description 3
- 230000002776 aggregation Effects 0.000 description 3
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- 125000000524 functional group Chemical group 0.000 description 3
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- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 3
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- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 3
- 239000005416 organic matter Substances 0.000 description 3
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 3
- 230000010287 polarization Effects 0.000 description 3
- 230000002829 reductive effect Effects 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 2
- ATHHXGZTWNVVOU-UHFFFAOYSA-N N-methylformamide Chemical compound CNC=O ATHHXGZTWNVVOU-UHFFFAOYSA-N 0.000 description 2
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 2
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 2
- 238000001069 Raman spectroscopy Methods 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000033558 biomineral tissue development Effects 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 125000002091 cationic group Chemical group 0.000 description 2
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- 239000000725 suspension Substances 0.000 description 2
- 238000004065 wastewater treatment Methods 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- MKYBYDHXWVHEJW-UHFFFAOYSA-N N-[1-oxo-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propan-2-yl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(C(C)NC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 MKYBYDHXWVHEJW-UHFFFAOYSA-N 0.000 description 1
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- DLGYNVMUCSTYDQ-UHFFFAOYSA-N azane;pyridine Chemical compound N.C1=CC=NC=C1 DLGYNVMUCSTYDQ-UHFFFAOYSA-N 0.000 description 1
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- XMEVHPAGJVLHIG-FMZCEJRJSA-N chembl454950 Chemical compound [Cl-].C1=CC=C2[C@](O)(C)[C@H]3C[C@H]4[C@H]([NH+](C)C)C(O)=C(C(N)=O)C(=O)[C@@]4(O)C(O)=C3C(=O)C2=C1O XMEVHPAGJVLHIG-FMZCEJRJSA-N 0.000 description 1
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- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 1
- 238000000024 high-resolution transmission electron micrograph Methods 0.000 description 1
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- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Inorganic materials O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- MMIPFLVOWGHZQD-UHFFFAOYSA-N manganese(3+) Chemical compound [Mn+3] MMIPFLVOWGHZQD-UHFFFAOYSA-N 0.000 description 1
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Images
Classifications
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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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- B01J35/394—
-
- B01J35/60—
-
- B01J35/61—
-
- B01J35/63—
-
- 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
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
-
- 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
- C02F2101/34—Organic compounds containing oxygen
- C02F2101/345—Phenols
-
- 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
- C02F2101/38—Organic compounds containing nitrogen
-
- 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
Definitions
- the invention belongs to the field of materials, and relates to a Fenton material, in particular to a Mn 2 O 3 @N doped porous carbon hybrid-like Fenton material and a preparation method and application thereof.
- Traditional Fenton oxidation includes homogeneous Fenton method and heterogeneous Fenton method, in which homogeneous Fenton is degraded by the reaction of Fe 2+ with H 2 O 2 to generate hydroxyl radicals (HO ) with super oxidizing ability Process of contaminants in water.
- the traditional Fenton technology has many defects, such as strict acidic conditions (pH ⁇ 3), the production of iron sludge during the reaction process, and the extremely low utilization rate of the oxidant, which greatly limit the traditional Fenton method in practical wastewater treatment. application.
- heterogeneous Fenton catalysis has attracted widespread attention.
- the invention application with the application number of 201911252787.X discloses a manganese oxide nanowire-supported ferroferric oxide magnetic Fenton catalyst and its one-step synthesis method and application.
- the divalent iron on the surface of the catalyst can convert oxidants into free radicals, and There is no precipitation of metal ions, and the magnetic ferric oxide particles make the catalyst easy to recover, and the porous structure also exposes more active sites to the catalyst.
- the whole reaction still follows the mechanism of the classical Fenton reaction, and this catalyst still relies on the redox reaction of a single metal site to achieve the activation of hydrogen peroxide, and the utilization rate of hydrogen peroxide in the system is still very low.
- the invention application with the application number of 201911304515.X discloses a preparation method of a high-efficiency iron single-atom Fenton catalytic material.
- the iron active material prepared by this method is anchored on a nitrogen-doped carbon carrier in the form of a single atom, and the loading amount is 0.3 to 10 wt %.
- the method is simple, quick, and relatively inexpensive. However, it is unavoidable that the activity of the metals in the catalyst decreases during the continuous valence conversion, thereby reducing the catalytic performance, thereby reducing the service life of the catalyst.
- the invention application with the application number of 201911250618.2 discloses a heterogeneous Fenton catalyst with high hydrogen peroxide utilization rate and its preparation method and application, which is a preparation method of a heterogeneous copper-based catalyst composite catalyst.
- the introduction of the second metal can significantly inhibit the ineffective decomposition of hydrogen peroxide (decomposition into oxygen and water), and promote the decomposition of hydrogen peroxide into hydroxyl radicals ( OH) with strong oxidizing properties, which increases the unit mole of hydrogen peroxide.
- the amount of quinoline decomposed, that is, the utilization rate of hydrogen peroxide is improved.
- the concentration of hydrogen peroxide required in the entire Fenton reaction process is too high, and due to the self-decomposition of hydrogen peroxide and the reaction with hydroxyl radicals in the system, a large amount of oxidant will be wasted.
- the invention application with the application number of 201911224312.X discloses a preparation method of ultra-small ferric oxide densely coated three-dimensional reduced graphene oxide-based Fenton catalyst.
- the invention solves the problems of non-uniform, weak and few catalytically active sites of Fe 3 O 4 supported on graphene by the existing method.
- the prepared ultra-small ferric oxide densely coated three-dimensional reduced graphene oxide-based Fenton catalyst has significantly improved catalytic performance, degrades tetracycline hydrochloride for 20 min, the degradation rate can reach 100%, and has excellent cycle stability.
- the graphene used in this catalytic material has limitations in practical wastewater treatment and is easily deactivated.
- MnOx Since the valence state changes (II, III, IV) of MnOx in catalytic reactions involve single electron transfer, MnOx is considered to be a promising Fenton-like catalyst. Furthermore, previous studies have shown that MnOx with ultra-nanoscale not only has a high specific surface area, but also shortens the mass/electron transfer pathway, resulting in high catalytic activity. However, due to the large surface energy of ultrafine MnOx , it is easy to aggregate in solution, which severely reduces the exposure of active sites and even leads to irreversible deactivation of the catalyst.
- the present invention provides a Mn 2 O 3 @N-doped porous carbon hybrid Fenton-like material and a preparation method and application thereof, so as to overcome the defects of the prior art.
- the present invention provides a method for preparing a Mn 2 O 3 @N doped porous carbon hybrid Fenton-like material, which has the following characteristics: comprising the following steps: step 1, mixing manganese nitrate hexahydrate, homobenzene Tricarboxylic acid and 2,2'-bipyridine were added to the mixed solution of N,N-dimethylformamide and ethanol, and stirred; in step 2, the mixture obtained in step 1 was transferred to a polytetrafluoroethylene lined high pressure In the kettle, a closed hydrothermal reaction is carried out to obtain the Mn-MOF solid matter; step 3, the Mn-MOF solid matter obtained in the cleaning step 2 is dried again; step 4, the dried Mn-MOF solid matter is calcined in a muffle furnace , to obtain Fenton catalytic materials.
- the present invention provides a method for preparing a Mn 2 O 3 @N-doped porous carbon hybrid Fenton-like material, which may also have the following characteristics: wherein, in step 1, every 40-100 mL of N,N-dimethylformaldehyde 2.51g of manganese nitrate hexahydrate, 0.3-1.2g of trimesic acid and 0.45-1.5g of 2,2'-bipyridine; N,N-dimethylformamide and ethanol were added to the mixed solution of methylformamide and ethanol The volume ratio is 1:1.
- the present invention provides a preparation method of Mn 2 O 3 @N doped porous carbon hybrid Fenton-like material, which may also have the following characteristics: wherein, in step 1, magnetic stirring is used, and the stirring rate is 100-200 r/min , the stirring time is 3-12h.
- the present invention provides a preparation method of Mn 2 O 3 @N doped porous carbon hybrid Fenton-like material, which may also have the following characteristics: wherein, in step 2, the reaction temperature of the hydrothermal reaction is 120-220 °C °C, the reaction time is 15-25h.
- the present invention provides a preparation method of Mn 2 O 3 @N doped porous carbon hybrid Fenton-like material, which may also have the following characteristics: wherein, in step 3, the Mn-MOF solid substance is washed with ethanol and water three times.
- the present invention provides a preparation method of Mn 2 O 3 @N doped porous carbon hybrid Fenton-like material, which may also have the following characteristics: wherein, in step 3, the drying temperature is 60°C-100°C.
- the present invention provides a preparation method of Mn 2 O 3 @N doped porous carbon hybrid Fenton-like material, which may also have the following characteristics: wherein, in step 4, the heating rate of calcination in the muffle furnace is 5 -10°C, the calcination temperature is 400-600°C, and the calcination time is 2-6h.
- the present invention also provides a Mn 2 O 3 @N-doped porous carbon hybrid Fenton-like material, which is prepared by the above preparation method.
- the structural formula of the Fenton material is Mn 2 O 3 -C x -N y , x, y Indicates the addition amounts of trimesic acid and 2,2'-bipyridine, respectively.
- the present invention also provides an application of Mn 2 O 3 @N doped porous carbon hybrid Fenton-like material and PMS in water to treat and degrade organic pollutants.
- the present invention provides an application of a Mn 2 O 3 @N doped porous carbon hybrid Fenton-like material, which can also have the characteristics that the organic pollutants are rhodamine B, bisphenol A and methyl orange. either.
- the Fenton catalytic material is based on the construction of a core-shell structure of ultra-fine nano - Mn 2 O 3 and nitrogen - containing inorganic carbon. material, wherein the thickness of the surface carbon layer is about 5-10 nm. According to the nitrogen adsorption and desorption isotherm and pore size distribution, it can be seen that the synthesized Fenton-like catalyst mainly has mesoporous structure.
- the MOFs-derived carbon shell increases the BET specific surface area and pore volume of the catalyst, thereby facilitating the interfacial reaction and mass transfer process. Due to the formation of the surface porous nitrogen-containing carbon layer, the catalytic material can realize the synergistic effect of the double-reaction active center and the free radical conversion mechanism when catalyzing the degradation of phenolic pollutants.
- the present invention obtains the Mn 2 O 3 type Fenton catalyst whose surface is wrapped with a nitrogen-containing carbon layer by carbonizing the MOFs precursor.
- Ultrafine Mn 2 O 3 is in situ generated and uniformly dispersed in the carbon meshes derived from N-doped MOFs, which improves the stability of the nanocatalysts.
- the cation- ⁇ interaction and Mn - N coordination in Mn2O3@N - doped porous carbon hybrids lead to the formation of a double reaction center, which promotes electron transfer from the electron-rich Mn center to transfer of PMS and generate a large number of free radicals.
- the invention not only synthesizes an efficient Fenton-like double-reaction center catalyst, but also provides a new method for the degradation of organic matter under low-dose PMS.
- the nitrogen atom-doped carbon layer structure and metal generate double reaction active centers through the interaction of cationic ⁇ bond and metal-N bond, avoiding the rate-limiting step in the traditional Fenton-like reaction, avoiding the ineffective decomposition of hydrogen peroxide, and improving the catalyst. catalytic activity.
- the carbon layer structure doped with nitrogen atoms provides adsorption sites for PMS and BPA, and the reaction is carried out on the surface of the catalyst, which reduces the migration distance of free radicals and improves the utilization rate of free radicals, thereby greatly improving the catalytic degradation effect. Utilization of PMS.
- Fig. 1 is the scanning electron microscope image and transmission electron microscope image of the product Mn 2 O 3 -C 0.9 -N 1.2 of Example 3, and Mn 2 O 3 and Mn 2 O 3 -C 0.9 ;
- Fig. 2 is the N 2 adsorption-desorption curve and pore size distribution map of the product Mn 2 O 3 -C 0.9 -N 1.2 of Example 3, and Mn 2 O 3 and Mn 2 O 3 -C 0.9 ;
- Fig. 3A is the XRD pattern of Example 3 product Mn 2 O 3 -C 0.9 -N 1.2 , and Mn 3 O 4 , Mn 2 O 3 , Mn-MOF and Mn 2 O 3 -C 0.9 ;
- Figure 3B is the Raman spectrum of the product of Example 3 Mn 2 O 3 -C 0.9 -N 1.2 and Mn 2 O 3 ;
- Fig. 3C is the infrared spectrogram of Example 3 product Mn 2 O 3 -C 0.9 -N 1.2 , as well as Mn-MOF and Mn 2 O 3 -C 0.9 ;
- Fig. 3D is the EIS spectrum of Example 3 product Mn 2 O 3 -C 0.9 -N 1.2 , and Mn 3 O 4 , Mn 2 O 3 and Mn 2 O 3 -C 0.9 ;
- Fig. 4 is the XPS spectrum of C, O and N of the product Mn 2 O 3 -C 0.9 -N 1.2 of Example 3 with Mn-MOF;
- Fig. 5 is the catalytic effect diagram of the product Mn 2 O 3 -C x -N y of Example 1-4 (BPA 20ppm, Rh B 10ppm);
- 6A and B are TOC and PMS utilization diagrams of the products of Example 3, Mn 2 O 3 -C 0.9 -N 1.2 and Mn 2 O 3 , respectively;
- Figures 7A and B are the results of the cycle experiment of Mn 2 O 3 and the product of Example 3, Mn 2 O 3 -C 0.9 -N 1.2 , respectively;
- Fig. 7C is the result diagram of the metal leaching experiment of the product Mn 2 O 3 -C 0.9 -N 1.2 and Mn 2 O 3 of Example 3;
- Figure 7D is a structural diagram of the product Mn 2 O 3 -C 0.9 -N 1.2 ;
- Figure 8 is a diagram of the catalytic mechanism of the product Mn 2 O 3 -C 0.9 -N 1.2 .
- This embodiment provides a preparation method and application of a Mn 2 O 3 @N doped porous carbon hybrid Fenton-like material.
- the preparation method includes the following steps:
- Step 1 Add 2.51g manganese nitrate hexahydrate, 0.9g trimesic acid and 0.45g 2,2'-bipyridine into a mixed solution of 30mL N,N-dimethylformamide (DMF) and 30mL ethanol, And magnetic stirring for 6h, stirring rate of 100-200r/min.
- DMF N,N-dimethylformamide
- step 2 the mixture obtained in step 1 was transferred to a polytetrafluoroethylene-lined autoclave, heated at 180° C. for 18 hours, and subjected to a closed hydrothermal reaction to obtain a Mn-MOF solid substance.
- Step 3 Wash the Mn-MOF solid substance obtained in Step 2 three times with ethanol and water, and then dry at 80°C.
- Step 4 calcining the dried Mn-MOF solid material in a muffle furnace, the heating rate of calcination is 5-10°C, the calcination temperature is 500°C, and the calcination time is 4h, and finally the Fenton catalytic material is obtained.
- the product Fenton material is combined with PMS in water to form a Fenton-like system, which is used to treat and degrade organic pollutants in water.
- Organic pollutants include rhodamine B, bisphenol A or methyl orange.
- the product Mn 2 O 3 -C 0.9 -N 0.45 is used in combination with PMS in water to treat and degrade bisphenol A in water, and the results are shown in FIG. 5 .
- This embodiment provides a preparation method and application of a Mn 2 O 3 @N doped porous carbon hybrid Fenton-like material.
- the preparation method includes the following steps:
- Step 1 Add 2.51g manganese nitrate hexahydrate, 0.9g trimesic acid and 0.9g 2,2'-bipyridine into a mixed solution of 30mL N,N-dimethylformamide (DMF) and 30mL ethanol, And magnetic stirring for 6h, stirring rate of 100-200r/min.
- DMF N,N-dimethylformamide
- step 2 the mixture obtained in step 1 was transferred to a polytetrafluoroethylene-lined autoclave, heated at 180° C. for 18 hours, and subjected to a closed hydrothermal reaction to obtain a Mn-MOF solid substance.
- Step 3 Wash the Mn-MOF solid substance obtained in Step 2 three times with ethanol and water, and then dry at 80°C.
- Step 4 calcining the dried Mn-MOF solid material in a muffle furnace, the heating rate of calcination is 5-10°C, the calcination temperature is 500°C, and the calcination time is 4h, and finally a Fenton-like catalytic material is obtained.
- the product Fenton material is combined with PMS in water to form a Fenton-like system, which is used to treat and degrade organic pollutants in water.
- Organic pollutants include rhodamine B, bisphenol A or methyl orange.
- the product Mn 2 O 3 -C 0.9 -N 0.9 is used in combination with PMS in water to treat and degrade bisphenol A in water, and the results are shown in FIG. 5 .
- This embodiment provides a preparation method and application of a Mn 2 O 3 @N doped porous carbon hybrid Fenton-like material.
- the preparation method includes the following steps:
- Step 1 Add 2.51g manganese nitrate hexahydrate, 0.9g trimesic acid and 1.2g 2,2'-bipyridine into a mixed solution of 30mL N,N-dimethylformamide (DMF) and 30mL ethanol, And magnetic stirring for 6h, stirring rate of 100-200r/min.
- DMF N,N-dimethylformamide
- step 2 the mixture obtained in step 1 was transferred to a polytetrafluoroethylene-lined autoclave, heated at 180° C. for 18 hours, and subjected to a closed hydrothermal reaction to obtain a Mn-MOF solid substance.
- Step 3 Wash the Mn-MOF solid substance obtained in Step 2 three times with ethanol and water, and then dry at 80°C.
- Step 4 calcining the dried Mn-MOF solid material in a muffle furnace, the heating rate of calcination is 5-10°C, the calcination temperature is 500°C, and the calcination time is 4h, and finally a Fenton-like catalytic material is obtained.
- the addition amount of trimesic acid is 0.9g, 2,2
- the addition amount of '-bipyridine was 0) for characterization by scanning electron microscopy and transmission electron microscopy, and the results are shown in Figure 1. It can be seen from Fig. 1 that pure Mn 2 O 3 has a dense surface, while Mn 2 O 3 -C 0.9 -N 1.2 has a porous structure. It can be observed in the TEM images that pure Mn2O3 is heavily aggregated due to its relatively high surface energy.
- Mn 2 O 3 nanoparticles are uniformly dispersed in Mn 2 O 3 -C x -N y .
- This strong dispersibility of Mn2O3 nanoparticles can be explained by the fact that during the synthesis, Mn was absorbed by the ligands ( trismellitic acid and 2,2' bipyridine) in the MOFs (Mn-MOFs-Ta-Bd) Chelation. After calcination, a carbon shell is formed on the surface, which prevents the aggregation of nano-manganese dioxide.
- the Mn2O3 - Cx - Ny with a core - shell structure can be clearly observed in the HRTEM images, and the carbon shell wraps the cubic Mn2O3 core.
- the lattice fringes (0.27 nm) also confirm the (222) facet of the cubic phase Mn 2 O 3 .
- Raman spectroscopy was performed on the products Mn 2 O 3 -C 0.9 -N 1.2 and Mn 2 O 3 , and the results are shown in Figure 3B.
- Raman spectroscopy can provide crystallographic information on the carbon skeleton.
- the characteristic peaks near 1360 cm -1 and 1590 cm -1 of Mn 2 O 3 -C 0.9 -N 1.2 represent the defect density and crystallinity of SP2 carbon, respectively, confirming the existence of the carbon shell.
- doping nitrogen heteroatoms in the carbon shell network affects the spin density and charge distribution of carbon atoms, leading to enhanced conductivity of Mn 2 O 3 -C 0.9 -N 1.2 , forming the so-called "active region" .
- the N peaks in Mn 2 O 3 -C 0.9 -N 1.2 can also be fitted to three peaks: 397.5 eV (pyridinic N), 400.2 eV (Mn-N), and 403.8 eV (nitric oxide).
- N has a smaller atomic diameter and stronger electronegativity than C
- doping N in the carbon shell can enhance electron transfer.
- the coordinating pyridine nitrogen may further enhance the polarization difference and promote the formation of dual-reaction centers.
- the product Fenton material is combined with PMS in water to form a Fenton-like system, which is used to treat and degrade organic pollutants in water.
- Organic pollutants include rhodamine B, bisphenol A or methyl orange.
- the product Mn 2 O 3 -C 0.9 -N 1.2 is used in combination with PMS in water to treat and degrade bisphenol A in water, and the results are shown in FIG. 5 .
- the salinity of BPA on different catalysts was evaluated by TOC removal rate, and the results are shown in FIG. 6 . It can be seen from the figure that the TOC removal rate of Mn 2 O 3 -C 0.9 -N 1.2 is much higher than that of Mn 2 O 3 .
- the utilization ratio ( ⁇ ) of PMS of Mn 2 O 3 and Mn 2 O 3 -C 0.9 -N 1.2 showed different trends with the change of reaction time. For the Mn2O3 suspension, the mineralization rate of BPA is slower than the consumption rate of PMS, resulting in low utilization rate at the initial stage of the reaction.
- the bisphenol A intermediate can be completely mineralized by free radicals, which improves the utilization rate of PMS.
- the Mn ( III ) in the Mn2O3 suspension is mostly converted to Mn(IV)
- the PMS activation rate slows down again, and ⁇ gradually decreases after 8 min.
- Mn 2 O 3 -C 0.9 -N 1.2 obtained very high PMS utilization at the beginning of the reaction, which indicated that it was a non-radical reaction ( 1 O 2 ).
- 1 O 2 can be produced by free radical chain reaction.
- the electron-rich Mn centers can donate electrons for PMS activation. Due to the synergistic effect of the dual reaction centers and the extremely high activity of ultrafine Mn2O3, a large amount of free radicals are generated instantaneously.
- the N-doped carbon shell can facilitate electron transfer from organic intermediates to electron-rich Mn centers through CO-Mn and CN-Mn bonds, thereby promoting the redox of Mn and avoiding the ineffective decomposition of PMS.
- the porous structure of the N-doped carbon shell not only promotes the recombination of radicals to generate 1 O 2 , but also provides a large number of adsorption sites for PMS and BPA.
- 1 O 2 has high electrophilicity and can selectively attack electron-rich functional groups and some unsaturated compounds (BPA, etc.). Therefore, with the prolongation of the reaction time, Mn 2 O 3 -CN can also obtain high PMS utilization at very low doses of PMS.
- the leaching amount of Mn 2 O 3 -CN (0.52 mg/L) was much lower than that of Mn 2 O 3 (1.77 mg/L).
- This improvement in stability of Mn 2 O 3 -C 0.9 -N 1.2 can be explained by: (1) the double reaction centers not only avoid the accumulation of high-valent manganese, but also prevent the ineffective decomposition of PMS; (2) N-doped The carbon shell is an effective protective layer against Mn leaching.
- the catalytic principle is as follows: As shown in Figure 8, the Mn 2 O 3 -Cx-Ny nano-doped porous carbon hybrid Fenton-like catalyst prepared by MOFs, the cationic ⁇ bond and the Mn-N complexation lead to the formation of electron-rich Mn centers , which provides electrons for the activation of PMS. Therefore, a large amount of O 2 ⁇ - can be generated by radical chain reaction.
- the porous structure of the N-doped carbon shell not only promotes the recombination of radicals (O 2 ⁇ -, ⁇ OH) to generate 1 O 2 , but also provides adsorption sites for organics, shortening the migration of 1 O 2 distance.
- the N-doped carbon shell acts as the electron-deficient center, which facilitates the electron transfer from R* to the electron-rich Mn center through CO-Mn and CN-Mn bonds, and promotes the transfer of Mn(IV) to Mn(III)/Mn( II) reduction. Due to the synergistic effect of the dual reaction centers, the high adsorption capacity of the N-doped carbon shell and the strong oxidative capacity of 1 O 2 , Mn 2 O 3 -C x -N y , even at a low dose of PMS (0.033 g/L), It can also significantly improve PMS utilization and organic matter mineralization.
- This embodiment provides a preparation method and application of a Mn 2 O 3 @N doped porous carbon hybrid Fenton-like material.
- the preparation method includes the following steps:
- Step 1 Add 2.51g manganese nitrate hexahydrate, 0.9g trimesic acid and 1.5g 2,2'-bipyridine into a mixed solution of 30mL N,N-dimethylformamide (DMF) and 30mL ethanol, And magnetic stirring for 6h, stirring rate of 100-200r/min.
- DMF N,N-dimethylformamide
- step 2 the mixture obtained in step 1 was transferred to a polytetrafluoroethylene-lined autoclave, heated at 180° C. for 18 hours, and subjected to a closed hydrothermal reaction to obtain a Mn-MOF solid substance.
- Step 3 Wash the Mn-MOF solid substance obtained in Step 2 three times with ethanol and water, and then dry at 80°C.
- Step 4 calcining the dried Mn-MOF solid material in a muffle furnace, the heating rate of calcination is 5-10°C, the calcination temperature is 500°C, and the calcination time is 4h, and finally a Fenton-like catalytic material is obtained.
- the product Fenton material is combined with PMS in water to form a Fenton-like system, which is used to treat and degrade organic pollutants in water.
- Organic pollutants include rhodamine B, bisphenol A or methyl orange.
- the product Mn 2 O 3 -C 0.9 -N 1.5 is used in combination with PMS in water to treat and degrade bisphenol A in water, and the results are shown in FIG. 5 .
- the removal rate of Mn 2 O 3 -C X by BPA was in the order of Mn 2 O 3 -C 0.9 >Mn 2 O 3 -C 0.6 >Mn 2 O 3 -C 1.2 >Mn 2 O 3 -C 0.3 .
- Mn(Ta) can degrade about 93% of BPA.
- the doping of N in the carbon shell not only promotes electron transfer and enhances the double reaction center, but also enhances the adsorption of BPA and PMS and shortens their migration distance.
- the catalytic performance of Mn 2 O 3 -C 0.9 -N y is in the order of Mn 2 O 3 -C 0.9 -N 1.2 >Mn 2 O 3 -C 0.9 -N 1.5 >Mn 2 O 3 -C 0.9 -N 0.9 >Mn 2 O 3 -C 0.9 -N 0.45 .
- organics are easily degraded in Fenton-like systems with relatively large doses of PMS (>1 g/L).
- BPA was also effectively degraded in Mn 2 O 3 -C 0.9 -N 1.2 under low dose of PMS (0.1 g/L), showing excellent catalytic activity of Mn 2 O 3 -C 0.9 -N 1.2 .
- PMS dose was further reduced from 0.1 g/L to 0.033 g/L, Mn 2 O 3 -C 0.9 -N 1.2 could still completely remove BPA within 16 minutes.
- This embodiment provides a preparation method of Mn 2 O 3 @N doped porous carbon hybrid Fenton-like material, comprising the following steps:
- Step 1 Add 2.51g manganese nitrate hexahydrate, 0.9g trimesic acid and 1.5g 2,2'-bipyridine into a mixed solution of 30mL N,N-dimethylformamide (DMF) and 30mL ethanol, And magnetic stirring for 6h, stirring rate of 100-200r/min.
- DMF N,N-dimethylformamide
- step 2 the mixture obtained in step 1 was transferred to a polytetrafluoroethylene-lined autoclave, heated at 180° C. for 18 hours, and subjected to a closed hydrothermal reaction to obtain a Mn-MOF solid substance.
- Step 3 Wash the Mn-MOF solid substance obtained in Step 2 three times with ethanol and water, and then dry at 80°C.
- Step 4 calcining the dried Mn-MOF solid material in a muffle furnace, the heating rate of calcination is 5-10°C, the calcination temperature is 450°C, and the calcination time is 4h, and finally a Fenton-like catalytic material is obtained.
- This embodiment provides a preparation method of Mn 2 O 3 @N doped porous carbon hybrid Fenton-like material, comprising the following steps:
- Step 1 Add 2.51g manganese nitrate hexahydrate, 0.9g trimesic acid and 1.5g 2,2'-bipyridine into a mixed solution of 30mL N,N-dimethylformamide (DMF) and 30mL ethanol, And magnetic stirring for 6h, stirring rate of 100-200r/min.
- DMF N,N-dimethylformamide
- step 2 the mixture obtained in step 1 was transferred to a polytetrafluoroethylene-lined autoclave, heated at 180° C. for 18 hours, and subjected to a closed hydrothermal reaction to obtain a Mn-MOF solid substance.
- Step 3 Wash the Mn-MOF solid substance obtained in Step 2 three times with ethanol and water, and then dry at 80°C.
- Step 4 calcining the dried Mn-MOF solid material in a muffle furnace, the heating rate of calcination is 5-10°C, the calcination temperature is 600°C, and the calcination time is 4h, and finally a Fenton-like catalytic material is obtained.
- This embodiment provides a preparation method of Mn 2 O 3 @N doped porous carbon hybrid Fenton-like material, comprising the following steps:
- Step 1 Add 2.51g manganese nitrate hexahydrate, 0.9g trimesic acid and 1.5g 2,2'-bipyridine into a mixed solution of 30mL N,N-dimethylformamide (DMF) and 30mL ethanol, And magnetic stirring for 6h, stirring rate of 100-200r/min.
- DMF N,N-dimethylformamide
- step 2 the mixture obtained in step 1 was transferred to a polytetrafluoroethylene-lined autoclave, heated at 180° C. for 18 hours, and subjected to a closed hydrothermal reaction to obtain a Mn-MOF solid substance.
- Step 3 Wash the Mn-MOF solid substance obtained in Step 2 three times with ethanol and water, and then dry at 80°C.
- Step 4 calcining the dried Mn-MOF solid material in a muffle furnace, the heating rate of calcination is 5-10°C, the calcination temperature is 500°C, and the calcination time is 2h, and finally a Fenton-like catalytic material is obtained.
- This embodiment provides a preparation method of Mn 2 O 3 @N doped porous carbon hybrid Fenton-like material, comprising the following steps:
- Step 1 Add 2.51g manganese nitrate hexahydrate, 0.9g trimesic acid and 1.5g 2,2'-bipyridine into a mixed solution of 30mL N,N-dimethylformamide (DMF) and 30mL ethanol, And magnetic stirring for 6h, stirring rate of 100-200r/min.
- DMF N,N-dimethylformamide
- step 2 the mixture obtained in step 1 was transferred to a polytetrafluoroethylene-lined autoclave, heated at 180° C. for 18 hours, and subjected to a closed hydrothermal reaction to obtain a Mn-MOF solid substance.
- Step 3 Wash the Mn-MOF solid substance obtained in Step 2 three times with ethanol and water, and then dry at 80°C.
- Step 4 calcining the dried Mn-MOF solid material in a muffle furnace, the heating rate of calcination is 5-10°C, the calcination temperature is 500°C, and the calcination time is 6h, and finally a Fenton-like catalytic material is obtained.
- This embodiment provides a preparation method of Mn 2 O 3 @N doped porous carbon hybrid Fenton-like material, comprising the following steps:
- Step 1 Add 2.51g manganese nitrate hexahydrate, 0.9g trimesic acid and 1.5g 2,2'-bipyridine into a mixed solution of 30mL N,N-dimethylformamide (DMF) and 30mL ethanol, And magnetic stirring for 6h, stirring rate of 100-200r/min.
- DMF N,N-dimethylformamide
- step 2 the mixture obtained in step 1 was transferred to a polytetrafluoroethylene-lined autoclave, heated at 150° C. for 18 hours, and subjected to a closed hydrothermal reaction to obtain Mn-MOF solid matter.
- Step 3 Wash the Mn-MOF solid substance obtained in Step 2 three times with ethanol and water, and then dry at 80°C.
- Step 4 calcining the dried Mn-MOF solid material in a muffle furnace, the heating rate of calcination is 5-10°C, the calcination temperature is 500°C, and the calcination time is 4h, and finally a Fenton-like catalytic material is obtained.
- This embodiment provides a preparation method of Mn 2 O 3 @N doped porous carbon hybrid Fenton-like material, comprising the following steps:
- Step 1 Add 2.51g manganese nitrate hexahydrate, 0.9g trimesic acid and 1.5g 2,2'-bipyridine into a mixed solution of 30mL N,N-dimethylformamide (DMF) and 30mL ethanol, And magnetic stirring for 6h, stirring rate of 100-200r/min.
- DMF N,N-dimethylformamide
- step 2 the mixture obtained in step 1 was transferred to a polytetrafluoroethylene-lined autoclave, heated at 200° C. for 18 hours, and subjected to a closed hydrothermal reaction to obtain Mn-MOF solid matter.
- Step 3 Wash the Mn-MOF solid substance obtained in Step 2 three times with ethanol and water, and then dry at 80°C.
- Step 4 calcining the dried Mn-MOF solid material in a muffle furnace, the heating rate of calcination is 5-10°C, the calcination temperature is 500°C, and the calcination time is 4h, and finally a Fenton-like catalytic material is obtained.
- This embodiment provides a preparation method of Mn 2 O 3 @N doped porous carbon hybrid Fenton-like material, comprising the following steps:
- Step 1 Add 2.51g manganese nitrate hexahydrate, 0.3g trimesic acid and 1.2g 2,2'-bipyridine into a mixed solution of 30mL N,N-dimethylformamide (DMF) and 30mL ethanol, And magnetic stirring for 3h, stirring rate of 100-200r/min.
- DMF N,N-dimethylformamide
- step 2 the mixture obtained in step 1 is transferred to a polytetrafluoroethylene-lined autoclave, heated at 120° C. for 25 hours, and subjected to a closed hydrothermal reaction to obtain a Mn-MOF solid substance.
- Step 3 Wash the Mn-MOF solid matter obtained in Step 2 with ethanol and water three times, and then dry at 60°C.
- Step 4 calcining the dried Mn-MOF solid material in a muffle furnace, the heating rate of calcination is 5-10°C, the calcination temperature is 400°C, and the calcination time is 4h, and finally a Fenton-like catalytic material is obtained.
- This embodiment provides a preparation method of Mn 2 O 3 @N doped porous carbon hybrid Fenton-like material, comprising the following steps:
- Step 1 Add 2.51g manganese nitrate hexahydrate, 1.2g trimesic acid and 1.2g 2,2'-bipyridine into a mixed solution of 30mL N,N-dimethylformamide (DMF) and 30mL ethanol, And magnetic stirring for 12h, stirring rate of 100-200r/min.
- DMF N,N-dimethylformamide
- step 2 the mixture obtained in step 1 is transferred to a polytetrafluoroethylene-lined autoclave, heated at 220° C. for 15 hours, and subjected to a closed hydrothermal reaction to obtain a Mn-MOF solid substance.
- Step 3 Wash the Mn-MOF solid matter obtained in Step 2 three times with ethanol and water, and then dry at 100°C.
- Step 4 calcining the dried Mn-MOF solid material in a muffle furnace, the heating rate of calcination is 5-10°C, the calcination temperature is 500°C, and the calcination time is 4h, and finally a Fenton-like catalytic material is obtained.
Abstract
Provided are an Mn2O3@N-doped porous carbon hybrid Fenton-like material, a preparation method therefor and an application thereof. The preparation method comprises the following steps: step one, adding manganese nitrate hexahydrate, trimesic acid and 2,2'-bipyridine into a hybrid solution of N,N-dimethylformamide and ethanol, and stirring; step two, transferring the mixture obtained in step one to a polytetrafluoroethylene-lined autoclave, and obtaining Mn-MOF solid material from closed hydrothermal reaction; step three, cleaning and drying the Mn-MOF solid material obtained in step two; and step four, obtaining a Fenton catalyst material through calcination of dried Mn-MOF solid material in a muffle furnace. The resulting material has a core-shell structure in which ultra-fine Mn 2 O 3 nanoparticles are uniformly distributed in a porous carbon layer structure, can effectively remove all kinds of organic toxic pollutants, especially phenol pollutants, under neutral conditions, and can achieve high-selectivity conversion of PMS.
Description
本发明属于材料领域，涉及一种芬顿材料，尤其涉及一种Mn
2O
3@N掺杂多孔碳杂化类芬顿材料及其制备方法和应用。
The invention belongs to the field of materials, and relates to a Fenton material, in particular to a Mn 2 O 3 @N doped porous carbon hybrid-like Fenton material and a preparation method and application thereof.
传统芬顿氧化包括均相芬顿法和非均相芬顿法，其中均相芬顿是利用Fe
2+与H
2O
2反应产生具有超强氧化能力的羟基自由基(HO·)来降解水中污染物的过程。然而，传统芬顿技术存在诸多缺陷，如严格的酸性条件(pH<3)，反应过程中铁泥的产生，以及对氧化剂极低的利用率都大大限制了传统芬顿法在实际废水处理中的应用。于是，多相相芬顿催化引起广泛关注，在多相芬顿催化研究中，一种双反应活性中心机理因其独特的优势如氧化剂利用率高，催化稳定性号等引起了研究人员极大的兴趣。然而，传统富电子Cu中心类芬顿催化剂依然存在许多不足之处阻碍其发展，如对酚类污染物的矿化度低，对分子量大的有机污染物降解效果差等。例如：
Traditional Fenton oxidation includes homogeneous Fenton method and heterogeneous Fenton method, in which homogeneous Fenton is degraded by the reaction of Fe 2+ with H 2 O 2 to generate hydroxyl radicals (HO ) with super oxidizing ability Process of contaminants in water. However, the traditional Fenton technology has many defects, such as strict acidic conditions (pH<3), the production of iron sludge during the reaction process, and the extremely low utilization rate of the oxidant, which greatly limit the traditional Fenton method in practical wastewater treatment. application. As a result, heterogeneous Fenton catalysis has attracted widespread attention. In the study of heterogeneous Fenton catalysis, a dual-reaction active center mechanism has attracted great attention from researchers due to its unique advantages such as high oxidant utilization and catalytic stability. interest of. However, traditional electron-rich Cu-centered Fenton-like catalysts still have many shortcomings that hinder their development, such as low salinity for phenolic pollutants and poor degradation of organic pollutants with large molecular weights. E.g:
申请号为201911252787.X的发明申请公开了一种氧化锰纳米线负载四氧化三铁磁性芬顿催化剂及其一步合成方法及应用，该催化剂表面的二价铁可以将氧化剂转化为自由基，且不存在金属离子析出的现象，另外磁性四氧化三铁颗粒使催化剂极易回收，多孔的结构也是催化剂暴露更多的活性位点。然而整个反应仍然是遵守着经典芬顿反应的机理，并且这种催化剂还是依靠金属单一位点的氧化还原反应实现过氧化氢的活化，体系中过氧化氢的利用率仍然很低。The invention application with the application number of 201911252787.X discloses a manganese oxide nanowire-supported ferroferric oxide magnetic Fenton catalyst and its one-step synthesis method and application. The divalent iron on the surface of the catalyst can convert oxidants into free radicals, and There is no precipitation of metal ions, and the magnetic ferric oxide particles make the catalyst easy to recover, and the porous structure also exposes more active sites to the catalyst. However, the whole reaction still follows the mechanism of the classical Fenton reaction, and this catalyst still relies on the redox reaction of a single metal site to achieve the activation of hydrogen peroxide, and the utilization rate of hydrogen peroxide in the system is still very low.
申请号为201911304515.X的发明申请公开了一种高效铁单原子芬顿催化材料的制备方法，用该种方法制备的铁活性物质以单原子形式锚定于氮掺杂碳载体上，负载量为0.3～10wt％。该方法简单快捷，且成本相对低廉。然而不可避免的会出现由于催化剂中的金属在不断的价态转化中造成活性降低，从而催化性能下降的现象，进而降低催化剂的使用寿命。The invention application with the application number of 201911304515.X discloses a preparation method of a high-efficiency iron single-atom Fenton catalytic material. The iron active material prepared by this method is anchored on a nitrogen-doped carbon carrier in the form of a single atom, and the loading amount is 0.3 to 10 wt %. The method is simple, quick, and relatively inexpensive. However, it is unavoidable that the activity of the metals in the catalyst decreases during the continuous valence conversion, thereby reducing the catalytic performance, thereby reducing the service life of the catalyst.
申请号为201911250618.2的发明申请公开了一种高过氧化氢利用率的非均相芬顿催化剂及其制备方法和应用，是一种非均相铜基催化剂复合催化剂的制备方法。其中第二金属的引入能够显著抑制过氧化氢的无效分解(分解成氧气和水)，并促进过氧化氢分解成为具有强氧化性的羟基自由基(·OH)，提高了单位摩尔过氧化氢的喹啉分解量，即提高了过氧化氢的利用率。然而，整个芬顿反应过程需要的双氧水浓度过高，由于双氧水的自分解作用以及会与体系中的羟基自由基反应，因此会造成大量氧化剂的浪费。The invention application with the application number of 201911250618.2 discloses a heterogeneous Fenton catalyst with high hydrogen peroxide utilization rate and its preparation method and application, which is a preparation method of a heterogeneous copper-based catalyst composite catalyst. The introduction of the second metal can significantly inhibit the ineffective decomposition of hydrogen peroxide (decomposition into oxygen and water), and promote the decomposition of hydrogen peroxide into hydroxyl radicals ( OH) with strong oxidizing properties, which increases the unit mole of hydrogen peroxide. The amount of quinoline decomposed, that is, the utilization rate of hydrogen peroxide is improved. However, the concentration of hydrogen peroxide required in the entire Fenton reaction process is too high, and due to the self-decomposition of hydrogen peroxide and the reaction with hydroxyl radicals in the system, a large amount of oxidant will be wasted.
申请号为201911224312.X的发明申请公开了一种超小四氧化三铁致密包覆三维还原氧化石墨烯类芬顿催化剂的制备方法。该发明解决现有方法在石墨烯上负载Fe
3O
4不均匀、不牢固和催化活性位点少的问题。制备的超小四氧化三铁致密包覆三维还原氧化石墨烯类芬顿催化剂的催化性能明显提升，降解盐酸四环素20min，降解率可达100％，并且具有优异的循环稳定性。然而该催化材料使用的石墨烯在实际废水处理中具有局限性，且极容易失活。
The invention application with the application number of 201911224312.X discloses a preparation method of ultra-small ferric oxide densely coated three-dimensional reduced graphene oxide-based Fenton catalyst. The invention solves the problems of non-uniform, weak and few catalytically active sites of Fe 3 O 4 supported on graphene by the existing method. The prepared ultra-small ferric oxide densely coated three-dimensional reduced graphene oxide-based Fenton catalyst has significantly improved catalytic performance, degrades tetracycline hydrochloride for 20 min, the degradation rate can reach 100%, and has excellent cycle stability. However, the graphene used in this catalytic material has limitations in practical wastewater treatment and is easily deactivated.
由于MnO
x在催化反应中的价态变化(Ⅱ，Ⅲ，Ⅳ)涉及单电子转移，因此MnO
x被认为是一种很有前途的类Fenton催化剂。此外，以往的研究表明，具有超纳米尺度的MnO
x不仅具有高比表面积，而且缩短了质量/电子转移途径，具有较高的催化活性。然而，超细MnO
x由于表面能较大，容易在溶液中聚集，严重降低了活性中心的暴露，甚至导致催化剂的不可逆失活。另外自由基转化生成单线态氧的过程也需要体系内能在短时间内产生大量自由基且提供自由基复合的空间结构。要实现双反应活性中心与自由基转化的协同作用存在几个技术难题需要解决：(1)如何构建MnO
x结构使材料中的锰氧化物能够避免团聚而使活性位点丧失；(2)足够 强的极化差异才能实现双反应活性中心机理，因此要选择设计合适配体以及键合作用使催化材料表面形成极化差异；(3)如何构建催化材料使其表面产生合适的纳米限域效应来促使自由基复合转化成单线态氧。
Since the valence state changes (II, III, IV) of MnOx in catalytic reactions involve single electron transfer, MnOx is considered to be a promising Fenton-like catalyst. Furthermore, previous studies have shown that MnOx with ultra-nanoscale not only has a high specific surface area, but also shortens the mass/electron transfer pathway, resulting in high catalytic activity. However, due to the large surface energy of ultrafine MnOx , it is easy to aggregate in solution, which severely reduces the exposure of active sites and even leads to irreversible deactivation of the catalyst. In addition, the process of free radical conversion to generate singlet oxygen also requires the system to generate a large number of free radicals in a short time and provide a spatial structure for free radical recombination. To achieve the synergistic effect of dual-reactive active centers and radical transformation, there are several technical difficulties to be solved: (1) how to construct the MnOx structure so that the manganese oxide in the material can avoid agglomeration and the loss of active sites; (2) sufficient Only strong polarization difference can realize the dual-reaction active center mechanism, so it is necessary to choose suitable ligands and bonding to form polarization difference on the surface of the catalytic material; (3) How to construct the catalytic material to produce a suitable nano-confinement effect on the surface to promote the recombination of free radicals into singlet oxygen.
发明内容SUMMARY OF THE INVENTION
本发明提供一种Mn
2O
3@N掺杂多孔碳杂化类芬顿材料及其制备方法和应用，以克服现有技术的缺陷。
The present invention provides a Mn 2 O 3 @N-doped porous carbon hybrid Fenton-like material and a preparation method and application thereof, so as to overcome the defects of the prior art.
为实现上述目的，本发明提供一种Mn
2O
3@N掺杂多孔碳杂化类芬顿材料的制备方法，具有这样的特征：包括以下步骤：步骤一、将六水合硝酸锰、均苯三甲酸和2,2'-联吡啶加入至N,N-二甲基甲酰胺和乙醇的混合溶液中，并进行搅拌；步骤二、将步骤一得到的混合物转移到聚四氟乙烯内衬高压釜中，进行密闭水热反应得到Mn-MOF固体物质；步骤三、清洗步骤二得到的Mn-MOF固体物质再干燥；步骤四、将烘干后的Mn-MOF固体物质在马弗炉中煅烧，得到芬顿催化材料。
In order to achieve the above object, the present invention provides a method for preparing a Mn 2 O 3 @N doped porous carbon hybrid Fenton-like material, which has the following characteristics: comprising the following steps: step 1, mixing manganese nitrate hexahydrate, homobenzene Tricarboxylic acid and 2,2'-bipyridine were added to the mixed solution of N,N-dimethylformamide and ethanol, and stirred; in step 2, the mixture obtained in step 1 was transferred to a polytetrafluoroethylene lined high pressure In the kettle, a closed hydrothermal reaction is carried out to obtain the Mn-MOF solid matter; step 3, the Mn-MOF solid matter obtained in the cleaning step 2 is dried again; step 4, the dried Mn-MOF solid matter is calcined in a muffle furnace , to obtain Fenton catalytic materials.
进一步，本发明提供一种Mn
2O
3@N掺杂多孔碳杂化类芬顿材料的制备方法，还可以具有这样的特征：其中，步骤一中，每40-100mL N,N-二甲基甲酰胺和乙醇的混合溶液中加入2.51g六水合硝酸锰、0.3-1.2g均苯三甲酸和0.45-1.5g的2,2'-联吡啶；N,N-二甲基甲酰胺和乙醇的体积比为1∶1。
Further, the present invention provides a method for preparing a Mn 2 O 3 @N-doped porous carbon hybrid Fenton-like material, which may also have the following characteristics: wherein, in step 1, every 40-100 mL of N,N-dimethylformaldehyde 2.51g of manganese nitrate hexahydrate, 0.3-1.2g of trimesic acid and 0.45-1.5g of 2,2'-bipyridine; N,N-dimethylformamide and ethanol were added to the mixed solution of methylformamide and ethanol The volume ratio is 1:1.
进一步，本发明提供一种Mn
2O
3@N掺杂多孔碳杂化类芬顿材料的制备方法，还可以具有这样的特征：其中，步骤一采用磁力搅拌，搅拌速率为100-200r/min，搅拌时间为3-12h。
Further, the present invention provides a preparation method of Mn 2 O 3 @N doped porous carbon hybrid Fenton-like material, which may also have the following characteristics: wherein, in step 1, magnetic stirring is used, and the stirring rate is 100-200 r/min , the stirring time is 3-12h.
进一步，本发明提供一种Mn
2O
3@N掺杂多孔碳杂化类芬顿材料的制备方法，还可以具有这样的特征：其中，步骤二中，水热反应的反应温度为120-220℃，反应时间为15-25h。
Further, the present invention provides a preparation method of Mn 2 O 3 @N doped porous carbon hybrid Fenton-like material, which may also have the following characteristics: wherein, in step 2, the reaction temperature of the hydrothermal reaction is 120-220 ℃ ℃, the reaction time is 15-25h.
进一步，本发明提供一种Mn
2O
3@N掺杂多孔碳杂化类芬顿材料的制备方法，还可以具有这样的特征：其中，步骤三中，用乙醇和水清洗Mn-MOF固体物质三次。
Further, the present invention provides a preparation method of Mn 2 O 3 @N doped porous carbon hybrid Fenton-like material, which may also have the following characteristics: wherein, in step 3, the Mn-MOF solid substance is washed with ethanol and water three times.
进一步，本发明提供一种Mn
2O
3@N掺杂多孔碳杂化类芬顿材料的制备方法，还可以具有这样的特征：其中，步骤三中，烘干温度为60℃-100℃。
Further, the present invention provides a preparation method of Mn 2 O 3 @N doped porous carbon hybrid Fenton-like material, which may also have the following characteristics: wherein, in step 3, the drying temperature is 60°C-100°C.
进一步，本发明提供一种Mn
2O
3@N掺杂多孔碳杂化类芬顿材料的制备方法，还可以具有这样的特征：其中，步骤四中，马弗炉中煅烧的升温速率为5-10℃，煅烧温度为400-600℃，煅烧时间为2-6h。
Further, the present invention provides a preparation method of Mn 2 O 3 @N doped porous carbon hybrid Fenton-like material, which may also have the following characteristics: wherein, in step 4, the heating rate of calcination in the muffle furnace is 5 -10℃, the calcination temperature is 400-600℃, and the calcination time is 2-6h.
本发明还提供一种Mn
2O
3@N掺杂多孔碳杂化类芬顿材料，由上述制备方法制得，芬顿材料的结构式为Mn
2O
3-C
x-N
y，x，y分别表示均苯三甲酸和2,2'-联吡啶的添加量。
The present invention also provides a Mn 2 O 3 @N-doped porous carbon hybrid Fenton-like material, which is prepared by the above preparation method. The structural formula of the Fenton material is Mn 2 O 3 -C x -N y , x, y Indicates the addition amounts of trimesic acid and 2,2'-bipyridine, respectively.
本发明还提供一种Mn
2O
3@N掺杂多孔碳杂化类芬顿材料与PMS在水中联用处理降解有机污染物的应用。
The present invention also provides an application of Mn 2 O 3 @N doped porous carbon hybrid Fenton-like material and PMS in water to treat and degrade organic pollutants.
进一步，本发明提供一种Mn
2O
3@N掺杂多孔碳杂化类芬顿材料的应用，还可以具有这样的特征：有机污染物为罗丹明B、双酚A和甲基橙中的任一种。
Further, the present invention provides an application of a Mn 2 O 3 @N doped porous carbon hybrid Fenton-like material, which can also have the characteristics that the organic pollutants are rhodamine B, bisphenol A and methyl orange. either.
芬顿催化材料基于超细纳米Mn
2O
3与含氮无机碳的核壳结构的构建，其基本结构以Mn
2O
3为基体，表面通过碳化MOFs结构产生含氮碳层，形成核壳结构材料，其中表面碳层厚度大约为5-10nm。根据氮气吸脱附等温线和孔径分布图可知合成的类芬顿催化剂中主要存在介孔结构。MOFs衍生的碳壳增加了催化剂的BET比表面积和孔容，从而促进了界面反应和传质过程。所述催化材料由于表面多孔含氮碳层的形成，使得在催化降解酚类污染物时可以实现双反应活性 中心与自由基转化机制的协同作用。
The Fenton catalytic material is based on the construction of a core-shell structure of ultra-fine nano - Mn 2 O 3 and nitrogen - containing inorganic carbon. material, wherein the thickness of the surface carbon layer is about 5-10 nm. According to the nitrogen adsorption and desorption isotherm and pore size distribution, it can be seen that the synthesized Fenton-like catalyst mainly has mesoporous structure. The MOFs-derived carbon shell increases the BET specific surface area and pore volume of the catalyst, thereby facilitating the interfacial reaction and mass transfer process. Due to the formation of the surface porous nitrogen-containing carbon layer, the catalytic material can realize the synergistic effect of the double-reaction active center and the free radical conversion mechanism when catalyzing the degradation of phenolic pollutants.
本发明通过碳化MOFs前驱体获得表面包裹含氮碳层的Mn
2O
3类芬顿催化剂。超细Mn
2O
3原位生成，均匀分散在N掺杂MOFs衍生的碳网孔中，提高了纳米催化剂的稳定性。与经典的Fenton反应不同，Mn
2O
3@N掺杂多孔碳杂化物中的阳离子-π相互作用和Mn-N配位作用导致了双反应中心的形成，促进了电子从富电子Mn中心向PMS的转移，并产生了大量的自由基。更重要的是，大量的自由基在纳米约束下重组，产生
1O
2，用于降解有机物。此外，Mn-N络合可以降低催化剂表面的吸附能，增强PMS的吸附，也有利于电子转移。因此，即使在低剂量下，PMS的活化和利用率也显著提高。本发明不仅合成了一种高效的类Fenton双反应中心催化剂，而且为低剂量PMS下有机物的降解提供了一种新的方法。
The present invention obtains the Mn 2 O 3 type Fenton catalyst whose surface is wrapped with a nitrogen-containing carbon layer by carbonizing the MOFs precursor. Ultrafine Mn 2 O 3 is in situ generated and uniformly dispersed in the carbon meshes derived from N-doped MOFs, which improves the stability of the nanocatalysts. Different from the classical Fenton reaction, the cation-π interaction and Mn - N coordination in Mn2O3@N - doped porous carbon hybrids lead to the formation of a double reaction center, which promotes electron transfer from the electron-rich Mn center to transfer of PMS and generate a large number of free radicals. More importantly, a large number of free radicals recombine under nano-confinement to generate 1 O 2 , which is used to degrade organic matter. In addition, the Mn-N complexation can reduce the adsorption energy on the catalyst surface, enhance the adsorption of PMS, and also facilitate electron transfer. Therefore, even at low doses, the activation and utilization of PMS is significantly improved. The invention not only synthesizes an efficient Fenton-like double-reaction center catalyst, but also provides a new method for the degradation of organic matter under low-dose PMS.
本发明的有益效果在于：The beneficial effects of the present invention are:
一、MOFs制备超细Mn
2O
3纳米颗粒，不仅防止团聚现象的发生同时具备超高活性，另外生成的立方晶型的Mn
2O
3暴露更多活性位点。
1. The preparation of ultra-fine Mn 2 O 3 nanoparticles by MOFs not only prevents the occurrence of agglomeration, but also has ultra-high activity, and the generated cubic Mn 2 O 3 exposes more active sites.
二、氮原子掺杂的碳层结构与金属通过阳离子Π键与金属-N键作用产生双反应活性中心，避免了传统类芬顿反应中的限速步骤，避免双氧水的无效分解，提高了催化剂的催化活性。2. The nitrogen atom-doped carbon layer structure and metal generate double reaction active centers through the interaction of cationic Π bond and metal-N bond, avoiding the rate-limiting step in the traditional Fenton-like reaction, avoiding the ineffective decomposition of hydrogen peroxide, and improving the catalyst. catalytic activity.
三、超细Mn
2O
3纳米颗粒的超强活性协同双反应产生大量自由基，这些自由基在氮原子掺杂的碳层结构内复合产生具有强亲电作用的单线态氧
1O
2，提高了BPA的降解催化效果。
3. The ultra-strong activity of ultrafine Mn 2 O 3 nanoparticles produces a large number of free radicals in the synergistic double reaction, and these free radicals recombine in the carbon layer structure doped with nitrogen atoms to generate singlet oxygen 1 O 2 with strong electrophilic effect, The degradation catalytic effect of BPA was improved.
四、氮原子掺杂的碳层结构提供PMS和BPA吸附位点，是反应处在催化剂表面进行，减少了自由基的迁移距离，提高了自由基的利用率，从而大大提升了催化降解效果和PMS的利用率。4. The carbon layer structure doped with nitrogen atoms provides adsorption sites for PMS and BPA, and the reaction is carried out on the surface of the catalyst, which reduces the migration distance of free radicals and improves the utilization rate of free radicals, thereby greatly improving the catalytic degradation effect. Utilization of PMS.
图1是实施例3产物Mn
2O
3-C
0.9-N
1.2、以及Mn
2O
3和Mn
2O
3-C
0.9的扫描电镜图和透射电镜图；
Fig. 1 is the scanning electron microscope image and transmission electron microscope image of the product Mn 2 O 3 -C 0.9 -N 1.2 of Example 3, and Mn 2 O 3 and Mn 2 O 3 -C 0.9 ;
图2是实施例3产物Mn
2O
3-C
0.9-N
1.2、以及Mn
2O
3和Mn
2O
3-C
0.9的N
2吸脱附曲线和孔径分布图谱；
Fig. 2 is the N 2 adsorption-desorption curve and pore size distribution map of the product Mn 2 O 3 -C 0.9 -N 1.2 of Example 3, and Mn 2 O 3 and Mn 2 O 3 -C 0.9 ;
图3A是实施例3产物Mn
2O
3-C
0.9-N
1.2、以及Mn
3O
4、Mn
2O
3、Mn-MOF和Mn
2O
3-C
0.9的XRD图谱；
Fig. 3A is the XRD pattern of Example 3 product Mn 2 O 3 -C 0.9 -N 1.2 , and Mn 3 O 4 , Mn 2 O 3 , Mn-MOF and Mn 2 O 3 -C 0.9 ;
图3B是实施例3产物Mn
2O
3-C
0.9-N
1.2以及Mn
2O
3的拉曼光谱图；
Figure 3B is the Raman spectrum of the product of Example 3 Mn 2 O 3 -C 0.9 -N 1.2 and Mn 2 O 3 ;
图3C是实施例3产物Mn
2O
3-C
0.9-N
1.2、以及Mn-MOF和Mn
2O
3-C
0.9等的红外光谱图；
Fig. 3C is the infrared spectrogram of Example 3 product Mn 2 O 3 -C 0.9 -N 1.2 , as well as Mn-MOF and Mn 2 O 3 -C 0.9 ;
图3D是实施例3产物Mn
2O
3-C
0.9-N
1.2、以及Mn
3O
4、Mn
2O
3和Mn
2O
3-C
0.9的EIS图谱；
Fig. 3D is the EIS spectrum of Example 3 product Mn 2 O 3 -C 0.9 -N 1.2 , and Mn 3 O 4 , Mn 2 O 3 and Mn 2 O 3 -C 0.9 ;
图4是实施例3产物Mn
2O
3-C
0.9-N
1.2以Mn-MOF的C、O和N的XPS图谱；
Fig. 4 is the XPS spectrum of C, O and N of the product Mn 2 O 3 -C 0.9 -N 1.2 of Example 3 with Mn-MOF;
图5是实施例1-4产物Mn
2O
3-C
x-N
y的催化效果图(BPA 20ppm，Rh B 10ppm)；
Fig. 5 is the catalytic effect diagram of the product Mn 2 O 3 -C x -N y of Example 1-4 (BPA 20ppm, Rh B 10ppm);
图6A和B分别是实施例3产物Mn
2O
3-C
0.9-N
1.2以及Mn
2O
3的TOC和PMS利用率图；
6A and B are TOC and PMS utilization diagrams of the products of Example 3, Mn 2 O 3 -C 0.9 -N 1.2 and Mn 2 O 3 , respectively;
图7A和B分别是Mn
2O
3和实施例3产物Mn
2O
3-C
0.9-N
1.2的循环实验结果图；
Figures 7A and B are the results of the cycle experiment of Mn 2 O 3 and the product of Example 3, Mn 2 O 3 -C 0.9 -N 1.2 , respectively;
图7C是实施例3产物Mn
2O
3-C
0.9-N
1.2以及Mn
2O
3的金属滤出实验结果图；
Fig. 7C is the result diagram of the metal leaching experiment of the product Mn 2 O 3 -C 0.9 -N 1.2 and Mn 2 O 3 of Example 3;
图7D是产物Mn
2O
3-C
0.9-N
1.2的结构图；
Figure 7D is a structural diagram of the product Mn 2 O 3 -C 0.9 -N 1.2 ;
图8是产物Mn
2O
3-C
0.9-N
1.2的催化机理图。
Figure 8 is a diagram of the catalytic mechanism of the product Mn 2 O 3 -C 0.9 -N 1.2 .
以下结合具体实施例对本发明作进一步说明。The present invention will be further described below in conjunction with specific embodiments.
实施例1Example 1
本实施例提供一种Mn
2O
3@N掺杂多孔碳杂化类芬顿材料的制备方法及其应用。
This embodiment provides a preparation method and application of a Mn 2 O 3 @N doped porous carbon hybrid Fenton-like material.
制备方法包括以下步骤：The preparation method includes the following steps:
步骤一、将2.51g六水合硝酸锰、0.9g均苯三甲酸和0.45g 2,2'-联吡啶加入至30mL N,N-二甲基甲酰胺(DMF)和30mL乙醇的混合溶液中，并磁力搅拌6h，搅拌速率为100-200r/min。Step 1. Add 2.51g manganese nitrate hexahydrate, 0.9g trimesic acid and 0.45g 2,2'-bipyridine into a mixed solution of 30mL N,N-dimethylformamide (DMF) and 30mL ethanol, And magnetic stirring for 6h, stirring rate of 100-200r/min.
步骤二、将步骤一得到的混合物转移到聚四氟乙烯内衬高压釜中，在180℃下加热18h进行密闭水热反应得到Mn-MOF固体物质。In step 2, the mixture obtained in step 1 was transferred to a polytetrafluoroethylene-lined autoclave, heated at 180° C. for 18 hours, and subjected to a closed hydrothermal reaction to obtain a Mn-MOF solid substance.
步骤三、用乙醇和水清洗步骤二得到的Mn-MOF固体物质三次，再于80℃干燥。Step 3: Wash the Mn-MOF solid substance obtained in Step 2 three times with ethanol and water, and then dry at 80°C.
步骤四、将烘干后的Mn-MOF固体物质在马弗炉中煅烧，煅烧的升温速率为5-10℃，煅烧温度为500℃，煅烧时间为4h，最终得到芬顿催化材料。Step 4: calcining the dried Mn-MOF solid material in a muffle furnace, the heating rate of calcination is 5-10°C, the calcination temperature is 500°C, and the calcination time is 4h, and finally the Fenton catalytic material is obtained.
产物芬顿材料与PMS在水中联用，形成类芬顿体系，用来处理降解水中的有机污染物。有机污染物包括罗丹明B、双酚A或甲基橙。本实施例将产物Mn
2O
3-C
0.9-N
0.45与PMS在水中联用，处理降解水中的双酚A，结果如图5所示。
The product Fenton material is combined with PMS in water to form a Fenton-like system, which is used to treat and degrade organic pollutants in water. Organic pollutants include rhodamine B, bisphenol A or methyl orange. In this example, the product Mn 2 O 3 -C 0.9 -N 0.45 is used in combination with PMS in water to treat and degrade bisphenol A in water, and the results are shown in FIG. 5 .
实施例2Example 2
本实施例提供一种Mn
2O
3@N掺杂多孔碳杂化类芬顿材料的制备方法及其应用。
This embodiment provides a preparation method and application of a Mn 2 O 3 @N doped porous carbon hybrid Fenton-like material.
制备方法包括以下步骤：The preparation method includes the following steps:
步骤一、将2.51g六水合硝酸锰、0.9g均苯三甲酸和0.9g 2,2'-联吡啶加入至30mL N,N-二甲基甲酰胺(DMF)和30mL乙醇的混合溶液中，并磁力搅拌6h，搅拌速率为100-200r/min。Step 1. Add 2.51g manganese nitrate hexahydrate, 0.9g trimesic acid and 0.9g 2,2'-bipyridine into a mixed solution of 30mL N,N-dimethylformamide (DMF) and 30mL ethanol, And magnetic stirring for 6h, stirring rate of 100-200r/min.
步骤二、将步骤一得到的混合物转移到聚四氟乙烯内衬高压釜中，在180℃下加热18h进行密闭水热反应得到Mn-MOF固体物质。In step 2, the mixture obtained in step 1 was transferred to a polytetrafluoroethylene-lined autoclave, heated at 180° C. for 18 hours, and subjected to a closed hydrothermal reaction to obtain a Mn-MOF solid substance.
步骤三、用乙醇和水清洗步骤二得到的Mn-MOF固体物质三次，再于80℃干燥。Step 3: Wash the Mn-MOF solid substance obtained in Step 2 three times with ethanol and water, and then dry at 80°C.
步骤四、将烘干后的Mn-MOF固体物质在马弗炉中煅烧，煅烧的升温速率为5-10℃，煅烧温度为500℃，煅烧时间为4h，最终得到类芬顿催化材料。Step 4: calcining the dried Mn-MOF solid material in a muffle furnace, the heating rate of calcination is 5-10°C, the calcination temperature is 500°C, and the calcination time is 4h, and finally a Fenton-like catalytic material is obtained.
产物芬顿材料与PMS在水中联用，形成类芬顿体系，用来处理降解水中的有机污染物。有机污染物包括罗丹明B、双酚A或甲基橙。本实施例将产物Mn
2O
3-C
0.9-N
0.9与PMS在水中联用，处理降解水中的双酚A，结果如图5所示。
The product Fenton material is combined with PMS in water to form a Fenton-like system, which is used to treat and degrade organic pollutants in water. Organic pollutants include rhodamine B, bisphenol A or methyl orange. In this example, the product Mn 2 O 3 -C 0.9 -N 0.9 is used in combination with PMS in water to treat and degrade bisphenol A in water, and the results are shown in FIG. 5 .
实施例3Example 3
本实施例提供一种Mn
2O
3@N掺杂多孔碳杂化类芬顿材料的制备方法及其应用。
This embodiment provides a preparation method and application of a Mn 2 O 3 @N doped porous carbon hybrid Fenton-like material.
制备方法包括以下步骤：The preparation method includes the following steps:
步骤一、将2.51g六水合硝酸锰、0.9g均苯三甲酸和1.2g 2,2'-联吡啶加入至30mL N,N- 二甲基甲酰胺(DMF)和30mL乙醇的混合溶液中，并磁力搅拌6h，搅拌速率为100-200r/min。Step 1. Add 2.51g manganese nitrate hexahydrate, 0.9g trimesic acid and 1.2g 2,2'-bipyridine into a mixed solution of 30mL N,N-dimethylformamide (DMF) and 30mL ethanol, And magnetic stirring for 6h, stirring rate of 100-200r/min.
步骤二、将步骤一得到的混合物转移到聚四氟乙烯内衬高压釜中，在180℃下加热18h进行密闭水热反应得到Mn-MOF固体物质。In step 2, the mixture obtained in step 1 was transferred to a polytetrafluoroethylene-lined autoclave, heated at 180° C. for 18 hours, and subjected to a closed hydrothermal reaction to obtain a Mn-MOF solid substance.
步骤三、用乙醇和水清洗步骤二得到的Mn-MOF固体物质三次，再于80℃干燥。Step 3: Wash the Mn-MOF solid substance obtained in Step 2 three times with ethanol and water, and then dry at 80°C.
步骤四、将烘干后的Mn-MOF固体物质在马弗炉中煅烧，煅烧的升温速率为5-10℃，煅烧温度为500℃，煅烧时间为4h，最终得到类芬顿催化材料。Step 4: calcining the dried Mn-MOF solid material in a muffle furnace, the heating rate of calcination is 5-10°C, the calcination temperature is 500°C, and the calcination time is 4h, and finally a Fenton-like catalytic material is obtained.
对产物进行如下表征：The product was characterized as follows:
对产物Mn
2O
3-C
0.9-N
1.2、以及Mn
2O
3和Mn
2O
3-C
0.9(与本实施例的制备方法相同，均苯三甲酸的添加量为0.9g，2,2'-联吡啶的添加量为0)进行扫描电镜和透射电镜表征，结果如图1所示。从图1中可以看到，纯Mn
2O
3表面致密，而Mn
2O
3-C
0.9-N
1.2呈多孔结构。在透射电镜图像中可以观察到，纯Mn
2O
3由于其相对较高的表面能而严重聚集。相反，超细Mn
2O
3纳米粒子均匀地分散在Mn
2O
3-C
x-N
y中。Mn
2O
3纳米粒子的这种强分散性可以解释为：在合成过程中，Mn被MOFs(Mn-MOFs-Ta-Bd)中的配体(均苯三甲酸和2,2'联吡啶)螯合。煅烧后，表面形成碳壳，阻止了纳米二氧化锰的聚集。在HRTEM图像中可以清楚地观察到具有核壳结构的Mn
2O
3-C
x-N
y，碳壳包覆着立方状的Mn
2O
3核。晶格条纹(0.27nm)也证实了立方相Mn
2O
3的(222)面。
For the product Mn 2 O 3 -C 0.9 -N 1.2 , as well as Mn 2 O 3 and Mn 2 O 3 -C 0.9 (same as the preparation method of this embodiment, the addition amount of trimesic acid is 0.9g, 2,2 The addition amount of '-bipyridine was 0) for characterization by scanning electron microscopy and transmission electron microscopy, and the results are shown in Figure 1. It can be seen from Fig. 1 that pure Mn 2 O 3 has a dense surface, while Mn 2 O 3 -C 0.9 -N 1.2 has a porous structure. It can be observed in the TEM images that pure Mn2O3 is heavily aggregated due to its relatively high surface energy. In contrast, ultrafine Mn 2 O 3 nanoparticles are uniformly dispersed in Mn 2 O 3 -C x -N y . This strong dispersibility of Mn2O3 nanoparticles can be explained by the fact that during the synthesis, Mn was absorbed by the ligands ( trismellitic acid and 2,2' bipyridine) in the MOFs (Mn-MOFs-Ta-Bd) Chelation. After calcination, a carbon shell is formed on the surface, which prevents the aggregation of nano-manganese dioxide. The Mn2O3 - Cx - Ny with a core - shell structure can be clearly observed in the HRTEM images, and the carbon shell wraps the cubic Mn2O3 core. The lattice fringes (0.27 nm) also confirm the (222) facet of the cubic phase Mn 2 O 3 .
对产物Mn
2O
3-C
0.9-N
1.2、以及Mn
2O
3和Mn
2O
3-C
0.9进行N
2吸脱附曲线和孔径分布的测试，以分析催化剂的孔结构，结果如图2所示。由图2结果可知，此催化剂属于带有H3滞回曲线的IV型等温线。MOFs衍生的碳壳增加了催化剂的BET比表面积和孔容，从而促进了界面反应和传质过程。
The product Mn 2 O 3 -C 0.9 -N 1.2 , as well as Mn 2 O 3 and Mn 2 O 3 -C 0.9 were tested for N 2 adsorption-desorption curve and pore size distribution to analyze the pore structure of the catalyst. The results are shown in Figure 2 shown. It can be seen from the results in Fig. 2 that this catalyst belongs to the IV type isotherm with H3 hysteresis curve. The MOFs-derived carbon shell increases the BET specific surface area and pore volume of the catalyst, thereby facilitating the interfacial reaction and mass transfer process.
对产物Mn
2O
3-C
0.9-N
1.2、以及Mn
3O
4、Mn
2O
3、Mn-MOF和Mn
2O
3-C
0.9进行XRD表征，结果如图3A所示。由图可知，煅烧前，Mn-MOFs最典型的衍射峰与纯Mn
3O
4的标准图谱一致，由于结晶度较低，其强度相对较弱。煅烧后，Mn
2O
3-C
0.9和Mn
2O
3-C
0.9-N
1.2的典型衍射峰与纯Mn
2O
3的标准衍射峰一致，且由于形成了超细Mn
2O
3晶体，其强度明显提高。
The products Mn 2 O 3 -C 0.9 -N 1.2 , and Mn 3 O 4 , Mn 2 O 3 , Mn-MOF and Mn 2 O 3 -C 0.9 were characterized by XRD, and the results are shown in FIG. 3A . It can be seen from the figure that before calcination, the most typical diffraction peak of Mn - MOFs is consistent with the standard pattern of pure Mn3O4, and its intensity is relatively weak due to the low crystallinity. After calcination, the typical diffraction peaks of Mn 2 O 3 -C 0.9 and Mn 2 O 3 -C 0.9 -N 1.2 are consistent with the standard diffraction peaks of pure Mn 2 O 3 , and due to the formation of ultrafine Mn 2 O 3 crystals, the The strength is significantly improved.
对产物Mn
2O
3-C
0.9-N
1.2以及Mn
2O
3进行拉曼光谱表征，结果如图3B所示。拉曼光谱可以提供碳骨架的晶体学信息。Mn
2O
3-C
0.9-N
1.2的1360cm
-1和1590cm
-1附近的特征峰分别代表了SP2碳的缺陷密度和结晶度，证实了碳壳层的存在。
Raman spectroscopy was performed on the products Mn 2 O 3 -C 0.9 -N 1.2 and Mn 2 O 3 , and the results are shown in Figure 3B. Raman spectroscopy can provide crystallographic information on the carbon skeleton. The characteristic peaks near 1360 cm -1 and 1590 cm -1 of Mn 2 O 3 -C 0.9 -N 1.2 represent the defect density and crystallinity of SP2 carbon, respectively, confirming the existence of the carbon shell.
对产物Mn
2O
3-C
0.9-N
1.2、以及Mn-MOF和Mn
2O
3-C
0.9等进行红外测试，结果如图3C所示。FT-IR光谱可识别纳米复合材料的组分。对于Mn-MOFs，1576cm
-1和1670cm
-1处的两个特征峰分别归因于2，2'-联吡啶中C＝N键的拉伸和均苯三甲酸中羧基的C＝O振动，这表明金属有机螯合物的形成。煅烧后，这些极性基团峰(C＝N，C＝O)消失，同时观察到Mn
2O
3(665，572和524cm
-1)的Mn-O-Mn峰。催化剂表面极性基团数量的减少可以增强表面碳层与BPA的π-π相互作用，从而加速反应体系中的电子转移。
Infrared tests were performed on the products Mn 2 O 3 -C 0.9 -N 1.2 , as well as Mn-MOF and Mn 2 O 3 -C 0.9 , and the results are shown in Figure 3C. FT-IR spectroscopy identifies components of nanocomposites. For Mn-MOFs, the two characteristic peaks at 1576 cm -1 and 1670 cm -1 are attributed to the stretching of the C=N bond in 2,2'-bipyridine and the C=O vibration of the carboxyl group in trimesic acid, respectively, This indicates the formation of metal-organic chelates. After calcination, these polar group peaks (C=N, C=O) disappeared, while Mn-O-Mn peaks of Mn 2 O 3 (665, 572 and 524 cm −1 ) were observed. The reduction of the number of polar groups on the catalyst surface can enhance the π-π interaction between the surface carbon layer and BPA, thereby accelerating the electron transfer in the reaction system.
对产物Mn
2O
3-C
0.9-N
1.2、以及Mn
3O
4、Mn
2O
3和Mn
2O
3-C
0.9进行EIS表征，结果如图3D所示。由图可知，奈奎斯特直径遵循Mn
3O
4>Mn
2O
3>Mn
2O
3-C
0.9>Mn
2O
3-C
0.9-N
1.2的顺序，表明Mn
2O
3-C-N达到最高电荷转移率。一方面，Mn
2O
3-C-N的碳壳提供了一个三维电子网络，以便于电荷转移。另一方面，在碳壳网络中掺杂氮杂原子会影响碳原子的自旋密度和电荷分布，从而导致Mn
2O
3-C
0.9-N
1.2的导电性增强，形成所谓的“激活区”。
The products Mn 2 O 3 -C 0.9 -N 1.2 , and Mn 3 O 4 , Mn 2 O 3 and Mn 2 O 3 -C 0.9 were characterized by EIS, and the results are shown in FIG. 3D . It can be seen from the figure that the Nyquist diameter follows the order of Mn 3 O 4 >Mn 2 O 3 >Mn 2 O 3 -C 0.9 >Mn 2 O 3 -C 0.9 -N 1.2 , indicating that Mn 2 O 3 -CN reaches the highest charge transfer rate. On the one hand, the carbon shell of Mn 2 O 3 -CN provides a three-dimensional electronic network to facilitate charge transfer. On the other hand, doping nitrogen heteroatoms in the carbon shell network affects the spin density and charge distribution of carbon atoms, leading to enhanced conductivity of Mn 2 O 3 -C 0.9 -N 1.2 , forming the so-called "active region" .
对产物Mn
2O
3-C
0.9-N
1.2以Mn-MOF进行XPS表征，结果如图4所示。可以看到特征峰位于284.6eV,285.5eV和289.0eV分别代表C-C/C＝C,C＝O/C＝N和C-O/C-N。氧的三个拟合峰分别表 示O-Mn(529.8eV),O＝C(531.7eV)和O–C(533.2eV),其表明了Mn-MOFs表面羧基官能团的存在。相比于Mn-MOFs，Mn
2O
3-C
0.9-N
1.2中C–O和C＝O峰强变弱，这是因为煅烧过程大部分的官能团被去除。另外，Mn
2O
3-C
0.9-N
1.2中的N峰也可以拟合成三个峰：397.5eV(pyridinic N),400.2eV(Mn-N),and 403.8eV(nitric oxide)。值得注意的是，由于N具有比C更小的原子直径和更强的电负性，在碳壳中掺杂N可以增强电子转移。同时，配位吡啶氮可能进一步增强极化差异，促进双反应中心的形成。
The product Mn 2 O 3 -C 0.9 -N 1.2 was characterized by XPS with Mn-MOF, and the results are shown in Fig. 4 . It can be seen that the characteristic peaks are located at 284.6eV, 285.5eV and 289.0eV represent CC/C=C, C=O/C=N and CO/CN, respectively. The three fitting peaks of oxygen represent O-Mn (529.8 eV), O=C (531.7 eV) and O–C (533.2 eV), respectively, which indicate the existence of carboxyl functional groups on the surface of Mn-MOFs. Compared with Mn-MOFs, the intensity of C–O and C=O peaks in Mn 2 O 3 -C 0.9 -N 1.2 became weaker because most of the functional groups were removed during calcination. In addition, the N peaks in Mn 2 O 3 -C 0.9 -N 1.2 can also be fitted to three peaks: 397.5 eV (pyridinic N), 400.2 eV (Mn-N), and 403.8 eV (nitric oxide). Notably, since N has a smaller atomic diameter and stronger electronegativity than C, doping N in the carbon shell can enhance electron transfer. Meanwhile, the coordinating pyridine nitrogen may further enhance the polarization difference and promote the formation of dual-reaction centers.
芬顿材料的应用：Applications of Fenton materials:
产物芬顿材料与PMS在水中联用，形成类芬顿体系，用来处理降解水中的有机污染物。有机污染物包括罗丹明B、双酚A或甲基橙。本实施例将产物Mn
2O
3-C
0.9-N
1.2与PMS在水中联用，处理降解水中的双酚A，结果如图5所示。
The product Fenton material is combined with PMS in water to form a Fenton-like system, which is used to treat and degrade organic pollutants in water. Organic pollutants include rhodamine B, bisphenol A or methyl orange. In this example, the product Mn 2 O 3 -C 0.9 -N 1.2 is used in combination with PMS in water to treat and degrade bisphenol A in water, and the results are shown in FIG. 5 .
用TOC去除率评价不同催化剂(产物Mn
2O
3-C
0.9-N
1.2以及Mn
2O
3)上BPA的矿化度，结果如图6所示。由图可知，Mn
2O
3-C
0.9-N
1.2的TOC去除率远高于Mn
2O
3。此外，Mn
2O
3和Mn
2O
3-C
0.9-N
1.2的PMS的利用率(η)随反应时间的变化呈现出不同的变化趋势。对于Mn
2O
3悬浮液，BPA矿化速率比PMS消耗速率慢，导致反应初期利用率低。随着反应时间的延长(2～8min)，双酚A中间体可被自由基完全矿化，提高了PMS的利用率。然而，由于Mn
2O
3悬浮液中Mn(Ⅲ)大部分转化为Mn(Ⅳ)，PMS活化速率再次减慢，8min后η逐渐降低。
The salinity of BPA on different catalysts (products Mn 2 O 3 -C 0.9 -N 1.2 and Mn 2 O 3 ) was evaluated by TOC removal rate, and the results are shown in FIG. 6 . It can be seen from the figure that the TOC removal rate of Mn 2 O 3 -C 0.9 -N 1.2 is much higher than that of Mn 2 O 3 . In addition, the utilization ratio (η) of PMS of Mn 2 O 3 and Mn 2 O 3 -C 0.9 -N 1.2 showed different trends with the change of reaction time. For the Mn2O3 suspension, the mineralization rate of BPA is slower than the consumption rate of PMS, resulting in low utilization rate at the initial stage of the reaction. With the prolongation of the reaction time (2-8 min), the bisphenol A intermediate can be completely mineralized by free radicals, which improves the utilization rate of PMS. However, since the Mn ( III ) in the Mn2O3 suspension is mostly converted to Mn(IV), the PMS activation rate slows down again, and η gradually decreases after 8 min.
Mn
2O
3-C
0.9-N
1.2在反应开始时获得了极高的PMS利用率，这表明它是一种非自由基反应(
1O
2)。一般来说，
1O
2可以通过自由基链式反应产生。在Mn
2O
3-C
0.9-N
1.2复合材料中，富电子Mn中心可以为PMS活化提供电子。由于双反应中心的协同作用和超细Mn
2O
3的极高活性，瞬间产生了大量的自由基。此外，N掺杂的碳壳可以通过C-O-Mn和C-N-Mn键促进有机中间基向富电子Mn中心的电子转移，从而促进Mn的氧化还原，避免PMS的无效分解。更重要的是，N掺杂碳壳的多孔结构不仅促进了自由基的复合生成
1O
2，而且为PMS和BPA提供了大量的吸附位点。
1O
2具有较高的亲电性，能选择性地攻击富含电子的官能团和一些不饱和化合物(BPA等)。因此，随着反应时间的延长，Mn
2O
3-C-N在极低剂量PMS下也能获得较高的PMS利用率。
Mn 2 O 3 -C 0.9 -N 1.2 obtained very high PMS utilization at the beginning of the reaction, which indicated that it was a non-radical reaction ( 1 O 2 ). Generally speaking, 1 O 2 can be produced by free radical chain reaction. In the Mn 2 O 3 -C 0.9 -N 1.2 composites, the electron-rich Mn centers can donate electrons for PMS activation. Due to the synergistic effect of the dual reaction centers and the extremely high activity of ultrafine Mn2O3, a large amount of free radicals are generated instantaneously. In addition, the N-doped carbon shell can facilitate electron transfer from organic intermediates to electron-rich Mn centers through CO-Mn and CN-Mn bonds, thereby promoting the redox of Mn and avoiding the ineffective decomposition of PMS. More importantly, the porous structure of the N-doped carbon shell not only promotes the recombination of radicals to generate 1 O 2 , but also provides a large number of adsorption sites for PMS and BPA. 1 O 2 has high electrophilicity and can selectively attack electron-rich functional groups and some unsaturated compounds (BPA, etc.). Therefore, with the prolongation of the reaction time, Mn 2 O 3 -CN can also obtain high PMS utilization at very low doses of PMS.
对反应后的催化剂进行稳定性表征，如图7A-C所示。如图7A和B所示，Mn
2O
3-C
0.9-N
1.2在PMS活化方面表现出比Mn
2O
3更高的催化稳定性。连续5次试验后，BPA对Mn
2O
3的降解率从44％下降到19％(图7A)，而Mn
2O
3-C
0.9-N
1.2在连续5次试验后16min内，BPA的去除率仍保持在97％以上。
The stability of the reacted catalyst was characterized, as shown in Figure 7A-C. As shown in Figure 7A and B, Mn 2 O 3 -C 0.9 -N 1.2 exhibited higher catalytic stability than Mn 2 O 3 in terms of PMS activation. After 5 consecutive experiments, the degradation rate of Mn 2 O 3 by BPA decreased from 44% to 19% (Fig. 7A), while Mn 2 O 3 -C 0.9 -N 1.2 within 16 min after 5 consecutive experiments, the removal of BPA The rate remains above 97%.
如图7C所示，Mn
2O
3-C-N(0.52mg/L)的浸出量远低于Mn
2O
3(1.77mg/L)的浸出量。Mn
2O
3-C
0.9-N
1.2的这种稳定性的改善可以解释为：(1)双反应中心不仅避免了高价锰的积累，而且防止了PMS的无效分解；(2)N掺杂的碳壳是防止Mn浸出的有效保护层。
As shown in Fig. 7C, the leaching amount of Mn 2 O 3 -CN (0.52 mg/L) was much lower than that of Mn 2 O 3 (1.77 mg/L). This improvement in stability of Mn 2 O 3 -C 0.9 -N 1.2 can be explained by: (1) the double reaction centers not only avoid the accumulation of high-valent manganese, but also prevent the ineffective decomposition of PMS; (2) N-doped The carbon shell is an effective protective layer against Mn leaching.
催化原理为：如图8所示，MOFs制备的Mn
2O
3-Cx-Ny纳米掺杂多孔碳杂化类芬顿催化剂，阳离子π键和Mn-N络合作用导致富电子Mn中心的形成，为PMS的活化提供了电子。因此，大量的O
2·-可以通过自由基链式反应产生。值得注意的是，N掺杂碳壳的多孔结构不仅促进了自由基(O
2·-，·OH)复合生成
1O
2，而且还为有机物提供了吸附位点，缩短了
1O
2的迁移距离。另一方面，N掺杂碳壳作为缺电子中心，通过C-O-Mn和C-N-Mn键促进了R*向富电子Mn中心的电子转移，促进了Mn(Ⅳ)向Mn(Ⅲ)/Mn(Ⅱ)的还原。由于双反应中心的协同效应，N掺杂碳壳的高吸附能力和
1O
2、Mn
2O
3-C
x-N
y的强氧化能力，即使在低剂量PMS(0.033g/L)下，也能显著提高PMS利用率和有机物矿化。
The catalytic principle is as follows: As shown in Figure 8, the Mn 2 O 3 -Cx-Ny nano-doped porous carbon hybrid Fenton-like catalyst prepared by MOFs, the cationic π bond and the Mn-N complexation lead to the formation of electron-rich Mn centers , which provides electrons for the activation of PMS. Therefore, a large amount of O 2 ·- can be generated by radical chain reaction. Notably, the porous structure of the N-doped carbon shell not only promotes the recombination of radicals (O 2 ·-, ·OH) to generate 1 O 2 , but also provides adsorption sites for organics, shortening the migration of 1 O 2 distance. On the other hand, the N-doped carbon shell acts as the electron-deficient center, which facilitates the electron transfer from R* to the electron-rich Mn center through CO-Mn and CN-Mn bonds, and promotes the transfer of Mn(IV) to Mn(III)/Mn( II) reduction. Due to the synergistic effect of the dual reaction centers, the high adsorption capacity of the N-doped carbon shell and the strong oxidative capacity of 1 O 2 , Mn 2 O 3 -C x -N y , even at a low dose of PMS (0.033 g/L), It can also significantly improve PMS utilization and organic matter mineralization.
实施例4Example 4
本实施例提供一种Mn
2O
3@N掺杂多孔碳杂化类芬顿材料的制备方法及其应用。
This embodiment provides a preparation method and application of a Mn 2 O 3 @N doped porous carbon hybrid Fenton-like material.
制备方法包括以下步骤：The preparation method includes the following steps:
步骤一、将2.51g六水合硝酸锰、0.9g均苯三甲酸和1.5g 2,2'-联吡啶加入至30mL N,N-二甲基甲酰胺(DMF)和30mL乙醇的混合溶液中，并磁力搅拌6h，搅拌速率为100-200r/min。Step 1. Add 2.51g manganese nitrate hexahydrate, 0.9g trimesic acid and 1.5g 2,2'-bipyridine into a mixed solution of 30mL N,N-dimethylformamide (DMF) and 30mL ethanol, And magnetic stirring for 6h, stirring rate of 100-200r/min.
步骤二、将步骤一得到的混合物转移到聚四氟乙烯内衬高压釜中，在180℃下加热18h进行密闭水热反应得到Mn-MOF固体物质。In step 2, the mixture obtained in step 1 was transferred to a polytetrafluoroethylene-lined autoclave, heated at 180° C. for 18 hours, and subjected to a closed hydrothermal reaction to obtain a Mn-MOF solid substance.
步骤三、用乙醇和水清洗步骤二得到的Mn-MOF固体物质三次，再于80℃干燥。Step 3: Wash the Mn-MOF solid substance obtained in Step 2 three times with ethanol and water, and then dry at 80°C.
步骤四、将烘干后的Mn-MOF固体物质在马弗炉中煅烧，煅烧的升温速率为5-10℃，煅烧温度为500℃，煅烧时间为4h，最终得到类芬顿催化材料。Step 4: calcining the dried Mn-MOF solid material in a muffle furnace, the heating rate of calcination is 5-10°C, the calcination temperature is 500°C, and the calcination time is 4h, and finally a Fenton-like catalytic material is obtained.
产物芬顿材料与PMS在水中联用，形成类芬顿体系，用来处理降解水中的有机污染物。有机污染物包括罗丹明B、双酚A或甲基橙。本实施例将产物Mn
2O
3-C
0.9-N
1.5与PMS在水中联用，处理降解水中的双酚A，结果如图5所示。
The product Fenton material is combined with PMS in water to form a Fenton-like system, which is used to treat and degrade organic pollutants in water. Organic pollutants include rhodamine B, bisphenol A or methyl orange. In this example, the product Mn 2 O 3 -C 0.9 -N 1.5 is used in combination with PMS in water to treat and degrade bisphenol A in water, and the results are shown in FIG. 5 .
通过对双酚A的降解实验来评价各催化剂(实施例1-4产物)对PMS的活化性能，如图5所示，Mn
2O
3-C
X(x＝0.3，0.6，0.9，1.2)显示出比纯Mn
2O
3和Mn
3O
4更高的催化活性。BPA对Mn
2O
3-C
X的去除率依次为Mn
2O
3-C
0.9>Mn
2O
3-C
0.6>Mn
2O
3-C
1.2>Mn
2O
3-C
0.3。在16min内，Mn(Ta)可以降解约93％的BPA。在合成过程中过量添加Ta可在步骤2中形成过厚的碳壳层，这可能对PMS与Mn2O3的反应产生不利影响。因此，在Mn
2O
3-C
X的合成过程中，以0.9g的TA为最佳用量。
The activation performance of each catalyst (products of Examples 1-4) to PMS was evaluated by the degradation experiment of bisphenol A, as shown in Figure 5, Mn 2 O 3 -C X (x=0.3, 0.6, 0.9, 1.2) showed higher catalytic activity than pure Mn2O3 and Mn3O4 . The removal rate of Mn 2 O 3 -C X by BPA was in the order of Mn 2 O 3 -C 0.9 >Mn 2 O 3 -C 0.6 >Mn 2 O 3 -C 1.2 >Mn 2 O 3 -C 0.3 . Within 16 min, Mn(Ta) can degrade about 93% of BPA. Excessive addition of Ta during the synthesis can form an excessively thick carbon shell in step 2, which may adversely affect the reaction of PMS with Mn2O3. Therefore, in the synthesis process of Mn 2 O 3 -C X , 0.9g of TA is the optimal amount.
与Mn
2O
3-C
0.9相比，Mn
2O
3-C
0.9-N
y(y＝0.45、0.9、1.2、1.5)的催化活性显著提高。碳壳中N的掺杂不仅促进了电子转移，增强了双反应中心，而且增强了BPA和PMS的吸附，缩短了它们的迁移距离。Mn
2O
3-C
0.9-N
y的催化性能依次为Mn
2O
3-C
0.9-N
1.2>Mn
2O
3-C
0.9-N
1.5>Mn
2O
3-C
0.9-N
0.9>Mn
2O
3-C
0.9-N
0.45。对于Mn
2O
3-C
0.9-N
1.2，20mg/L的双酚A在4min内完全降解(PMS＝0.1g/L)，表现出良好的催化活性。因此，选择Mn
2O
3-C
0.9-N
1.2作为进一步研究的最佳催化剂。一般来说，有机物在相对大剂量PMS(>1g/L)的Fenton样体系中才容易被降解。在本申请中，在低剂量PMS(0.1g/L)下，BPA在Mn
2O
3-C
0.9-N
1.2也被有效降解，显示了Mn
2O
3-C
0.9-N
1.2的优异催化活性。此外，随着PMS剂量从0.1g/L进一步降低到0.033g/L，Mn
2O
3-C
0.9-N
1.2仍能在16分钟内完全去除BPA。
Compared with Mn 2 O 3 -C 0.9 , the catalytic activity of Mn 2 O 3 -C 0.9 -N y (y=0.45, 0.9, 1.2, 1.5) was significantly improved. The doping of N in the carbon shell not only promotes electron transfer and enhances the double reaction center, but also enhances the adsorption of BPA and PMS and shortens their migration distance. The catalytic performance of Mn 2 O 3 -C 0.9 -N y is in the order of Mn 2 O 3 -C 0.9 -N 1.2 >Mn 2 O 3 -C 0.9 -N 1.5 >Mn 2 O 3 -C 0.9 -N 0.9 >Mn 2 O 3 -C 0.9 -N 0.45 . For Mn 2 O 3 -C 0.9 -N 1.2 , 20 mg/L of bisphenol A was completely degraded within 4 min (PMS=0.1 g/L), showing good catalytic activity. Therefore, Mn 2 O 3 -C 0.9 -N 1.2 was selected as the best catalyst for further study. In general, organics are easily degraded in Fenton-like systems with relatively large doses of PMS (>1 g/L). In this application, BPA was also effectively degraded in Mn 2 O 3 -C 0.9 -N 1.2 under low dose of PMS (0.1 g/L), showing excellent catalytic activity of Mn 2 O 3 -C 0.9 -N 1.2 . Furthermore, as the PMS dose was further reduced from 0.1 g/L to 0.033 g/L, Mn 2 O 3 -C 0.9 -N 1.2 could still completely remove BPA within 16 minutes.
实施例5Example 5
本实施例提供一种Mn
2O
3@N掺杂多孔碳杂化类芬顿材料的制备方法，包括以下步骤：
This embodiment provides a preparation method of Mn 2 O 3 @N doped porous carbon hybrid Fenton-like material, comprising the following steps:
步骤一、将2.51g六水合硝酸锰、0.9g均苯三甲酸和1.5g 2,2'-联吡啶加入至30mL N,N-二甲基甲酰胺(DMF)和30mL乙醇的混合溶液中，并磁力搅拌6h，搅拌速率为100-200r/min。Step 1. Add 2.51g manganese nitrate hexahydrate, 0.9g trimesic acid and 1.5g 2,2'-bipyridine into a mixed solution of 30mL N,N-dimethylformamide (DMF) and 30mL ethanol, And magnetic stirring for 6h, stirring rate of 100-200r/min.
步骤二、将步骤一得到的混合物转移到聚四氟乙烯内衬高压釜中，在180℃下加热18h进行密闭水热反应得到Mn-MOF固体物质。In step 2, the mixture obtained in step 1 was transferred to a polytetrafluoroethylene-lined autoclave, heated at 180° C. for 18 hours, and subjected to a closed hydrothermal reaction to obtain a Mn-MOF solid substance.
步骤三、用乙醇和水清洗步骤二得到的Mn-MOF固体物质三次，再于80℃干燥。Step 3: Wash the Mn-MOF solid substance obtained in Step 2 three times with ethanol and water, and then dry at 80°C.
步骤四、将烘干后的Mn-MOF固体物质在马弗炉中煅烧，煅烧的升温速率为5-10℃，煅烧温度为450℃，煅烧时间为4h，最终得到类芬顿催化材料。Step 4: calcining the dried Mn-MOF solid material in a muffle furnace, the heating rate of calcination is 5-10°C, the calcination temperature is 450°C, and the calcination time is 4h, and finally a Fenton-like catalytic material is obtained.
实施例6Example 6
本实施例提供一种Mn
2O
3@N掺杂多孔碳杂化类芬顿材料的制备方法，包括以下步骤：
This embodiment provides a preparation method of Mn 2 O 3 @N doped porous carbon hybrid Fenton-like material, comprising the following steps:
步骤一、将2.51g六水合硝酸锰、0.9g均苯三甲酸和1.5g 2,2'-联吡啶加入至30mL N,N-二甲基甲酰胺(DMF)和30mL乙醇的混合溶液中，并磁力搅拌6h，搅拌速率为100-200r/min。Step 1. Add 2.51g manganese nitrate hexahydrate, 0.9g trimesic acid and 1.5g 2,2'-bipyridine into a mixed solution of 30mL N,N-dimethylformamide (DMF) and 30mL ethanol, And magnetic stirring for 6h, stirring rate of 100-200r/min.
步骤二、将步骤一得到的混合物转移到聚四氟乙烯内衬高压釜中，在180℃下加热18h进行密闭水热反应得到Mn-MOF固体物质。In step 2, the mixture obtained in step 1 was transferred to a polytetrafluoroethylene-lined autoclave, heated at 180° C. for 18 hours, and subjected to a closed hydrothermal reaction to obtain a Mn-MOF solid substance.
步骤三、用乙醇和水清洗步骤二得到的Mn-MOF固体物质三次，再于80℃干燥。Step 3: Wash the Mn-MOF solid substance obtained in Step 2 three times with ethanol and water, and then dry at 80°C.
步骤四、将烘干后的Mn-MOF固体物质在马弗炉中煅烧，煅烧的升温速率为5-10℃，煅烧温度为600℃，煅烧时间为4h，最终得到类芬顿催化材料。Step 4: calcining the dried Mn-MOF solid material in a muffle furnace, the heating rate of calcination is 5-10°C, the calcination temperature is 600°C, and the calcination time is 4h, and finally a Fenton-like catalytic material is obtained.
实施例7Example 7
本实施例提供一种Mn
2O
3@N掺杂多孔碳杂化类芬顿材料的制备方法，包括以下步骤：
This embodiment provides a preparation method of Mn 2 O 3 @N doped porous carbon hybrid Fenton-like material, comprising the following steps:
步骤一、将2.51g六水合硝酸锰、0.9g均苯三甲酸和1.5g 2,2'-联吡啶加入至30mL N,N-二甲基甲酰胺(DMF)和30mL乙醇的混合溶液中，并磁力搅拌6h，搅拌速率为100-200r/min。Step 1. Add 2.51g manganese nitrate hexahydrate, 0.9g trimesic acid and 1.5g 2,2'-bipyridine into a mixed solution of 30mL N,N-dimethylformamide (DMF) and 30mL ethanol, And magnetic stirring for 6h, stirring rate of 100-200r/min.
步骤二、将步骤一得到的混合物转移到聚四氟乙烯内衬高压釜中，在180℃下加热18h进行密闭水热反应得到Mn-MOF固体物质。In step 2, the mixture obtained in step 1 was transferred to a polytetrafluoroethylene-lined autoclave, heated at 180° C. for 18 hours, and subjected to a closed hydrothermal reaction to obtain a Mn-MOF solid substance.
步骤三、用乙醇和水清洗步骤二得到的Mn-MOF固体物质三次，再于80℃干燥。Step 3: Wash the Mn-MOF solid substance obtained in Step 2 three times with ethanol and water, and then dry at 80°C.
步骤四、将烘干后的Mn-MOF固体物质在马弗炉中煅烧，煅烧的升温速率为5-10℃，煅烧温度为500℃，煅烧时间为2h，最终得到类芬顿催化材料。Step 4: calcining the dried Mn-MOF solid material in a muffle furnace, the heating rate of calcination is 5-10°C, the calcination temperature is 500°C, and the calcination time is 2h, and finally a Fenton-like catalytic material is obtained.
实施例8Example 8
本实施例提供一种Mn
2O
3@N掺杂多孔碳杂化类芬顿材料的制备方法，包括以下步骤：
This embodiment provides a preparation method of Mn 2 O 3 @N doped porous carbon hybrid Fenton-like material, comprising the following steps:
步骤一、将2.51g六水合硝酸锰、0.9g均苯三甲酸和1.5g 2,2'-联吡啶加入至30mL N,N-二甲基甲酰胺(DMF)和30mL乙醇的混合溶液中，并磁力搅拌6h，搅拌速率为100-200r/min。Step 1. Add 2.51g manganese nitrate hexahydrate, 0.9g trimesic acid and 1.5g 2,2'-bipyridine into a mixed solution of 30mL N,N-dimethylformamide (DMF) and 30mL ethanol, And magnetic stirring for 6h, stirring rate of 100-200r/min.
步骤二、将步骤一得到的混合物转移到聚四氟乙烯内衬高压釜中，在180℃下加热18h进行密闭水热反应得到Mn-MOF固体物质。In step 2, the mixture obtained in step 1 was transferred to a polytetrafluoroethylene-lined autoclave, heated at 180° C. for 18 hours, and subjected to a closed hydrothermal reaction to obtain a Mn-MOF solid substance.
步骤三、用乙醇和水清洗步骤二得到的Mn-MOF固体物质三次，再于80℃干燥。Step 3: Wash the Mn-MOF solid substance obtained in Step 2 three times with ethanol and water, and then dry at 80°C.
步骤四、将烘干后的Mn-MOF固体物质在马弗炉中煅烧，煅烧的升温速率为5-10℃，煅烧温度为500℃，煅烧时间为6h，最终得到类芬顿催化材料。Step 4: calcining the dried Mn-MOF solid material in a muffle furnace, the heating rate of calcination is 5-10°C, the calcination temperature is 500°C, and the calcination time is 6h, and finally a Fenton-like catalytic material is obtained.
实施例9Example 9
本实施例提供一种Mn
2O
3@N掺杂多孔碳杂化类芬顿材料的制备方法，包括以下步骤：
This embodiment provides a preparation method of Mn 2 O 3 @N doped porous carbon hybrid Fenton-like material, comprising the following steps:
步骤一、将2.51g六水合硝酸锰、0.9g均苯三甲酸和1.5g 2,2'-联吡啶加入至30mL N,N-二甲基甲酰胺(DMF)和30mL乙醇的混合溶液中，并磁力搅拌6h，搅拌速率为100-200r/min。Step 1. Add 2.51g manganese nitrate hexahydrate, 0.9g trimesic acid and 1.5g 2,2'-bipyridine into a mixed solution of 30mL N,N-dimethylformamide (DMF) and 30mL ethanol, And magnetic stirring for 6h, stirring rate of 100-200r/min.
步骤二、将步骤一得到的混合物转移到聚四氟乙烯内衬高压釜中，在150℃下加热18h进行密闭水热反应得到Mn-MOF固体物质。In step 2, the mixture obtained in step 1 was transferred to a polytetrafluoroethylene-lined autoclave, heated at 150° C. for 18 hours, and subjected to a closed hydrothermal reaction to obtain Mn-MOF solid matter.
步骤三、用乙醇和水清洗步骤二得到的Mn-MOF固体物质三次，再于80℃干燥。Step 3: Wash the Mn-MOF solid substance obtained in Step 2 three times with ethanol and water, and then dry at 80°C.
步骤四、将烘干后的Mn-MOF固体物质在马弗炉中煅烧，煅烧的升温速率为5-10℃，煅烧温度为500℃，煅烧时间为4h，最终得到类芬顿催化材料。Step 4: calcining the dried Mn-MOF solid material in a muffle furnace, the heating rate of calcination is 5-10°C, the calcination temperature is 500°C, and the calcination time is 4h, and finally a Fenton-like catalytic material is obtained.
实施例10Example 10
本实施例提供一种Mn
2O
3@N掺杂多孔碳杂化类芬顿材料的制备方法，包括以下步骤：
This embodiment provides a preparation method of Mn 2 O 3 @N doped porous carbon hybrid Fenton-like material, comprising the following steps:
步骤一、将2.51g六水合硝酸锰、0.9g均苯三甲酸和1.5g 2,2'-联吡啶加入至30mL N,N-二甲基甲酰胺(DMF)和30mL乙醇的混合溶液中，并磁力搅拌6h，搅拌速率为100-200r/min。Step 1. Add 2.51g manganese nitrate hexahydrate, 0.9g trimesic acid and 1.5g 2,2'-bipyridine into a mixed solution of 30mL N,N-dimethylformamide (DMF) and 30mL ethanol, And magnetic stirring for 6h, stirring rate of 100-200r/min.
步骤二、将步骤一得到的混合物转移到聚四氟乙烯内衬高压釜中，在200℃下加热18h进行密闭水热反应得到Mn-MOF固体物质。In step 2, the mixture obtained in step 1 was transferred to a polytetrafluoroethylene-lined autoclave, heated at 200° C. for 18 hours, and subjected to a closed hydrothermal reaction to obtain Mn-MOF solid matter.
步骤三、用乙醇和水清洗步骤二得到的Mn-MOF固体物质三次，再于80℃干燥。Step 3: Wash the Mn-MOF solid substance obtained in Step 2 three times with ethanol and water, and then dry at 80°C.
步骤四、将烘干后的Mn-MOF固体物质在马弗炉中煅烧，煅烧的升温速率为5-10℃，煅烧温度为500℃，煅烧时间为4h，最终得到类芬顿催化材料。Step 4: calcining the dried Mn-MOF solid material in a muffle furnace, the heating rate of calcination is 5-10°C, the calcination temperature is 500°C, and the calcination time is 4h, and finally a Fenton-like catalytic material is obtained.
实施例11Example 11
本实施例提供一种Mn
2O
3@N掺杂多孔碳杂化类芬顿材料的制备方法，包括以下步骤：
This embodiment provides a preparation method of Mn 2 O 3 @N doped porous carbon hybrid Fenton-like material, comprising the following steps:
步骤一、将2.51g六水合硝酸锰、0.3g均苯三甲酸和1.2g 2,2'-联吡啶加入至30mL N,N-二甲基甲酰胺(DMF)和30mL乙醇的混合溶液中，并磁力搅拌3h，搅拌速率为100-200r/min。Step 1. Add 2.51g manganese nitrate hexahydrate, 0.3g trimesic acid and 1.2g 2,2'-bipyridine into a mixed solution of 30mL N,N-dimethylformamide (DMF) and 30mL ethanol, And magnetic stirring for 3h, stirring rate of 100-200r/min.
步骤二、将步骤一得到的混合物转移到聚四氟乙烯内衬高压釜中，在120℃下加热25h进行密闭水热反应得到Mn-MOF固体物质。In step 2, the mixture obtained in step 1 is transferred to a polytetrafluoroethylene-lined autoclave, heated at 120° C. for 25 hours, and subjected to a closed hydrothermal reaction to obtain a Mn-MOF solid substance.
步骤三、用乙醇和水清洗步骤二得到的Mn-MOF固体物质三次，再于60℃干燥。Step 3: Wash the Mn-MOF solid matter obtained in Step 2 with ethanol and water three times, and then dry at 60°C.
步骤四、将烘干后的Mn-MOF固体物质在马弗炉中煅烧，煅烧的升温速率为5-10℃，煅烧温度为400℃，煅烧时间为4h，最终得到类芬顿催化材料。Step 4: calcining the dried Mn-MOF solid material in a muffle furnace, the heating rate of calcination is 5-10°C, the calcination temperature is 400°C, and the calcination time is 4h, and finally a Fenton-like catalytic material is obtained.
实施例12Example 12
本实施例提供一种Mn
2O
3@N掺杂多孔碳杂化类芬顿材料的制备方法，包括以下步骤：
This embodiment provides a preparation method of Mn 2 O 3 @N doped porous carbon hybrid Fenton-like material, comprising the following steps:
步骤一、将2.51g六水合硝酸锰、1.2g均苯三甲酸和1.2g 2,2'-联吡啶加入至30mL N,N- 二甲基甲酰胺(DMF)和30mL乙醇的混合溶液中，并磁力搅拌12h，搅拌速率为100-200r/min。Step 1. Add 2.51g manganese nitrate hexahydrate, 1.2g trimesic acid and 1.2g 2,2'-bipyridine into a mixed solution of 30mL N,N-dimethylformamide (DMF) and 30mL ethanol, And magnetic stirring for 12h, stirring rate of 100-200r/min.
步骤二、将步骤一得到的混合物转移到聚四氟乙烯内衬高压釜中，在220℃下加热15h进行密闭水热反应得到Mn-MOF固体物质。In step 2, the mixture obtained in step 1 is transferred to a polytetrafluoroethylene-lined autoclave, heated at 220° C. for 15 hours, and subjected to a closed hydrothermal reaction to obtain a Mn-MOF solid substance.
步骤三、用乙醇和水清洗步骤二得到的Mn-MOF固体物质三次，再于100℃干燥。Step 3: Wash the Mn-MOF solid matter obtained in Step 2 three times with ethanol and water, and then dry at 100°C.
步骤四、将烘干后的Mn-MOF固体物质在马弗炉中煅烧，煅烧的升温速率为5-10℃，煅烧温度为500℃，煅烧时间为4h，最终得到类芬顿催化材料。Step 4: calcining the dried Mn-MOF solid material in a muffle furnace, the heating rate of calcination is 5-10°C, the calcination temperature is 500°C, and the calcination time is 4h, and finally a Fenton-like catalytic material is obtained.
Claims (10)
- 一种Mn 2O 3@N掺杂多孔碳杂化类芬顿材料的制备方法，其特征在于： A method for preparing a Mn 2 O 3 @N-doped porous carbon hybrid Fenton-like material, characterized in that:包括以下步骤：Include the following steps:步骤一、将六水合硝酸锰、均苯三甲酸和2,2'-联吡啶加入至N,N-二甲基甲酰胺和乙醇的混合溶液中，并进行搅拌；Step 1, adding manganese nitrate hexahydrate, trimesic acid and 2,2'-bipyridine into the mixed solution of N,N-dimethylformamide and ethanol, and stirring;步骤二、将步骤一得到的混合物转移到聚四氟乙烯内衬高压釜中，进行密闭水热反应得到Mn-MOF固体物质；Step 2, the mixture obtained in step 1 is transferred to a polytetrafluoroethylene lined autoclave, and a closed hydrothermal reaction is carried out to obtain Mn-MOF solid matter;步骤三、清洗步骤二得到的Mn-MOF固体物质再干燥；Step 3, the Mn-MOF solid matter obtained in cleaning step 2 is dried again;步骤四、将烘干后的Mn-MOF固体物质在马弗炉中煅烧，得到芬顿催化材料。Step 4: calcining the dried Mn-MOF solid material in a muffle furnace to obtain a Fenton catalytic material.
- 根据权利要求1所述的Mn 2O 3@N掺杂多孔碳杂化类芬顿材料的制备方法，其特征在于： The preparation method of Mn 2 O 3 @N doped porous carbon hybrid Fenton-like material according to claim 1, characterized in that:其中，步骤一中，每40-100mL N,N-二甲基甲酰胺和乙醇的混合溶液中加入2.51g六水合硝酸锰、0.3-1.2g均苯三甲酸和0.45-1.5g的2,2'-联吡啶；Wherein, in step 1, 2.51g of manganese nitrate hexahydrate, 0.3-1.2g of trimesic acid and 0.45-1.5g of 2,2 '-bipyridine;N,N-二甲基甲酰胺和乙醇的体积比为1∶1。The volume ratio of N,N-dimethylformamide and ethanol was 1:1.
- 根据权利要求1所述的Mn 2O 3@N掺杂多孔碳杂化类芬顿材料的制备方法，其特征在于： The preparation method of Mn 2 O 3 @N doped porous carbon hybrid Fenton-like material according to claim 1, characterized in that:其中，步骤一采用磁力搅拌，搅拌速率为100-200r/min，搅拌时间为3-12h。Wherein, step 1 adopts magnetic stirring, the stirring rate is 100-200r/min, and the stirring time is 3-12h.
- 根据权利要求1所述的Mn 2O 3@N掺杂多孔碳杂化类芬顿材料的制备方法，其特征在于： The preparation method of Mn 2 O 3 @N doped porous carbon hybrid Fenton-like material according to claim 1, characterized in that:其中，步骤二中，水热反应的反应温度为120-220℃，反应时间为15-25h。Wherein, in the second step, the reaction temperature of the hydrothermal reaction is 120-220° C., and the reaction time is 15-25 h.
- 根据权利要求1所述的Mn 2O 3@N掺杂多孔碳杂化类芬顿材料的制备方法，其特征在于： The preparation method of Mn 2 O 3 @N doped porous carbon hybrid Fenton-like material according to claim 1, characterized in that:其中，步骤三中，用乙醇和水清洗Mn-MOF固体物质三次。Wherein, in step 3, the Mn-MOF solid matter is washed three times with ethanol and water.
- 根据权利要求1所述的Mn 2O 3@N掺杂多孔碳杂化类芬顿材料的制备方法，其特征在于： The preparation method of Mn 2 O 3 @N doped porous carbon hybrid Fenton-like material according to claim 1, characterized in that:其中，步骤三中，烘干温度为60℃-100℃。Wherein, in step 3, the drying temperature is 60°C-100°C.
- 根据权利要求1所述的Mn 2O 3@N掺杂多孔碳杂化类芬顿材料的制备方法，其特征在于： The preparation method of Mn 2 O 3 @N doped porous carbon hybrid Fenton-like material according to claim 1, characterized in that:其中，步骤四中，马弗炉中煅烧的升温速率为5-10℃，煅烧温度为400-600℃，煅烧时间为2-6h。Wherein, in step 4, the heating rate of calcination in the muffle furnace is 5-10°C, the calcination temperature is 400-600°C, and the calcination time is 2-6h.
- 一种Mn 2O 3@N掺杂多孔碳杂化类芬顿材料，其特征在于：由权利要求1-7任一项所述的制备方法制得，芬顿材料的结构式为Mn 2O 3-C x-N y，x，y分别表示均苯三甲酸和2,2'-联吡啶的添加量。 A Mn 2 O 3 @N-doped porous carbon hybrid Fenton-like material, characterized in that: it is prepared by the preparation method described in any one of claims 1-7, and the structural formula of the Fenton material is Mn 2 O 3 -C x -N y , x, y represent the addition amounts of trimesic acid and 2,2'-bipyridine, respectively.
- 如权利要求8所述的Mn 2O 3@N掺杂多孔碳杂化类芬顿材料与PMS在水中联用处理降解有机污染物的应用。 The application of the Mn 2 O 3 @N doped porous carbon hybrid Fenton-like material and PMS in water treatment to degrade organic pollutants as claimed in claim 8 .
- 根据权利要求9所述的Mn 2O 3@N掺杂多孔碳杂化类芬顿材料的应用，其特征在于： The application of the Mn 2 O 3 @N-doped porous carbon hybrid Fenton-like material according to claim 9, wherein:所述有机污染物为罗丹明B、双酚A和甲基橙中的任一种。The organic pollutant is any one of Rhodamine B, Bisphenol A and methyl orange.
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