CN111841617B - Mn (manganese)2O3@ N doped porous carbon hybrid Fenton material and preparation method and application thereof - Google Patents
Mn (manganese)2O3@ N doped porous carbon hybrid Fenton material and preparation method and application thereof Download PDFInfo
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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 43
- 239000011572 manganese Substances 0.000 title claims description 111
- 229910052748 manganese Inorganic materials 0.000 title claims description 8
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 title claims description 5
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims abstract description 69
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 66
- GEYXPJBPASPPLI-UHFFFAOYSA-N manganese(III) oxide Inorganic materials O=[Mn]O[Mn]=O GEYXPJBPASPPLI-UHFFFAOYSA-N 0.000 claims abstract description 64
- 238000001354 calcination Methods 0.000 claims abstract description 62
- 239000013239 manganese-based metal-organic framework Substances 0.000 claims abstract description 56
- 239000007787 solid Substances 0.000 claims abstract description 47
- 239000000126 substance Substances 0.000 claims abstract description 46
- 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 44
- 230000003197 catalytic effect Effects 0.000 claims abstract description 35
- 238000006243 chemical reaction Methods 0.000 claims abstract description 34
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- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical compound N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 claims abstract description 22
- -1 polytetrafluoroethylene Polymers 0.000 claims abstract description 19
- 238000001035 drying Methods 0.000 claims abstract description 17
- 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
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- 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 38
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 34
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- 230000015556 catabolic process Effects 0.000 claims description 8
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- 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
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- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 abstract description 3
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- 239000003054 catalyst Substances 0.000 description 31
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 20
- 150000003254 radicals Chemical class 0.000 description 18
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 11
- 230000015572 biosynthetic process Effects 0.000 description 10
- 239000010410 layer Substances 0.000 description 10
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
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- 229910052757 nitrogen Inorganic materials 0.000 description 8
- 230000027756 respiratory electron transport chain Effects 0.000 description 8
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 7
- 238000000354 decomposition reaction Methods 0.000 description 7
- 230000000593 degrading effect Effects 0.000 description 7
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- 229910016978 MnOx Inorganic materials 0.000 description 4
- 229910018648 Mn—N Inorganic materials 0.000 description 4
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- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 4
- 230000002195 synergetic effect Effects 0.000 description 4
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 3
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- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 3
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- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-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
- 230000009471 action Effects 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
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- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 2
- 239000011943 nanocatalyst Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-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
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 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
- 229910052802 copper Inorganic materials 0.000 description 1
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- 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
- 239000002114 nanocomposite Substances 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
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- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 238000007348 radical reaction Methods 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
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- 239000002904 solvent Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 229960004989 tetracycline hydrochloride Drugs 0.000 description 1
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- 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
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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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/391—Physical properties of the active metal ingredient
- B01J35/394—Metal dispersion value, e.g. percentage or fraction
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/63—Pore volume
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- 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
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/38—Organic compounds containing nitrogen
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/40—Organic compounds containing sulfur
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Abstract
The invention discloses Mn2O3The @ N doped porous carbon hybrid Fenton material and the preparation method and the application thereof are disclosed, wherein the preparation method comprises the following steps: step one, adding manganese nitrate hexahydrate, trimesic acid and 2,2' -bipyridine into a mixed solution of N, N-dimethylformamide and ethanol, and stirring; step two, transferring the mixture obtained in the step one into a polytetrafluoroethylene lining high-pressure kettle, and carrying out closed hydrothermal reaction to obtain a Mn-MOF solid substance; step three, washing the Mn-MOF solid substance obtained in the step two and then drying; and step four, calcining the dried Mn-MOF solid substance in a muffle furnace to obtain the Fenton catalytic material. The material is of a core-shell structure, and the inside of the material is superfine Mn2O3The nano particles are uniformly distributed in the porous carbon layer structure, have good removal effect on various toxic and harmful organic pollutants, particularly phenolic pollutants, under the neutral condition, and can realize high-selectivity conversion on PMS.
Description
Technical Field
The invention belongs to the field of materials, relates to a Fenton material, and particularly relates to Mn2O3@ N doped porous carbon hybrid Fenton material and preparation method and application thereof.
Background
Conventional Fenton oxidation includes a homogeneous Fenton process and a heterogeneous Fenton process, wherein homogeneous Fenton is achieved using Fe2+And H2O2The reaction generates hydroxyl free radical (HO) with super oxidation capacity to degrade the pollutants in the water. However, the conventional Fenton technique has many drawbacks, such as strict acidic conditions (pH)<3) Generation of iron sludge during the reaction, andthe extremely low utilization rate of the oxidant greatly limits the application of the traditional Fenton method in the actual wastewater treatment. Thus, heterogeneous phase fenton catalysis has attracted much attention, and in the research of heterogeneous fenton catalysis, a dual-reactive-center mechanism has attracted great interest to researchers due to its unique advantages, such as high oxidant utilization rate, catalytic stability, etc. However, the traditional electron-rich Cu-centered fenton-like catalyst still has many defects to hinder the development thereof, such as low mineralization degree on phenolic pollutants, poor degradation effect on organic pollutants with large molecular weight, and the like. For example:
the invention application with the application number of 201911252787.X discloses a manganese oxide nanowire-supported ferroferric oxide magnetic Fenton catalyst, a one-step synthesis method and application thereof. However, the whole reaction still obeys the mechanism of the classical fenton reaction, and the catalyst still relies on the oxidation-reduction reaction of a single site of metal to realize the activation of the hydrogen peroxide, and the utilization rate of the hydrogen peroxide in the system is still 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, wherein an iron active substance prepared by the method is anchored on a nitrogen-doped carbon carrier in a single-atom form, and the load is 0.3-10 wt%. The method is simple and rapid, and has relatively low cost. However, it is inevitable that the catalytic performance is reduced due to the reduction of activity of the metal in the catalyst in the continuous valence state conversion, 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, a preparation method and application thereof, and relates to a preparation method of a heterogeneous copper-based catalyst composite catalyst. The introduction of the second metal can remarkably inhibit ineffective decomposition of hydrogen peroxide (into oxygen and water), promote the decomposition of hydrogen peroxide into hydroxyl radicals (OH) with strong oxidizing property, and improve the quinoline decomposition amount per unit mole of hydrogen peroxide, namely the utilization rate of hydrogen peroxide. However, the concentration of hydrogen peroxide required in the entire fenton reaction process is too high, and a large amount of oxidant is wasted due to the self-decomposition of hydrogen peroxide and the reaction with hydroxyl radicals in the system.
The invention application with the application number of 201911224312.X discloses a preparation method of an ultra-small ferroferric oxide dense-coated three-dimensional reduced graphene oxide Fenton catalyst. The invention solves the problem that the existing method loads Fe on graphene3O4Non-uniformity, weakness and few catalytically active sites. The prepared ultra-small ferroferric oxide compact-coated three-dimensional reduced graphene oxide Fenton catalyst has the advantages that the catalytic performance is obviously improved, tetracycline hydrochloride is degraded for 20min, the degradation rate can reach 100%, and the excellent circulation stability is realized. However, graphene used in the catalytic material has limitations in actual wastewater treatment and is very easily inactivated.
Due to MnOxThe valence state change (II, III, IV) in the catalytic reaction involves a single electron transfer, so that MnOxIs considered to be a very promising Fenton-like catalyst. In addition, previous studies have shown that MnO of ultra-nanometer scalexNot only has high specific surface area, but also shortens mass/electron transfer path and has higher catalytic activity. However, ultra-fine MnOxDue to the large surface energy, the catalyst is easy to aggregate in solution, the exposure of active centers is seriously reduced, and even the irreversible deactivation of the catalyst is caused. In addition, the process of converting free radicals into singlet oxygen also requires a space structure which can generate a large amount of free radicals in a short time and provide free radical recombination in the system. There are several technical problems to be solved in order to realize the synergistic effect of the double reaction active center and the free radical conversion: (1) how to construct MnOxThe structure enables the manganese oxide in the material to avoid agglomeration to lose active sites; (2) polarization difference is strong enough to realize a double-reaction active center mechanism, so that polarization difference is formed on the surface of the catalytic material by selecting and designing proper ligands and bonding; (3) how to construct the catalytic material to produce suitable nano-particles on its surfaceThe milliconfinement effect promotes the recombination and conversion of free radicals into singlet oxygen.
Disclosure of Invention
The invention provides Mn2O3The @ N doped porous carbon hybrid Fenton material and the preparation method and the application thereof overcome the defects of the prior art.
In order to achieve the above object, the present invention provides Mn2O3The preparation method of the @ N doped porous carbon hybrid Fenton material has the following characteristics: the method comprises the following steps: step one, adding manganese nitrate hexahydrate, trimesic acid and 2,2' -bipyridine into a mixed solution of N, N-dimethylformamide and ethanol, and stirring; step two, transferring the mixture obtained in the step one into a polytetrafluoroethylene lining high-pressure kettle, and carrying out closed hydrothermal reaction to obtain a Mn-MOF solid substance; step three, washing the Mn-MOF solid substance obtained in the step two and then drying; and step four, calcining the dried Mn-MOF solid substance in a muffle furnace to obtain the Fenton catalytic material.
Further, the present invention provides a Mn2O3The preparation method of the @ N doped porous carbon hybrid Fenton material can also have the following characteristics: in the first step, 2.51g of manganese nitrate hexahydrate, 0.3-1.2g of trimesic acid and 0.45-1.5g of 2,2' -bipyridyl are added into 40-100mL of a mixed solution of N, N-dimethylformamide and ethanol; the volume ratio of the N, N-dimethylformamide to the ethanol is 1: 1.
Further, the present invention provides a Mn2O3The preparation method of the @ N doped porous carbon hybrid Fenton material can also have the following characteristics: wherein, the first step adopts magnetic stirring, the stirring speed is 100-200r/min, and the stirring time is 3-12 h.
Further, the present invention provides a Mn2O3The preparation method of the @ N doped porous carbon hybrid Fenton material can also have the following characteristics: wherein, in the second step, the reaction temperature of the hydrothermal reaction is 120-220 ℃, and the reaction time is 15-25 h.
Further, the present invention provides a Mn2O3@ N doping of porous carbon hybrid Fenton-like materialThe preparation method can also have the following characteristics: in the third step, the Mn-MOF solid matter is washed three times by ethanol and water.
Further, the present invention provides a Mn2O3The preparation method of the @ N doped porous carbon hybrid Fenton material can also have the following characteristics: wherein, in the third step, the drying temperature is 60-100 ℃.
Further, the present invention provides a Mn2O3The preparation method of the @ N doped porous carbon hybrid Fenton material can also have the following characteristics: wherein, in the fourth step, the temperature rising rate of the calcination in the muffle furnace is 5-10 ℃, the calcination temperature is 400-600 ℃, and the calcination time is 2-6 h.
The invention also provides Mn2O3The @ N doped porous carbon hybrid Fenton material is prepared by the preparation method, and the structural formula of the Fenton material is Mn2O3-Cx-NyAnd x and y respectively represent the addition amounts of trimesic acid and 2,2' -bipyridine.
The invention also provides Mn2O3The application of the @ N doped porous carbon hybrid Fenton material and PMS in water combined treatment and degradation of organic pollutants.
Further, the present invention provides a Mn2O3The application of the @ N doped porous carbon hybrid Fenton-like material can also have the following characteristics: the organic pollutant is any one of rhodamine B, bisphenol A and methyl orange.
Fenton catalytic material based on superfine nano Mn2O3The basic structure of the core-shell structure of the inorganic carbon containing nitrogen is Mn2O3And (3) as a substrate, generating a nitrogen-containing carbon layer on the surface of the substrate through carbonizing the MOFs structure to form a core-shell structure material, wherein the thickness of the surface carbon layer is about 5-10 nm. According to the nitrogen adsorption and desorption isotherm and the pore size distribution diagram, the synthetic Fenton-like catalyst mainly has a mesoporous structure. The MOFs-derived carbon shell increases the BET specific surface area and pore volume of the catalyst, thereby promoting interfacial reactions and mass transfer processes. The catalytic material can be used for catalyzing and degrading phenolic pollutants due to the formation of the porous nitrogen-containing carbon layer on the surfaceRealizing the synergistic effect of the double reaction active centers and the free radical conversion mechanism.
The method obtains Mn with the surface wrapped with a nitrogen-containing carbon layer by carbonizing MOFs precursor2O3A fenton-like catalyst. Ultra-fine Mn2O3The nano-catalyst is generated in situ and uniformly dispersed in carbon meshes derived from N-doped MOFs, so that the stability of the nano-catalyst is improved. Unlike the classical Fenton reaction, Mn2O3The cation-pi interaction and Mn-N coordination in the @ N doped porous carbon hybrid lead to the formation of double reaction centers, promote the transfer of electrons from the electron-rich Mn center to PMS, and generate a large number of free radicals. More importantly, a large number of free radicals recombine under nano-constraints to produce1O2For degrading organic substances. In addition, Mn-N complexation can reduce the adsorption energy on the surface of the catalyst, enhance the adsorption of PMS and is also beneficial to electron transfer. Thus, the activation and utilization of PMS is significantly improved even at low doses. The invention not only synthesizes a high-efficiency Fenton-like double reaction center catalyst, but also provides a new method for degrading organic matters under low-dose PMS.
The invention has the beneficial effects that:
first, MOFs preparation of ultra-fine Mn2O3The nano particles not only prevent the occurrence of agglomeration phenomenon, but also have ultrahigh activity, and in addition, the generated cubic crystal form Mn2O3Exposing more active sites.
And secondly, the nitrogen atom-doped carbon layer structure and metal generate double reaction active centers through the action of cation N bonds and metal-N bonds, so that the speed-limiting step in the traditional Fenton-like reaction is avoided, the ineffective decomposition of hydrogen peroxide is avoided, and the catalytic activity of the catalyst is improved.
III, superfine Mn2O3The ultra-strong activity of the nano-particles is cooperated with double reactions to generate a large amount of free radicals, and the free radicals are compounded in a nitrogen atom doped carbon layer structure to generate singlet oxygen with strong electrophilic action1O2And the degradation catalytic effect of BPA is improved.
And fourthly, the nitrogen atom-doped carbon layer structure provides PMS and BPA adsorption sites, the reaction is carried out on the surface of the catalyst, the migration distance of free radicals is reduced, and the utilization rate of the free radicals is improved, so that the catalytic degradation effect and the utilization rate of PMS are greatly improved.
Drawings
FIG. 1 is Mn as a product of example 32O3-C0.9-N1.2And Mn2O3And Mn2O3-C0.9Scanning electron microscope images and transmission electron microscope images of;
FIG. 2 is Mn as a product of example 32O3-C0.9-N1.2And Mn2O3And Mn2O3-C0.9N of (A)2Adsorption and desorption curves and pore size distribution maps;
FIG. 3A is Mn as a product of example 32O3-C0.9-N1.2And Mn3O4、Mn2O3Mn-MOF and Mn2O3-C0.9An XRD pattern of (a);
FIG. 3B is Mn as a product of example 32O3-C0.9-N1.2And Mn2O3(ii) a Raman spectrogram;
FIG. 3C is Mn as a product of example 32O3-C0.9-N1.2And Mn-MOF and Mn2O3-C0.9Etc. infrared spectrograms;
FIG. 3D is Mn as a product of example 32O3-C0.9-N1.2And Mn3O4、Mn2O3And Mn2O3-C0.9An EIS map of (a);
FIG. 4 is Mn as a product of example 32O3-C0.9-N1.2C, O and XPS spectra for N with Mn-MOF;
FIG. 5 shows Mn as a product of examples 1 to 42O3-Cx-NyFIG. (BPA 20ppm, Rh B10 ppm);
FIGS. 6A and B are Mn, respectively, for the product of example 32O3-C0.9-N1.2And Mn2O3TOC and PMS utilization maps of;
FIGS. 7A and B are Mn, respectively2O3And Mn as a product of example 32O3-C0.9-N1.2A cycle test result chart of (1);
FIG. 7C is Mn as a product of example 32O3-C0.9-N1.2And Mn2O3The metal leaching experiment result chart of (1);
FIG. 7D is product Mn2O3-C0.9-N1.2The structure of (1);
FIG. 8 shows Mn as a product2O3-C0.9-N1.2The catalytic mechanism diagram of (1).
Detailed Description
The present invention is further illustrated by the following specific examples.
Example 1
This example provides a Mn2O3A preparation method and application of the @ N doped porous carbon hybrid Fenton material.
The preparation method comprises the following steps:
step one, adding 2.51g of manganese nitrate hexahydrate, 0.9g of trimesic acid and 0.45g of 2,2' -bipyridyl into a mixed solution of 30mL of N, N-Dimethylformamide (DMF) and 30mL of ethanol, and magnetically stirring for 6h at the stirring speed of 100-200 r/min.
And step two, transferring the mixture obtained in the step one into a polytetrafluoroethylene lining high-pressure kettle, heating at 180 ℃ for 18h, and carrying out closed hydrothermal reaction to obtain a Mn-MOF solid substance.
And step three, washing the Mn-MOF solid substance obtained in the step two with ethanol and water for three times, and drying at 80 ℃.
And step four, calcining the dried Mn-MOF solid substance in a muffle furnace, wherein the temperature rising rate of the calcination is 5-10 ℃, the calcination temperature is 500 ℃, and the calcination time is 4 hours, so as to finally obtain the Fenton catalytic material.
The product Fenton material and PMS are combined in water to form a Fenton-like system which is used for treating and degrading organic pollutants in water. Organic pollutant bagIncluding rhodamine B, bisphenol a or methyl orange. This example gives Mn as a product2O3-C0.9-N0.45The treatment of bisphenol A in degraded water, in combination with PMS in water, is shown in FIG. 5.
Example 2
This example provides a Mn2O3A preparation method and application of the @ N doped porous carbon hybrid Fenton material.
The preparation method comprises the following steps:
step one, adding 2.51g of manganese nitrate hexahydrate, 0.9g of trimesic acid and 0.9g of 2,2' -bipyridyl into a mixed solution of 30mL of N, N-Dimethylformamide (DMF) and 30mL of ethanol, and magnetically stirring for 6h at the stirring speed of 100-200 r/min.
And step two, transferring the mixture obtained in the step one into a polytetrafluoroethylene lining high-pressure kettle, heating at 180 ℃ for 18h, and carrying out closed hydrothermal reaction to obtain a Mn-MOF solid substance.
And step three, washing the Mn-MOF solid substance obtained in the step two with ethanol and water for three times, and drying at 80 ℃.
And step four, calcining the dried Mn-MOF solid substance in a muffle furnace, wherein the temperature rise rate of the calcination is 5-10 ℃, the calcination temperature is 500 ℃, and the calcination time is 4 hours, so as to finally obtain the Fenton-like catalytic material.
The product Fenton material and PMS are combined in water to form a Fenton-like system which is used for treating and degrading organic pollutants in water. The organic pollutants comprise rhodamine B, bisphenol A or methyl orange. This example gives Mn as a product2O3-C0.9-N0.9The treatment of bisphenol A in degraded water, in combination with PMS in water, is shown in FIG. 5.
Example 3
This example provides a Mn2O3A preparation method and application of the @ N doped porous carbon hybrid Fenton material.
The preparation method comprises the following steps:
step one, adding 2.51g of manganese nitrate hexahydrate, 0.9g of trimesic acid and 1.2g of 2,2' -bipyridyl into a mixed solution of 30mL of N, N-Dimethylformamide (DMF) and 30mL of ethanol, and magnetically stirring for 6h at the stirring speed of 100-200 r/min.
And step two, transferring the mixture obtained in the step one into a polytetrafluoroethylene lining high-pressure kettle, heating at 180 ℃ for 18h, and carrying out closed hydrothermal reaction to obtain a Mn-MOF solid substance.
And step three, washing the Mn-MOF solid substance obtained in the step two with ethanol and water for three times, and drying at 80 ℃.
And step four, calcining the dried Mn-MOF solid substance in a muffle furnace, wherein the temperature rise rate of the calcination is 5-10 ℃, the calcination temperature is 500 ℃, and the calcination time is 4 hours, so as to finally obtain the Fenton-like catalytic material.
The product was characterized as follows:
for product Mn2O3-C0.9-N1.2And Mn2O3And Mn2O3-C0.9(the amount of trimesic acid added was 0.9g and the amount of 2,2' -bipyridine added was 0, as in the preparation method of this example) were evaluated by scanning electron microscopy and transmission electron microscopy, and the results are shown in FIG. 1. As can be seen from FIG. 1, pure Mn2O3Surface densification, while Mn2O3-C0.9-N1.2Is in a porous structure. As can be observed in transmission electron microscope images, pure Mn2O3Which are heavily agglomerated due to their relatively high surface energy. In contrast, ultra-fine Mn2O3The nanoparticles are uniformly dispersed in Mn2O3-Cx-NyIn (1). Mn2O3This strong dispersibility of the nanoparticles can be explained by: during the synthesis, Mn is chelated by ligands (trimesic acid and 2,2' bipyridine) in the MOFs (Mn-MOFs-Ta-Bd). After calcination, a carbon shell is formed on the surface, and the aggregation of the nano manganese dioxide is prevented. Mn having a core-shell structure can be clearly observed in HRTEM images2O3-Cx-NyCarbon shell coated cubic Mn2O3And (4) a core. The lattice fringes (0.27nm) also confirm the cubic phase Mn2O3The (222) plane of (1).
For product Mn2O3-C0.9-N1.2And Mn2O3And Mn2O3-C0.9Carry out N2Adsorption and desorption curves and pore size distribution were measured to analyze the pore structure of the catalyst, and the results are shown in fig. 2. From the results in FIG. 2, it can be seen that the catalyst belongs to the type IV isotherm with the hysteresis curve of H3. The MOFs-derived carbon shell increases the BET specific surface area and pore volume of the catalyst, thereby promoting interfacial reactions and mass transfer processes.
For product Mn2O3-C0.9-N1.2And Mn3O4、Mn2O3Mn-MOF and Mn2O3-C0.9XRD characterization was performed, and the results are shown in FIG. 3A. As can be seen, the most typical diffraction peaks of Mn-MOFs before calcination are associated with pure Mn3O4The standard patterns of (A) are consistent, and the intensity is relatively weak due to low crystallinity. After calcination, Mn2O3-C0.9And Mn2O3-C0.9-N1.2Typical diffraction peak of (2) and pure Mn2O3Has consistent standard diffraction peak and is due to the formation of ultra-fine Mn2O3The strength of the crystal is obviously improved.
For product Mn2O3-C0.9-N1.2And Mn2O3Raman spectroscopy characterization was performed and the results are shown in fig. 3B. Raman spectroscopy can provide crystallographic information of the carbon skeleton. Mn2O3-C0.9-N1.21360cm-1And 1590cm-1The nearby characteristic peaks represent the defect density and crystallinity of SP2 carbon, respectively, confirming the presence of a carbon shell layer.
For product Mn2O3-C0.9-N1.2And Mn-MOF and Mn2O3-C0.9Etc. were subjected to infrared testing, the results are shown in fig. 3C. The FT-IR spectrum identifies the components of the nanocomposite. 1576cm for Mn-MOFs-1And 1670cm-1The two characteristic peaks at (a) are respectively due to stretching of the C ═ N bond in 2,2' -bipyridine and C ═ O vibration of the carboxyl group in trimesic acid, indicating the formation of metal-organic chelates.After calcination, these polar group peaks (C ═ N, C ═ O) disappeared, while Mn was observed2O3(665, 572 and 524cm-1) Mn-O-Mn peak of (1). The reduction of the number of polar groups on the surface of the catalyst can enhance the pi-pi interaction between the surface carbon layer and BPA, thereby accelerating the electron transfer in a reaction system.
For product Mn2O3-C0.9-N1.2And Mn3O4、Mn2O3And Mn2O3-C0.9EIS characterization was performed and the results are shown in FIG. 3D. As can be seen, the Nyquist diameter follows Mn3O4>Mn2O3>Mn2O3-C0.9>Mn2O3-C0.9-N1.2Indicates Mn2O3The highest charge transfer rate is achieved by-C-N. In one aspect, Mn2O3The carbon shell of-C-N 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 the carbon atoms, resulting in Mn2O3-C0.9-N1.2The conductivity of (a) is enhanced to form a so-called "active region".
For product Mn2O3-C0.9-N1.2XPS characterization with Mn-MOF showed the results in FIG. 4. Characteristic peaks are seen at 284.6eV,285.5eV and 289.0eV representing C-C/C-C, C-O/C-N and C-O/C-N, respectively. The three fitted peaks for oxygen represent O-Mn (529.8eV), O ═ C (531.7eV) and O-C (533.2eV), respectively, indicating the presence of carboxyl functionality on the Mn-MOFs surface. Mn in comparison with Mn-MOFs2O3-C0.9-N1.2The peaks of medium C-O and C ═ O are weaker because most of the functional groups are removed during calcination. Further, Mn2O3-C0.9-N1.2The N peak in (b) can also be fit to three peaks: 397.5eV (pyridine N), 400.2eV (Mn-N), and 403.8eV (nitrile oxide). Notably, doping the carbon shell with N may enhance electron transfer because N has a smaller atomic diameter and a stronger electronegativity than C. At the same time, the coordinating pyridine nitrogen mayCan further enhance polarization difference and promote the formation of double reaction centers.
Application of Fenton material:
the product Fenton material and PMS are combined in water to form a Fenton-like system which is used for treating and degrading organic pollutants in water. The organic pollutants comprise rhodamine B, bisphenol A or methyl orange. This example gives Mn as a product2O3-C0.9-N1.2The treatment of bisphenol A in degraded water, in combination with PMS in water, is shown in FIG. 5.
Evaluation of the different catalysts with TOC removal (product Mn)2O3-C0.9-N1.2And Mn2O3) The results are shown in FIG. 6. As can be seen from the figure, Mn2O3-C0.9-N1.2The TOC removal rate of the catalyst is far higher than that of Mn2O3. Further, Mn2O3And Mn2O3-C0.9-N1.2The utilization rate (eta) of the PMS shows different change trends along with the change of the reaction time. For Mn2O3The suspension, BPA mineralization rate was slower than PMS consumption rate, resulting in low utilization at the initial stage of the reaction. Along with the extension of the reaction time (2-8 min), the bisphenol A intermediate can be completely mineralized by free radicals, and the utilization rate of PMS is improved. However, due to Mn2O3Most of Mn (III) in the suspension is converted into Mn (IV), the activation rate of PMS is slowed down again, and eta is gradually reduced after 8 min.
Mn2O3-C0.9-N1.2Very high PMS utilization was obtained at the beginning of the reaction, indicating that it is a non-radical reaction (1O2). In general terms, the amount of the solvent to be used,1O2can be produced by a free radical chain reaction. In Mn2O3-C0.9-N1.2In the composite material, the electron-rich Mn center can provide electrons for PMS activation. Due to the synergistic effect of double reaction centers and the superfine Mn2O3The very high activity of (2) instantaneously generates a large amount of free radicals. In addition, the N-doped carbon shell can promote the electron transfer of an organic intermediate group to an electron-rich Mn center through C-O-Mn and C-N-Mn bonds,thereby promoting the oxidation reduction of Mn and avoiding the ineffective decomposition of PMS. More importantly, the porous structure of the N-doped carbon shell not only promotes the compound generation of free radicals1O2And provides a large number of adsorption sites for PMS and BPA.1O2Has high electrophilicity, and can selectively attack electron-rich functional groups and some unsaturated compounds (BPA and the like). Thus, Mn is present as the reaction time is prolonged2O3the-C-N can also obtain higher PMS utilization rate under the condition of extremely low dose PMS.
The stability of the catalyst after the reaction was characterized as shown in FIGS. 7A-C. Mn, as shown in FIGS. 7A and B2O3-C0.9-N1.2Exhibits specific Mn in terms of PMS activation2O3Higher catalytic stability. BPA vs Mn after 5 consecutive trials2O3The degradation rate of (C) decreased from 44% to 19% (FIG. 7A), while Mn2O3-C0.9-N1.2The BPA removal rate remained above 97% within 16min after 5 consecutive trials.
Mn, as shown in FIG. 7C2O3The leaching amount of-C-N (0.52mg/L) is far lower than that of Mn2O3(1.77 mg/L). Mn2O3-C0.9-N1.2This improvement in stability can be explained as: (1) the double reaction centers not only avoid the accumulation of high-valence manganese, but also prevent the ineffective decomposition of PMS; (2) the N-doped carbon shell is an effective protective layer against Mn leaching.
The catalysis principle is as follows: mn from MOFs, as shown in FIG. 82O3the-Cx-Ny nano doped porous carbon hybrid Fenton catalyst has the advantages that the cation pi bond and Mn-N complexation cause the formation of an electron-rich Mn center, and electrons are provided for the activation of PMS. Therefore, a large amount of O2Can be generated by a free radical chain reaction. Notably, the porous structure of the N-doped carbon shell not only promotes free radicals (O)2Complex formation of-,. OH)1O2But also provides adsorption sites for organic matters, and shortens1O2The migration distance of (c). On the other hand, the N-doped carbon shell serves as an electron-deficient center through C-O-MThe N and C-N-Mn bonds promote electron transfer of R to the electron-rich Mn center and promote reduction of Mn (IV) to Mn (III)/Mn (II). High adsorption capacity of N-doped carbon shell due to synergistic effect of double reaction centers1O2、Mn2O3-Cx-NyThe strong oxidizing ability of the composite oxide can also obviously improve the utilization rate of PMS and the mineralization of organic matters even under the condition of low dosage of PMS (0.033 g/L).
Example 4
This example provides a Mn2O3A preparation method and application of the @ N doped porous carbon hybrid Fenton material.
The preparation method comprises the following steps:
step one, adding 2.51g of manganese nitrate hexahydrate, 0.9g of trimesic acid and 1.5g of 2,2' -bipyridyl into a mixed solution of 30mL of N, N-Dimethylformamide (DMF) and 30mL of ethanol, and magnetically stirring for 6h at the stirring speed of 100-200 r/min.
And step two, transferring the mixture obtained in the step one into a polytetrafluoroethylene lining high-pressure kettle, heating at 180 ℃ for 18h, and carrying out closed hydrothermal reaction to obtain a Mn-MOF solid substance.
And step three, washing the Mn-MOF solid substance obtained in the step two with ethanol and water for three times, and drying at 80 ℃.
And step four, calcining the dried Mn-MOF solid substance in a muffle furnace, wherein the temperature rise rate of the calcination is 5-10 ℃, the calcination temperature is 500 ℃, and the calcination time is 4 hours, so as to finally obtain the Fenton-like catalytic material.
The product Fenton material and PMS are combined in water to form a Fenton-like system which is used for treating and degrading organic pollutants in water. The organic pollutants comprise rhodamine B, bisphenol A or methyl orange. This example gives Mn as a product2O3-C0.9-N1.5The treatment of bisphenol A in degraded water, in combination with PMS in water, is shown in FIG. 5.
The activation performance of each catalyst (products of examples 1 to 4) on PMS was evaluated by a degradation test on bisphenol A, as shown in FIG. 5, Mn2O3-CX(x ═ 0.3, 0.6, 0.9, 1.2) shows better than pure Mn2O3And Mn3O4Higher catalytic activity. BPA vs Mn2O3-CXThe removal rate of (B) is Mn in order2O3-C0.9>Mn2O3-C0.6>Mn2O3-C1.2> Mn2O3-C0.3. Within 16min, Mn (Ta) can degrade about 93% of the BPA. Excessive addition of Ta during synthesis can form an excessively thick carbon shell layer in step 2, which may adversely affect the reaction of PMS with Mn2O 3. Thus, in Mn2O3-CXIn the synthesis process of (3), 0.9g of TA is used as the optimum amount.
With Mn2O3-C0.9In contrast, Mn2O3-C0.9-NyThe catalytic activity was significantly improved when (y) was 0.45, 0.9, 1.2, and 1.5. The doping of N in the carbon shell not only promotes the electron transfer and enhances the double reaction centers, but also enhances the adsorption of BPA and PMS and shortens the migration distance of BPA and PMS. Mn2O3-C0.9-NyHas the catalytic properties of Mn2O3-C0.9-N1.2>Mn2O3-C0.9-N1.5>Mn2O3-C0.9-N0.9>Mn2O3-C0.9-N0.45. For Mn2O3-C0.9-N1.2In addition, 20mg/L of bisphenol A was completely degraded within 4min (PMS ═ 0.1g/L), and good catalytic activity was exhibited. Therefore, Mn is selected2O3-C0.9-N1.2As the best catalyst for further study. Generally, the organic material is present in a relatively large amount of PMS (A), (B), (C) and a) and C) and a) and D) in a)>1g/L) of the catalyst is easily degraded in a Fenton-like system. In the present application, BPA is present in Mn at a low dose of PMS (0.1g/L)2O3-C0.9-N1.2Also effectively degraded, showing Mn2O3-C0.9-N1.2Excellent catalytic activity. In addition, Mn was further reduced from 0.1g/L to 0.033g/L with PMS dosage2O3-C0.9-N1.2BPA was still completely removed within 16 minutes.
Example 5
This example provides a Mn2O3The preparation method of the @ N doped porous carbon hybrid Fenton material comprises the following steps:
step one, adding 2.51g of manganese nitrate hexahydrate, 0.9g of trimesic acid and 1.5g of 2,2' -bipyridyl into a mixed solution of 30mL of N, N-Dimethylformamide (DMF) and 30mL of ethanol, and magnetically stirring for 6h at the stirring speed of 100-200 r/min.
And step two, transferring the mixture obtained in the step one into a polytetrafluoroethylene lining high-pressure kettle, heating at 180 ℃ for 18h, and carrying out closed hydrothermal reaction to obtain a Mn-MOF solid substance.
And step three, washing the Mn-MOF solid substance obtained in the step two with ethanol and water for three times, and drying at 80 ℃.
And step four, calcining the dried Mn-MOF solid substance in a muffle furnace, wherein the temperature rise rate of the calcination is 5-10 ℃, the calcination temperature is 450 ℃, and the calcination time is 4h, so as to finally obtain the Fenton-like catalytic material.
Example 6
This example provides a Mn2O3The preparation method of the @ N doped porous carbon hybrid Fenton material comprises the following steps:
step one, adding 2.51g of manganese nitrate hexahydrate, 0.9g of trimesic acid and 1.5g of 2,2' -bipyridyl into a mixed solution of 30mL of N, N-Dimethylformamide (DMF) and 30mL of ethanol, and magnetically stirring for 6h at the stirring speed of 100-200 r/min.
And step two, transferring the mixture obtained in the step one into a polytetrafluoroethylene lining high-pressure kettle, heating at 180 ℃ for 18h, and carrying out closed hydrothermal reaction to obtain a Mn-MOF solid substance.
And step three, washing the Mn-MOF solid substance obtained in the step two with ethanol and water for three times, and drying at 80 ℃.
And step four, calcining the dried Mn-MOF solid substance in a muffle furnace, wherein the temperature rise rate of the calcination is 5-10 ℃, the calcination temperature is 600 ℃, and the calcination time is 4 hours, so as to finally obtain the Fenton-like catalytic material.
Example 7
This example provides a Mn2O3The preparation method of the @ N doped porous carbon hybrid Fenton material comprises the following steps:
step one, adding 2.51g of manganese nitrate hexahydrate, 0.9g of trimesic acid and 1.5g of 2,2' -bipyridyl into a mixed solution of 30mL of N, N-Dimethylformamide (DMF) and 30mL of ethanol, and magnetically stirring for 6h at the stirring speed of 100-200 r/min.
And step two, transferring the mixture obtained in the step one into a polytetrafluoroethylene lining high-pressure kettle, heating at 180 ℃ for 18h, and carrying out closed hydrothermal reaction to obtain a Mn-MOF solid substance.
And step three, washing the Mn-MOF solid substance obtained in the step two with ethanol and water for three times, and drying at 80 ℃.
And step four, calcining the dried Mn-MOF solid substance in a muffle furnace, wherein the temperature rise rate of the calcination is 5-10 ℃, the calcination temperature is 500 ℃, and the calcination time is 2 hours, so as to finally obtain the Fenton-like catalytic material.
Example 8
This example provides a Mn2O3The preparation method of the @ N doped porous carbon hybrid Fenton material comprises the following steps:
step one, adding 2.51g of manganese nitrate hexahydrate, 0.9g of trimesic acid and 1.5g of 2,2' -bipyridyl into a mixed solution of 30mL of N, N-Dimethylformamide (DMF) and 30mL of ethanol, and magnetically stirring for 6h at the stirring speed of 100-200 r/min.
And step two, transferring the mixture obtained in the step one into a polytetrafluoroethylene lining high-pressure kettle, heating at 180 ℃ for 18h, and carrying out closed hydrothermal reaction to obtain a Mn-MOF solid substance.
And step three, washing the Mn-MOF solid substance obtained in the step two with ethanol and water for three times, and drying at 80 ℃.
And step four, calcining the dried Mn-MOF solid substance in a muffle furnace, wherein the temperature rise rate of the calcination is 5-10 ℃, the calcination temperature is 500 ℃, and the calcination time is 6 hours, so as to finally obtain the Fenton-like catalytic material.
Example 9
The present embodiment providesMn (manganese)2O3The preparation method of the @ N doped porous carbon hybrid Fenton material comprises the following steps:
step one, adding 2.51g of manganese nitrate hexahydrate, 0.9g of trimesic acid and 1.5g of 2,2' -bipyridyl into a mixed solution of 30mL of N, N-Dimethylformamide (DMF) and 30mL of ethanol, and magnetically stirring for 6h at the stirring speed of 100-200 r/min.
And step two, transferring the mixture obtained in the step one into a polytetrafluoroethylene lining high-pressure kettle, heating at 150 ℃ for 18h, and carrying out closed hydrothermal reaction to obtain a Mn-MOF solid substance.
And step three, washing the Mn-MOF solid substance obtained in the step two with ethanol and water for three times, and drying at 80 ℃.
And step four, calcining the dried Mn-MOF solid substance in a muffle furnace, wherein the temperature rise rate of the calcination is 5-10 ℃, the calcination temperature is 500 ℃, and the calcination time is 4 hours, so as to finally obtain the Fenton-like catalytic material.
Example 10
This example provides a Mn2O3The preparation method of the @ N doped porous carbon hybrid Fenton material comprises the following steps:
step one, adding 2.51g of manganese nitrate hexahydrate, 0.9g of trimesic acid and 1.5g of 2,2' -bipyridyl into a mixed solution of 30mL of N, N-Dimethylformamide (DMF) and 30mL of ethanol, and magnetically stirring for 6h at the stirring speed of 100-200 r/min.
And step two, transferring the mixture obtained in the step one into a polytetrafluoroethylene lining high-pressure kettle, heating at 200 ℃ for 18h, and carrying out closed hydrothermal reaction to obtain a Mn-MOF solid substance.
And step three, washing the Mn-MOF solid substance obtained in the step two with ethanol and water for three times, and drying at 80 ℃.
And step four, calcining the dried Mn-MOF solid substance in a muffle furnace, wherein the temperature rise rate of the calcination is 5-10 ℃, the calcination temperature is 500 ℃, and the calcination time is 4 hours, so as to finally obtain the Fenton-like catalytic material.
Example 11
This example provides a Mn2O3@ N doped polyThe preparation method of the porous carbon hybrid Fenton-like material comprises the following steps of:
step one, adding 2.51g of manganese nitrate hexahydrate, 0.3g of trimesic acid and 1.2g of 2,2' -bipyridyl into a mixed solution of 30mL of N, N-Dimethylformamide (DMF) and 30mL of ethanol, and magnetically stirring for 3h at the stirring speed of 100-200 r/min.
And step two, transferring the mixture obtained in the step one into a polytetrafluoroethylene lining high-pressure kettle, heating at 120 ℃ for 25 hours, and carrying out closed hydrothermal reaction to obtain a Mn-MOF solid substance.
And step three, washing the Mn-MOF solid substance obtained in the step two with ethanol and water for three times, and drying at 60 ℃.
And step four, calcining the dried Mn-MOF solid substance in a muffle furnace, wherein the temperature rise rate of the calcination is 5-10 ℃, the calcination temperature is 400 ℃, and the calcination time is 4 hours, so as to finally obtain the Fenton-like catalytic material.
Example 12
This example provides a Mn2O3The preparation method of the @ N doped porous carbon hybrid Fenton material comprises the following steps:
step one, adding 2.51g of manganese nitrate hexahydrate, 1.2g of trimesic acid and 1.2g of 2,2' -bipyridyl into a mixed solution of 30mL of N, N-Dimethylformamide (DMF) and 30mL of ethanol, and magnetically stirring for 12h at the stirring speed of 100-200 r/min.
And step two, transferring the mixture obtained in the step one into a polytetrafluoroethylene lining high-pressure kettle, heating for 15 hours at 220 ℃ and carrying out closed hydrothermal reaction to obtain a Mn-MOF solid substance.
And step three, washing the Mn-MOF solid substance obtained in the step two with ethanol and water for three times, and drying at 100 ℃.
And step four, calcining the dried Mn-MOF solid substance in a muffle furnace, wherein the temperature rise rate of the calcination is 5-10 ℃, the calcination temperature is 500 ℃, and the calcination time is 4 hours, so as to finally obtain the Fenton-like catalytic material.
Claims (8)
1. Mn (manganese)2O3A preparation method of @ N doped porous carbon hybrid Fenton material,the method is characterized in that:
the method comprises the following steps:
step one, adding manganese nitrate hexahydrate, trimesic acid and 2,2' -bipyridine into a mixed solution of N, N-dimethylformamide and ethanol, and stirring;
step two, transferring the mixture obtained in the step one into a polytetrafluoroethylene lining high-pressure kettle, and carrying out closed hydrothermal reaction to obtain a Mn-MOF solid substance;
step three, washing the Mn-MOF solid substance obtained in the step two and then drying;
step four, calcining the dried Mn-MOF solid substance in a muffle furnace to obtain a Fenton catalytic material; the heating rate of the muffle furnace for calcination is 5-10 ℃, the calcination temperature is 400-600 ℃, and the calcination time is 2-6 h;
preparation of the obtained Mn2O3The application of the @ N doped porous carbon hybrid Fenton material and PMS in water combined treatment and degradation of organic pollutants.
2. Mn according to claim 12O3The preparation method of the @ N doped porous carbon hybrid Fenton material is characterized by comprising the following steps of:
in the first step, 2.51g of manganese nitrate hexahydrate, 0.3-1.2g of trimesic acid and 0.45-1.5g of 2,2' -bipyridyl are added into 40-100mL of a mixed solution of N, N-dimethylformamide and ethanol;
the volume ratio of the N, N-dimethylformamide to the ethanol is 1: 1.
3. Mn according to claim 12O3The preparation method of the @ N doped porous carbon hybrid Fenton material is characterized by comprising the following steps of:
wherein, the first step adopts magnetic stirring, the stirring speed is 100-200r/min, and the stirring time is 3-12 h.
4. Mn according to claim 12O3The preparation method of the @ N doped porous carbon hybrid Fenton material is characterized by comprising the following steps of:
wherein, in the second step, the reaction temperature of the hydrothermal reaction is 120-220 ℃, and the reaction time is 15-25 h.
5. Mn according to claim 12O3The preparation method of the @ N doped porous carbon hybrid Fenton material is characterized by comprising the following steps of:
in the third step, the Mn-MOF solid matter is washed three times by ethanol and water.
6. Mn according to claim 12O3The preparation method of the @ N doped porous carbon hybrid Fenton material is characterized by comprising the following steps of:
wherein, in the third step, the drying temperature is 60-100 ℃.
7. Mn (manganese)2O3The @ N doped porous carbon hybrid Fenton material is characterized in that: the method of any one of claims 1 to 6, wherein the Fenton material has the formula Mn2O3-Cx-NyAnd x and y respectively represent the addition amounts of trimesic acid and 2,2' -bipyridine.
8. Mn according to claim 72O3Application of @ N doped porous carbon hybrid Fenton material is characterized in that:
the organic pollutant is any one of rhodamine B, bisphenol A and methyl orange.
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