CN117427681A - Carbon-supported manganese oxide/manganese carbide composite catalyst and preparation method and application thereof - Google Patents
Carbon-supported manganese oxide/manganese carbide composite catalyst and preparation method and application thereof Download PDFInfo
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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 title claims abstract description 351
- 239000011572 manganese Substances 0.000 title claims abstract description 134
- 239000003054 catalyst Substances 0.000 title claims abstract description 120
- 239000002131 composite material Substances 0.000 title claims abstract description 88
- 229910052748 manganese Inorganic materials 0.000 title claims abstract description 84
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 title claims abstract description 83
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 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 abstract description 53
- 229940043267 rhodamine b Drugs 0.000 claims abstract description 53
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 42
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 40
- FHHJDRFHHWUPDG-UHFFFAOYSA-L peroxysulfate(2-) Chemical compound [O-]OS([O-])(=O)=O FHHJDRFHHWUPDG-UHFFFAOYSA-L 0.000 claims abstract description 36
- 239000002957 persistent organic pollutant Substances 0.000 claims abstract description 28
- 239000000243 solution Substances 0.000 claims abstract description 23
- LENZDBCJOHFCAS-UHFFFAOYSA-N tris Chemical compound OCC(N)(CO)CO LENZDBCJOHFCAS-UHFFFAOYSA-N 0.000 claims abstract description 17
- CTENFNNZBMHDDG-UHFFFAOYSA-N Dopamine hydrochloride Chemical compound Cl.NCCC1=CC=C(O)C(O)=C1 CTENFNNZBMHDDG-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229960001149 dopamine hydrochloride Drugs 0.000 claims abstract description 16
- 239000007983 Tris buffer Substances 0.000 claims abstract description 11
- 238000001354 calcination Methods 0.000 claims abstract description 10
- 229910001437 manganese ion Inorganic materials 0.000 claims abstract description 10
- WAEMQWOKJMHJLA-UHFFFAOYSA-N Manganese(2+) Chemical compound [Mn+2] WAEMQWOKJMHJLA-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000003756 stirring Methods 0.000 claims abstract description 7
- 239000012299 nitrogen atmosphere Substances 0.000 claims abstract description 5
- 238000001035 drying Methods 0.000 claims abstract description 4
- 239000002105 nanoparticle Substances 0.000 claims abstract description 4
- 239000000975 dye Substances 0.000 claims description 21
- 239000002351 wastewater Substances 0.000 claims description 19
- 238000002474 experimental method Methods 0.000 claims description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 230000004913 activation Effects 0.000 claims description 10
- CNFDGXZLMLFIJV-UHFFFAOYSA-L manganese(II) chloride tetrahydrate Chemical compound O.O.O.O.[Cl-].[Cl-].[Mn+2] CNFDGXZLMLFIJV-UHFFFAOYSA-L 0.000 claims description 9
- 239000000463 material Substances 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 7
- 239000012190 activator Substances 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 6
- 239000002243 precursor Substances 0.000 claims description 6
- 238000005303 weighing Methods 0.000 claims description 6
- 239000000356 contaminant Substances 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 4
- 229910021641 deionized water Inorganic materials 0.000 claims description 4
- 239000000843 powder Substances 0.000 claims description 4
- 239000008187 granular material Substances 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract description 16
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 9
- 230000003197 catalytic effect Effects 0.000 abstract description 7
- 230000003213 activating effect Effects 0.000 abstract description 6
- 238000004064 recycling Methods 0.000 abstract description 5
- 238000010923 batch production Methods 0.000 abstract description 2
- 238000001308 synthesis method Methods 0.000 abstract description 2
- 238000005265 energy consumption Methods 0.000 abstract 1
- 239000002994 raw material Substances 0.000 abstract 1
- 229910000314 transition metal oxide Inorganic materials 0.000 abstract 1
- 238000006731 degradation reaction Methods 0.000 description 54
- 230000015556 catabolic process Effects 0.000 description 41
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 18
- XPFVYQJUAUNWIW-UHFFFAOYSA-N furfuryl alcohol Chemical compound OCC1=CC=CO1 XPFVYQJUAUNWIW-UHFFFAOYSA-N 0.000 description 18
- 238000010525 oxidative degradation reaction Methods 0.000 description 18
- 238000006243 chemical reaction Methods 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 11
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 7
- 238000004364 calculation method Methods 0.000 description 6
- 239000002077 nanosphere Substances 0.000 description 5
- 238000001878 scanning electron micrograph Methods 0.000 description 5
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 4
- -1 iron ion Chemical class 0.000 description 4
- 230000033116 oxidation-reduction process Effects 0.000 description 4
- 238000001179 sorption measurement Methods 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 230000001351 cycling effect Effects 0.000 description 3
- 238000000724 energy-dispersive X-ray spectrum Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 239000013543 active substance Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000003575 carbonaceous material Substances 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 230000000593 degrading effect Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 239000003574 free electron Substances 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000010791 quenching Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003623 transition metal compounds Chemical class 0.000 description 2
- 229910001428 transition metal ion Inorganic materials 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 1
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 238000009303 advanced oxidation process reaction Methods 0.000 description 1
- 239000007853 buffer solution Substances 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 229910001429 cobalt ion Inorganic materials 0.000 description 1
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229910001431 copper ion Inorganic materials 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000010919 dye waste Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 239000002638 heterogeneous catalyst Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000002906 medical waste Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910001453 nickel ion Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical class [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/722—Oxidation by peroxides
-
- 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
- C02F2101/308—Dyes; Colorants; Fluorescent agents
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Materials Engineering (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a carbon-supported manganese oxide/manganese carbide composite catalyst, a preparation method and application thereof. The preparation method comprises the steps of adding a manganese ion-containing solution and dopamine hydrochloride into a tris buffer solution, stirring for 24 hours, centrifugally drying, and calcining for 2 hours at 900 ℃ in a nitrogen atmosphere to obtain the catalyst. The carbon-supported manganese oxide/manganese carbide composite catalyst takes nitrogen doped carbon as a carrier, and the composite transition metal oxide/carbide nano particles have the advantages of high capacity of efficiently activating peroxymonosulfate, high catalytic activity, strong redox capacity, good stability, recycling and the like, can efficiently and rapidly degrade organic pollutants (99% rhodamine B dye can be removed in 5 minutes), and have high use value and good application prospect. The preparation method of the carbon-supported manganese oxide/manganese carbide composite catalyst has the advantages of simple synthesis method, low raw material cost, low energy consumption, short time consumption, easy control of conditions and the like, is suitable for continuous large-scale batch production, and is convenient for industrial utilization.
Description
Technical Field
The invention belongs to the fields of advanced oxidation technology, material preparation and environmental protection, and relates to a carbon-supported manganese oxide/manganese carbide composite catalyst, and a preparation method and application thereof.
Background
With the continuous progress of science and technology, the continuous development of industry and the continuous improvement of medical level, the discharge of dye waste water from factories and the daily use of medical waste by people pose a great threat to ecological environment and health of people. Most representative of the dyes are rhodamine B (RhB), whose complex structure determines its nondegradable nature. Advanced oxidation processes based on Peroxymonosulfate (PMS) can achieve efficient removal of organic contaminants. It is therefore urgent to develop a heterogeneous catalyst that can rapidly activate PMS.
The metal ion in the transition metal compound is a candidate catalyst for effectively activating Peroxomonosulfate (PMS). The most common transition metal ions include: cobalt ion, iron ion, copper ion, nickel ion, manganese ion, etc., among which manganese ion catalysts have been most widely studied. In addition, recently, surface carbon-based catalysts including graphene, activated carbon, biochar and the like have the capability of efficiently activating PMS, and carbon-based materials have rich hydroxyl sites and larger specific surface area, which are more beneficial to adsorbing organic pollutants in water. Therefore, the preparation of the composite catalyst by loading the transition metal compound on the carbon-based material has important research value for the activation of the peroxymonosulfate. Dopamine hydrochloride is used as a biomass material, has adhesiveness, reducibility, self-polymerization and the like, can form coordination bonds with metal ions, and can also be used as a carbon source and a nitrogen source. Therefore, the catalyst for preparing the nitrogen-doped carbon carrier composite metal compound by compositing the transition metal ions and the dopamine hydrochloride has important research significance.
Disclosure of Invention
The invention aims to overcome the defects of the prior art, provides a carbon-supported manganese oxide/manganese carbide composite catalyst which has high catalytic activity, strong oxidation-reduction capability and good stability and can be recycled, and also provides a preparation method of the carbon-supported manganese oxide/manganese carbide composite catalyst which is simple and convenient to operate, does not need harsh conditions and large-scale equipment, and an application of the carbon-supported manganese oxide/manganese carbide composite catalyst in treating organic pollutant wastewater.
In order to solve the technical problems, the invention adopts the following technical scheme:
the carbon-supported manganese oxide/manganese carbide composite catalyst comprises manganese oxide, manganese carbide and nitrogen-doped carbon, wherein the nitrogen-doped carbon is used as a carrier to be modified with the manganese oxide and the manganese carbide.
The carbon-supported manganese oxide/manganese carbide composite catalyst is further improved, wherein the addition amount of the precursor of dopamine hydrochloride and manganese chloride tetrahydrate in the carbon-supported manganese oxide/manganese carbide composite catalyst is 5:1, a step of; the nitrogen-doped carbon carrier is a nano spherical material; the manganese oxide and manganese carbide are nano granular materials.
The carbon-supported manganese oxide/manganese carbide composite catalyst is further improved, wherein the calcination temperature of the carbon-supported manganese oxide/manganese carbide composite catalyst is 900 ℃, the calcination time is 2 hours, and the nitrogen atmosphere is protected.
As a general technical concept, the invention provides a preparation method of the carbon-supported manganese oxide/manganese carbide composite catalyst, which comprises the following steps: and adding the manganese ion-containing solution and dopamine hydrochloride into the tris buffer solution, stirring uniformly, and centrifuging and drying to obtain precursor powder of the carbon-supported manganese oxide/manganese carbide composite catalyst.
In the preparation method, the concentration of the tris buffer solution is 0.1 mol/L, and the pH value of the tris buffer solution is adjusted to be about 8.5 by using concentrated hydrochloric acid; the addition amount of the dopamine hydrochloride and the manganese chloride tetrahydrate is 5:1.
the preparation method is further improved, and the preparation method of the tris buffer solution comprises the following steps: weighing 0.6057 g tris (hydroxymethyl) aminomethane, dissolving the tris (hydroxymethyl) aminomethane in 50 mL deionized water, uniformly stirring, and then dropwise adding about 123 mu L of concentrated hydrochloric acid to adjust the pH value to 8.5; the addition amount of the dopamine hydrochloride is 0.2 g.
In the preparation method, further improved, the manganese ion solution and the dopamine hydrochloride are added into a tris buffer solution, and are stirred for 24 hours.
As a general technical concept, the invention provides an application of the carbon-supported manganese oxide/manganese carbide composite catalyst or the carbon-supported manganese oxide/manganese carbide composite catalyst prepared by the preparation method in treating organic pollutants.
The above application, further improved, comprising the steps of: mixing the carbon-supported manganese oxide/manganese carbide composite catalyst with an organic pollutant aqueous solution, stirring, adding peroxymonosulfate, and then starting an activation experiment to complete the treatment of the organic pollutant aqueous solution; the addition amount of the carbon-supported manganese oxide/manganese carbide composite catalyst is 0.2. 0.2 g of the carbon-supported manganese oxide/manganese carbide composite catalyst added into each liter of organic pollutant wastewater; the addition amount of the activator peroxymonosulfate was 0.5. 0.5 mM.
The application is further improved, wherein the organic pollutants in the organic pollutant wastewater are organic dyes; the organic dye is rhodamine B; the initial concentration of the organic pollutants in the organic pollutant wastewater is 0.01 g/L; the initial pH value of the organic pollutant wastewater is 2-6; the carbon-supported manganese oxide/manganese carbide composite catalyst and the organic pollutant aqueous solution are mixed and stirred for 30 minutes; the time to start the activation experiment after the addition of peroxymonosulfate was 10 minutes.
The innovation point of the invention is that:
in the invention, nitrogen doped carbon (N-C), manganese oxide (MnO), manganese carbide (Mn) 5 C 2 ) Has pi-pi conjugated structure and Mn 2+ 、Mn 3+ The method can be used for quickly and efficiently synergistically activating the peroxymonosulfate, and has the advantages of high catalytic activity, strong oxidation-reduction capability and the like; meanwhile, the carbon-supported manganese oxide/manganese carbide composite catalyst constructed in the invention canActivation of the peroxomonosulfate ion to produce sulfate radical (SO 4 · - ) Persulfate radical (SO) 5 · - ) Singlet oxygen 1 O 2 ) And the like, the organic pollutant rhodamine B is oxidatively degraded into carbon dioxide and water. More importantly, the multivalent manganese ions can realize the repeated recycling of the transition metal manganese compound; in addition, the nitrogen-doped carbon carrier not only can provide free electrons to activate the peroxymonosulfate ions, but also has larger specific surface area, thereby being beneficial to adsorbing organic pollutants. Therefore, the carbon-supported manganese oxide/manganese carbide composite catalyst activates the peroxymonosulfate ion under the synergistic effect of the multivalent manganese ion and the nitrogen-doped carbon carrier to generate active groups such as sulfate radical, persulfate radical, singlet oxygen and the like, and efficiently and rapidly oxidizes and degrades organic pollutants.
Compared with the prior art, the invention has the advantages that:
(1) The invention provides a carbon-supported manganese oxide/manganese carbide composite catalyst, which takes nitrogen-doped carbon nanospheres as carriers and loads manganese oxide and manganese carbide nanoparticles, has the advantages of high catalytic activity, strong oxidation-reduction capability, good stability, recycling and the like, can quickly activate peroxomonosulfate, efficiently remove organic pollutants (99% rhodamine B dye can be removed in 5 minutes) in wastewater, and has high use value and good application prospect.
(2) The invention also provides a preparation method of the carbon-supported manganese oxide/manganese carbide composite catalyst, which has the advantages of definite synthesis method, simple and convenient operation, no need of harsh conditions and large-scale equipment, and the like, is suitable for continuous large-scale batch production, and is convenient for industrial utilization.
(3) The carbon-supported manganese oxide/manganese carbide composite catalyst can be used for degrading organic pollutants (such as dye rhodamine B) in water, has the advantages of stable catalytic performance, recycling, high pollutant degradation efficiency and the like, and has good practical application prospect.
Drawings
In order to make the objects, technical solutions and advantages of the embodiments of the present invention more clear, the technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present invention.
FIG. 1 is a carbon-supported manganese oxide/manganese carbide composite catalyst (MnO/Mn) prepared in example 1 of the present invention 5 C 2 @C-900), the carbon supported manganese oxide catalyst prepared in example 2 (MnO@C-800), the carbon supported manganese oxide catalyst prepared in example 3 (MnO@C-700), the SEM image of a nitrogen doped carbon support (PDA) prepared in comparative example 1, and the EDS spectrum profile of example 1. Wherein a and b are PDA, c and d are MnO@C-700, e and f are MnO@C-800, g and h are MnO/Mn 5 C 2 SEM image of @ C-900, i-l being MnO/Mn 5 C 2 EDS energy spectrum sweep at C-900.
FIG. 2 is a carbon-supported manganese oxide/manganese carbide composite catalyst (MnO/Mn) obtained in example 1 of the present invention 5 C 2 XRD patterns of carbon-supported manganese oxide catalyst prepared in example 2 (MnO@C-800), carbon-supported manganese oxide catalyst prepared in example 3 (MnO@C-700), nitrogen doped carbon support prepared in comparative example 1 (PDA).
FIG. 3 is a carbon-supported manganese oxide/manganese carbide composite catalyst (MnO/Mn) according to example 4 of the present invention 5 C 2 Time-degradation efficiency profile and respective corresponding degradation rate constant profile for activated peroxomonosulfate oxidative degradation dye rhodamine B of @ C-900), carbon-supported manganese oxide catalyst (mno @ C-800), carbon-supported manganese oxide catalyst (mno @ C-700), nitrogen-doped carbon support (PDA).
FIG. 4 shows a carbon-supported manganese oxide/manganese carbide composite catalyst (MnO/Mn) according to example 5 of the present invention 5 C 2 @ C-900) time-degradation efficiency profile and respective corresponding degradation rate constant profile for oxidative degradation of dye rhodamine B by peroxymonosulfate activated at different peroxymonosulfate dosages.
FIG. 5 is a carbon-supported manganese oxide/manganese carbide composite catalyst (MnO/Mn) according to example 5 of the present invention 5 C 2 @ C-900) time-degradation efficiency maps and respective corresponding degradation rate constant maps of the peroxomonosulfate oxidative degradation dye rhodamine B with different amounts of the composite catalyst.
FIG. 6 is a carbon of example 5 of the present inventionManganese oxide/manganese carbide supported composite catalyst (MnO/Mn) 5 C 2 @ C-900) time-degradation efficiency profile and respective corresponding degradation rate constant profile for the oxidative degradation of dye rhodamine B by the peroxymonosulfate at different initial pH values.
FIG. 7 is a carbon-supported manganese oxide/manganese carbide composite catalyst (MnO/Mn) according to example 6 of the present invention 5 C 2 @ C-900) time-degradation efficiency plot of activated peroxomonosulfate oxidative degradation dye rhodamine B, five cycles.
FIG. 8 is a carbon-supported manganese oxide/manganese carbide composite catalyst (MnO/Mn) according to example 7 of the present invention 5 C 2 @ C-900) time-degradation efficiency profile of activated peroxymonosulfate oxidative degradation dye rhodamine B, using different quenchers.
Detailed Description
The invention is further described below in connection with the drawings and the specific preferred embodiments, but the scope of protection of the invention is not limited thereby.
The materials and instruments used in the examples below are all commercially available.
Example 1
A carbon-supported manganese oxide/manganese carbide composite catalyst takes nitrogen-doped carbon nanospheres as carriers and is modified with manganese oxide and manganese carbide nanoparticles.
In the embodiment, the addition amount of the precursor of dopamine hydrochloride and manganese chloride tetrahydrate in the carbon-supported manganese oxide/manganese carbide composite catalyst is 5:1, a step of; the calcination temperature of the carbon-supported manganese oxide/manganese carbide composite catalyst is 900 ℃, the calcination time is 2 hours, and the carbon-supported manganese oxide/manganese carbide composite catalyst is protected by nitrogen atmosphere.
In the embodiment, the nitrogen-doped carbon carrier is a nano spherical material with the diameter of 100-200 nm; manganese oxide and manganese carbide are nano granular materials and are loaded on a nitrogen-doped carbon carrier.
The preparation method of the carbon-supported manganese oxide/manganese carbide composite catalyst in the embodiment comprises the following steps:
(1) 0.6057 g tris (hydroxymethyl) aminomethane is weighed and dissolved in 50 mL deionized water, stirred uniformly, and then added dropwise with about 123 mu L of concentrated hydrochloric acid to adjust the pH value to 8.5, so as to prepare a tris (hydroxymethyl) aminomethane buffer solution with the concentration of 0.1 mol/L.
(2) Dopamine hydrochloride (C) of 0.2. 0.2 g 8 H 11 NO 2 HCl) and 0.0417, g manganese chloride tetrahydrate (MnCl) 2 · 4H 2 O) is added into the 0.1 mol/L tris buffer solution, and the mol ratio of the precursor dopamine hydrochloride to the tetrahydrate manganese chloride is 5:1, a step of; after magnetic stirring for 24 hours, the resulting precipitate was centrifuged, washed three more times with deionized water, dried in a vacuum oven for 12 hours, and the product was placed in a mortar and ground into powder.
(3) Calcining the powder in a tube furnace at 900 ℃ for 2 hours under nitrogen atmosphere to obtain a carbon-supported manganese oxide/manganese carbide composite catalyst named MnO/Mn 5 C 2 @C-900。
Example 2
A carbon-supported manganese oxide composite catalyst substantially identical to that of example 1 except that: the carbon-supported manganese oxide composite catalyst of example 2 did not produce manganese carbide.
The preparation method of the manganese oxide composite catalyst of this example is basically the same as that of example 1, except that: in example 2, the calcination temperature was 800 ℃.
The manganese oxide composite catalyst prepared in example 2 was named MnO@C-800.
Example 3
A carbon-supported manganese oxide composite catalyst substantially identical to that of example 1 except that: the carbon-supported manganese oxide composite catalyst of example 3 did not produce manganese carbide.
The preparation method of the carbon-supported manganese oxide composite catalyst of this embodiment is basically the same as that of embodiment 1, except that: in example 3, the calcination temperature was 700 ℃.
The carbon-supported manganese oxide composite catalyst prepared in example 3 was named MnO@C-700.
Comparative example 1
A method for preparing nitrogen-doped carbon nanospheres, which is substantially the same as in example 1, except that: in comparative example 1, manganese chloride tetrahydrate was not added and the product was designated as PDA.
FIG. 1 is a carbon-supported manganese oxide/manganese carbide composite catalyst (MnO/Mn) prepared in example 1 of the present invention 5 C 2 @C-900), the carbon supported manganese oxide catalyst prepared in example 2 (MnO@C-800), the carbon supported manganese oxide catalyst prepared in example 3 (MnO@C-700), the SEM image of a nitrogen doped carbon support (PDA) prepared in comparative example 1, and the EDS spectrum profile of example 1. Wherein a and b are PDA, c and d are MnO@C-700, e and f are MnO@C-800, g and h are MnO/Mn 5 C 2 SEM image of @ C-900, i-l being MnO/Mn 5 C 2 EDS energy spectrum sweep at C-900. As can be seen from SEM images a and b, the size of the nitrogen-doped carbon nanospheres is about 200-400 a nm a, while the size of the nitrogen-doped carbon nanospheres is significantly smaller than about 100-200 a nm a after loading with manganese oxide and manganese carbide. As can be seen from the EDS spectrum scans i-l, the carbon-supported manganese oxide/manganese carbide composite catalyst (MnO/Mn) prepared in example 1 5 C 2 @ C-900) only four elements, C, N, O and Mn, were present on the surface, no other elements were detected, and they were uniformly distributed on the surface of the material.
MnO/Mn 5 C 2 X-ray diffraction analysis was performed on @ C-900 (example 1), mnO @ C-800 (example 2), mnO @ C-700 (example 3), and PDA (comparative example 1), and the results are shown in FIG. 2.
FIG. 2 is a carbon-supported manganese oxide/manganese carbide composite catalyst (MnO/Mn) obtained in example 1 of the present invention 5 C 2 XRD patterns of carbon-supported manganese oxide catalyst prepared in example 2 (MnO@C-800), carbon-supported manganese oxide catalyst prepared in example 3 (MnO@C-700), nitrogen doped carbon support prepared in comparative example 1 (PDA). As can be seen from FIG. 2, PDA (comparative example 1) is at 2θ There is one inclusion peak at = 22.41 °, which is graphitic carbon formed by nitrogen doping with carbon. MnO@C-800 (example 2) and MnO@C-700 (example 3) each contain 5 distinct diffraction peaks, each at 2θ Crystal planes (111), (200) (220), (311) corresponding to MnO (standard card: pdf#07-0230) at =34.98 °, 41.53 °, 57.54 °, 70.89 °, 74.56 °, respectivelyAnd (222); and MnO@C-800 (example 2) has a slightly greater diffraction peak intensity than MnO@C-700 (example 3). MnO/Mn 5 C 2 C-900 (example 1) in addition to the diffraction peaks with MnO (standard card: PDF#07-0230), a number of peaks, each at 2, appearθ =40.78 °, 42.62 °, 43.42 °, 43.93 °, 44.75 °, 45.50 ° and 47.26 °, respectively corresponding to Mn 5 C 2 (standard card: PDF#14-0176) crystal planes (-211), (120), (015), -213), -122, and (006); further, at 2θ A very pronounced C (002) plane diffraction peak appears at=26.21°.
Example 4
The application of the carbon-supported manganese oxide/manganese carbide composite catalyst in treating organic pollutants in water, in particular to the degradation of dye (rhodamine B) in wastewater by using the carbon-supported manganese oxide/manganese carbide composite catalyst, comprising the following steps of:
weighing MnO/Mn 5 C 2 @C-900 (example 1), mnO@C-800 (example 2), mnO@C-700 (example 3), PDA (comparative example 1), 0.2 each g, are added to rhodamine B wastewater of 50 mL, concentration of 0.01 g/L and initial pH value of 2-6, and magnetically stirred in the dark for 30 minutes to reach adsorption equilibrium; then adding activator peroxomonosulfate 0.5. 0.5 mM, starting timing, and after catalytic reaction for 10 minutes, completing the degradation of rhodamine B in the wastewater.
Determination of degradation efficiency: taking out the reaction solution of 4 mL every 5 minutes, filtering out the catalyst by a 0.45 mu m water-based filter membrane, then performing ultraviolet-visible spectrometer (UV-Vis) test to obtain the absorbance of the solution to be tested, and calculating the degradation efficiency and the reaction rate constant of the pollutant, as shown in figure 3.
The above calculation, further improved, degradation efficiency formula:
η = [(C 0 -C t )/C 0 ]×100%
in the formulaηThe (%) is the degradation rate of the polymer,C 0 for an initial concentration of (mg/L) contaminant,C t (mg/L) is the concentration of the contaminant at a particular time.
The calculation is further improved, and the reaction rate constant calculation formula is as follows:
-kt = ln (C t /C 0 )
the reaction of the catalyst-activated persulfate in example 4 of the present invention was simulated according to first order kinetics. In the formulak（min -1 ) In order to achieve a reaction rate constant in the degradation reaction,tis the reaction time. Drawing in ln # -C t /C 0 ) The change curve with time is used for calculating the slope value to obtain the degradation rate constant in the reaction processk。
FIG. 3 is a carbon-supported manganese oxide/manganese carbide composite catalyst (MnO/Mn) according to example 4 of the present invention 5 C 2 Time-degradation efficiency profile and respective corresponding degradation rate constant profile for activated peroxomonosulfate oxidative degradation dye rhodamine B of @ C-900), carbon-supported manganese oxide catalyst (mno @ C-800), carbon-supported manganese oxide catalyst (mno @ C-700), nitrogen-doped carbon support (PDA).
As can be seen from fig. 3:
the carbon-supported manganese oxide/manganese carbide composite catalyst (MnO/Mn) prepared in example 1 of the present invention 5 C 2 @ C-900) the degradation efficiency of rhodamine B after 10 minutes of the activation experiment was 99.9%, and the degradation rate constant was 0.488 min -1 。
The carbon-supported manganese oxide catalyst (MnO@C-800) prepared in example 2 of the invention has a degradation efficiency of 99.8% for rhodamine B after 10 minutes of an activation experiment, and a degradation rate constant of 0.328 min -1 。
The carbon-supported manganese oxide catalyst (MnO@C-700) prepared in example 3 of the invention had a degradation efficiency of 81.0% for rhodamine B after 10 minutes of the activation experiment, and a degradation rate constant of 0.141 min -1 。
The nitrogen-doped carbon carrier (PDA) prepared in comparative example 1 of the invention has a degradation efficiency of 40.0% for rhodamine B after 10 minutes of activation experiment, and a degradation rate constant of 0.022 min -1 。
The above results indicate that: the carbon-supported manganese oxide/manganese carbide composite catalyst (MnO/Mn) prepared in example 1 5 C 2 The removal rate of the rhodamine B can be optimized, the degradation efficiency of the rhodamine B after 10 minutes of activation of the peroxymonosulfate is 99.9 percent, and the catalytic degradation rate constant is 0.488 min -1 Degradation rate constants greater than 0.328 min for the other examples and comparative examples -1 、0.141 min -1 、0.022 min -1 . The main reason for this phenomenon is that the carbon-supported manganese oxide/manganese carbide composite catalyst of the present invention has a polyvalent transition metal manganese ion Mn 2+ 、Mn 3+ And the pi-pi conjugated structure of the nitrogen-doped carbon carrier can provide a large amount of free electrons, quickly and efficiently synergistically activate the peroxymonosulfate, and the nitrogen-doped carbon carrier has excellent catalytic activity and oxidation-reduction capability and can efficiently and rapidly oxidize and degrade organic pollutants.
Example 5
Examination of carbon-supported manganese oxide/manganese carbide composite catalyst (MnO/Mn) prepared in example 1 of the present invention 5 C 2 @ C-900) influencing factors in the oxidative degradation of rhodamine B by activated peroxymonosulfate, including: the dosage of the peroxomonosulfate, the dosage of the composite catalyst and the initial pH value.
The consumption of peroxymonosulfate: weighing five parts of MnO/Mn 5 C 2 0.2 g each of @ C-900 (example 1) was added to 50 mL, 0.01 g/L rhodamine B wastewater at an initial pH of 2 to 6, and magnetically stirred in the dark for 30 minutes to achieve adsorption equilibrium; then, the activator peroxomonosulfates of 0.1, 0.2, 0.5, 0.8 and 1.0 mM are respectively added, timing is started, and after the catalytic reaction is carried out for 10 minutes, the degradation of rhodamine B in the wastewater is completed.
The dosage of the composite catalyst is as follows: weighing five parts of MnO/Mn 5 C 2 @C-900 (example 1), wherein the mass of the mixture is 0.02, 0.04, 0.12, 0.20 and 0.24 g respectively, the mixture is added into rhodamine B wastewater with the concentration of 0.01 g/L and the initial pH value of 2-6 and the mixture is magnetically stirred in the dark for 30 minutes to reach adsorption balance; then adding activator peroxomonosulfate 0.5. 0.5 mM, starting timing, and after catalytic reaction for 10 min, finishingDegradation of rhodamine B in the wastewater.
Initial pH: weighing five parts of MnO/Mn 5 C 2 0.2 g each of which was added to rhodamine B wastewater of 50 mL at a concentration of 0.01 g/L and an initial pH of 2.0, 5.1, 6.0, 8.5, 12.0, respectively, and magnetically stirred in the dark for 30 minutes to reach adsorption equilibrium; then adding activator peroxomonosulfate 0.5. 0.5 mM, starting timing, and after catalytic reaction for 15 minutes, completing the degradation of rhodamine B in the wastewater.
Determination of degradation efficiency: the measurement procedure and calculation method were exactly the same as those of example 4. The degradation efficiency and reaction rate constant of the amount of peroxymonosulfate are shown in FIG. 4; the degradation efficiency and reaction rate constant of the amount of the composite catalyst are shown in fig. 5; the degradation efficiency and reaction rate constants for the initial pH are shown in FIG. 6.
FIG. 4 shows a carbon-supported manganese oxide/manganese carbide composite catalyst (MnO/Mn) according to example 5 of the present invention 5 C 2 @ C-900) time-degradation efficiency profile and respective corresponding degradation rate constant profile for oxidative degradation of dye rhodamine B by peroxymonosulfate activated at different peroxymonosulfate dosages.
As can be seen from fig. 4: with the increase of the consumption of the peroxymonosulfate, more and more active species can be generated, so that the removal rate of the RhB is improved; and too high a concentration may reduce the degradation rate of RhB due to self-quenching reaction itself. By calculation, different PMS concentrations are in MnO/Mn 5 C 2 The reaction rate constant contrast in the @ C-900/RhB system is: k [ 0.5. 0.5 mM (0.482 min) -1 ）] > k[1.0 mM（0.406 min -1 ）] > k[0.8 mM（0.389 min- 1 ）] > k[0.2 mM（0.189 min -1 ）] > k[0.1 mM（0.067 min -1 ）]. Thus, the optimum amount of peroxymonosulfate is 0.5. 0.5 mM.
FIG. 5 is a carbon-supported manganese oxide/manganese carbide composite catalyst (MnO/Mn) according to example 5 of the present invention 5 C 2 @ C-900) time-degradation efficiency maps and respective corresponding degradation rate constant maps of the peroxomonosulfate oxidative degradation dye rhodamine B with different amounts of the composite catalyst.
As can be seen from fig. 5: the degradation efficiency is continuously increased along with the increase of the dosage of the composite catalyst. By calculation, the dosage of different catalysts is MnO/Mn 5 C 2 The reaction rate constant contrast in the @ C-900/RhB system is: k [ 0.20. 0.20 g/L (0.386 min) -1 ）] > k[0.24 g/L（0.332 min -1 ）] > k[0.12 g/L（0.240 min -1 ）] > k[0.04 g/L（0.131 min -1 ）] > k[0.02 g/L（0.070 min -1 ）]. Therefore, to avoid wasting material, the optimum amount of catalyst is 0.20 g/L.
FIG. 6 is a carbon-supported manganese oxide/manganese carbide composite catalyst (MnO/Mn) according to example 5 of the present invention 5 C 2 @ C-900) time-degradation efficiency profile and respective corresponding degradation rate constant profile for the oxidative degradation of dye rhodamine B by the peroxymonosulfate at different initial pH values.
As can be seen from fig. 6: in the process of increasing the pH value from 2.0 to 12.0, the reaction rate in the system is firstly increased and then decreased: k [ ph=5.1 (0.320 min) -1 ）] > k[pH = 6.0（0.318 min -1 ）] > k[pH = 2.0（0.255 min -1 ）] > k[pH = 8.5（0.060 min -1 ）] > k[pH = 12（0.046 min -1 ）]. It can be seen that the removal rate of RhB is maintained above 90% when the system is acidic or neutral, and the removal rate of RhB is decreased when the reaction system is weakly alkaline or strongly alkaline. The reason may be OH in the system - Forms hydroxide with Mn species and shields the catalyst MnO/Mn 5 C 2 Some active sites of @ C-900, resulting in a decrease in the degradation rate of RhB. Therefore, the optimum range of the initial pH value is 2 to 6.
The above results indicate that: in example 5 of the present invention, the catalyst MnO/Mn 5 C 2 In the process of oxidizing and degrading rhodamine B by activating peroxymonosulfate, the optimal dosage of the peroxymonosulfate is 0.5 mM, the optimal dosage of the catalyst is 0.20 g/L, and the optimal range of the initial pH value is 2-6.
Example 6
Examination of carbon-supported manganese oxide/carbon prepared in example 1 of the present inventionManganese compound catalyst (MnO/Mn) 5 C 2 @ C-900) cycling stability during oxidative degradation of rhodamine B by activated peroxymonosulfate.
Catalyst MnO/Mn 5 C 2 Experimental procedure for oxidative degradation of rhodamine B by activated peroxomonosulfate at @ C-900 (example 1) was exactly the same as in example 5, and the optimal conditions in example 5 were chosen.
The degradation efficiency was measured in exactly the same manner as in example 4.
In the above example 6, the catalyst after each use was further improved by centrifugation, precipitation, separation, washing with water for 3 or more times, drying, and grinding, and then was further used for the next cycle experiment for a total of five times. The degradation efficiency of the cycling experiment is shown in figure 7.
FIG. 7 is a carbon-supported manganese oxide/manganese carbide composite catalyst (MnO/Mn) according to example 6 of the present invention 5 C 2 @ C-900) time-degradation efficiency plot of activated peroxomonosulfate oxidative degradation dye rhodamine B, five cycles.
As can be seen from fig. 7: catalyst MnO/Mn 5 C 2 After five times of repeated use @ C-900 (example 1), the catalyst still had excellent PMS activating performance, and the efficiency of RhB removal was maintained at 99.5% or more each time, indicating that the carbon-supported manganese oxide/manganese carbide composite catalyst (MnO/Mn) prepared in example 1 of the present invention 5 C 2 The @ C-900) has excellent cycling stability, is a novel composite catalyst with good stability and recycling for multiple times, and has very good practical application prospect.
Example 7
Examination of carbon-supported manganese oxide/manganese carbide composite catalyst (MnO/Mn) prepared in example 1 of the present invention 5 C 2 @ C-900) active species during oxidative degradation of rhodamine B by activated peroxymonosulfate.
Catalyst MnO/Mn 5 C 2 Experimental procedure for oxidative degradation of rhodamine B by activated peroxomonosulfate at C-900 (example 1) was exactly the same as in example 4.
The degradation efficiency was measured in exactly the same manner as in example 4.
In example 7, with further improvement, the reaction solution of 4 mL was taken out every 5 minutes, the catalyst was filtered off with a 0.45 μm aqueous filter, and then 200 mM methanol (MeOH), 200 mM Tertiary Butanol (TBA), 5 mM or 200 mM furfuryl alcohol (FFA) solution was added to quench the free radicals, to obtain a solution to be tested, and then an ultraviolet-visible spectrometer (UV-Vis) test was performed, as shown in fig. 8.
FIG. 8 is a carbon-supported manganese oxide/manganese carbide composite catalyst (MnO/Mn) according to example 7 of the present invention 5 C 2 @ C-900) time-degradation efficiency profile of activated peroxymonosulfate oxidative degradation dye rhodamine B, using different quenchers.
As can be seen from fig. 8: catalyst MnO/Mn 5 C 2 C-900 (example 1) singlet oxygen during the oxidative degradation of dye rhodamine B by activated peroxymonosulfate 1 O 2 Is the main active substance. Methanol (MeOH), tert-butanol (TBA), furfuryl alcohol (FFA) as OH, SO, respectively 4 · - 、 1 O 2 Is substantially free of MnO/Mn from methanol (MeOH) and Tertiary Butanol (TBA) 5 C 2 Degradation rate of RhB in the @ C-900/RhB system, and when furfuryl alcohol (FFA) concentration is increased to 200 mM, the degradation rate of RhB in the system is inhibited, indicating singlet oxygen 1 O 2 Is the main active substance.
The above examples are only preferred embodiments of the present invention, and the scope of the present invention is not limited to the above examples. All technical schemes belonging to the concept of the invention belong to the protection scope of the invention. It should be noted that modifications and adaptations to the present invention may occur to one skilled in the art without departing from the principles of the present invention and are intended to be within the scope of the present invention.
Claims (9)
1. The carbon-supported manganese oxide/manganese carbide composite catalyst is characterized by comprising manganese oxide, manganese carbide and nitrogen-doped carbon, wherein manganese oxide and manganese carbide nano-particles are supported on a nitrogen-doped carbon carrier; the addition amount of the precursor of dopamine hydrochloride and manganese chloride tetrahydrate in the carbon-supported manganese oxide/manganese carbide composite catalyst is 5:1, a step of; the nitrogen-doped carbon carrier is a nano spherical material; the manganese oxide and manganese carbide are nano granular materials.
2. The carbon supported manganese oxide/manganese carbide composite catalyst according to claim 1, wherein the calcination temperature of the carbon supported manganese oxide/manganese carbide composite catalyst is 900 ℃, the calcination time is 2 hours, and the nitrogen atmosphere is protected.
3. A method for preparing the carbon-supported manganese oxide/manganese carbide composite catalyst according to claim 1 or 2, comprising the steps of: and adding the manganese ion-containing solution and dopamine hydrochloride into the tris buffer solution, stirring uniformly, and centrifuging and drying to obtain precursor powder of the carbon-supported manganese oxide/manganese carbide composite catalyst.
4. The method of claim 3, wherein the tris buffer solution has a concentration of 0.1 mol/L and is adjusted to a pH of about 8.5 using concentrated hydrochloric acid; the addition amount of the dopamine hydrochloride and the manganese chloride tetrahydrate is 5:1.
5. the preparation method according to claim 4, wherein the preparation method of the tris buffer solution comprises the steps of: weighing 0.6057 g tris (hydroxymethyl) aminomethane, dissolving the tris (hydroxymethyl) aminomethane in 50 mL deionized water, uniformly stirring, and then dropwise adding about 123 mu L of concentrated hydrochloric acid to adjust the pH value to 8.5; the addition amount of the dopamine hydrochloride is 0.2 g.
6. The preparation method according to any one of claims 3 to 5, wherein the manganese ion solution and dopamine hydrochloride are added to a tris buffer solution and stirred for 24 hours.
7. Use of the carbon-supported manganese oxide/manganese carbide composite catalyst according to claim 1 or 2 or the carbon-supported manganese oxide/manganese carbide composite catalyst prepared by the preparation method according to any one of claims 3 to 6 for treating organic pollutants.
8. The use according to claim 7, characterized by the steps of: mixing the carbon-supported manganese oxide/manganese carbide composite catalyst with an organic pollutant aqueous solution, stirring, adding peroxymonosulfate, and then starting an activation experiment to complete the treatment of the organic pollutant aqueous solution; the addition amount of the carbon-supported manganese oxide/manganese carbide composite catalyst is 0.2. 0.2 g of the carbon-supported manganese oxide/manganese carbide composite catalyst added into each liter of organic pollutant wastewater; the addition amount of the activator peroxymonosulfate was 0.5. 0.5 mM.
9. The use according to claim 8, wherein the organic contaminants in the organic contaminant wastewater are organic dyes; the organic dye is rhodamine B; the initial concentration of the organic pollutants in the organic pollutant wastewater is 0.01 g/L; the initial pH value of the organic pollutant wastewater is 2-6; the carbon-supported manganese oxide/manganese carbide composite catalyst and the organic pollutant aqueous solution are mixed and stirred for 30 minutes; the time to start the activation experiment after the addition of peroxymonosulfate was 10 minutes.
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