CN114931963A - N-doped manganese-magnesium binary oxide and preparation method and application thereof - Google Patents
N-doped manganese-magnesium binary oxide and preparation method and application thereof Download PDFInfo
- Publication number
- CN114931963A CN114931963A CN202210522344.3A CN202210522344A CN114931963A CN 114931963 A CN114931963 A CN 114931963A CN 202210522344 A CN202210522344 A CN 202210522344A CN 114931963 A CN114931963 A CN 114931963A
- Authority
- CN
- China
- Prior art keywords
- magnesium
- mgmno
- solution
- binary oxide
- manganese
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- KBMLJKBBKGNETC-UHFFFAOYSA-N magnesium manganese Chemical compound [Mg].[Mn] KBMLJKBBKGNETC-UHFFFAOYSA-N 0.000 title claims abstract description 46
- 238000002360 preparation method Methods 0.000 title description 14
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 150
- 239000003054 catalyst Substances 0.000 claims abstract description 110
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 83
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims abstract description 80
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 73
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 39
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 23
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 23
- 239000001301 oxygen Substances 0.000 claims abstract description 23
- 230000003197 catalytic effect Effects 0.000 claims abstract description 19
- 239000000243 solution Substances 0.000 claims description 105
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 51
- 239000002244 precipitate Substances 0.000 claims description 37
- 239000004202 carbamide Substances 0.000 claims description 23
- XSQUKJJJFZCRTK-UHFFFAOYSA-N urea group Chemical group NC(=O)N XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 23
- 238000005406 washing Methods 0.000 claims description 22
- 238000003756 stirring Methods 0.000 claims description 20
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 claims description 18
- XZMCDFZZKTWFGF-UHFFFAOYSA-N Cyanamide Chemical compound NC#N XZMCDFZZKTWFGF-UHFFFAOYSA-N 0.000 claims description 17
- 239000007864 aqueous solution Substances 0.000 claims description 16
- 239000007789 gas Substances 0.000 claims description 16
- 238000010521 absorption reaction Methods 0.000 claims description 11
- 238000001816 cooling Methods 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 11
- 238000000227 grinding Methods 0.000 claims description 11
- 238000002156 mixing Methods 0.000 claims description 11
- 229920006395 saturated elastomer Polymers 0.000 claims description 11
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 5
- 230000015556 catabolic process Effects 0.000 claims description 4
- 238000006731 degradation reaction Methods 0.000 claims description 4
- 239000012153 distilled water Substances 0.000 claims description 4
- 238000001354 calcination Methods 0.000 claims description 3
- 238000006385 ozonation reaction Methods 0.000 claims description 3
- 239000012295 chemical reaction liquid Substances 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 31
- 230000003647 oxidation Effects 0.000 abstract description 6
- 238000007254 oxidation reaction Methods 0.000 abstract description 6
- 239000000843 powder Substances 0.000 description 54
- 239000011572 manganese Substances 0.000 description 24
- 239000011777 magnesium Substances 0.000 description 22
- 239000000126 substance Substances 0.000 description 21
- 239000008367 deionised water Substances 0.000 description 19
- 229910021641 deionized water Inorganic materials 0.000 description 19
- 238000001514 detection method Methods 0.000 description 19
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 17
- 239000008103 glucose Substances 0.000 description 17
- 239000007787 solid Substances 0.000 description 12
- 229910052749 magnesium Inorganic materials 0.000 description 11
- 229910052748 manganese Inorganic materials 0.000 description 11
- 229910052751 metal Inorganic materials 0.000 description 11
- 239000002184 metal Substances 0.000 description 11
- 229910052799 carbon Inorganic materials 0.000 description 10
- 238000002474 experimental method Methods 0.000 description 10
- HNSDLXPSAYFUHK-UHFFFAOYSA-N 1,4-bis(2-ethylhexyl) sulfosuccinate Chemical compound CCCCC(CC)COC(=O)CC(S(O)(=O)=O)C(=O)OCC(CC)CCCC HNSDLXPSAYFUHK-UHFFFAOYSA-N 0.000 description 9
- 238000004128 high performance liquid chromatography Methods 0.000 description 9
- 238000012216 screening Methods 0.000 description 9
- 239000006228 supernatant Substances 0.000 description 9
- 238000001291 vacuum drying Methods 0.000 description 9
- 238000005303 weighing Methods 0.000 description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 7
- 239000011949 solid catalyst Substances 0.000 description 6
- 239000002351 wastewater Substances 0.000 description 5
- 230000002153 concerted effect Effects 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 238000005470 impregnation Methods 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 229910052755 nonmetal Inorganic materials 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- 239000002253 acid Substances 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 3
- 229910052723 transition metal Inorganic materials 0.000 description 3
- PUAQLLVFLMYYJJ-UHFFFAOYSA-N 2-aminopropiophenone Chemical compound CC(N)C(=O)C1=CC=CC=C1 PUAQLLVFLMYYJJ-UHFFFAOYSA-N 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 230000000593 degrading effect Effects 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000007210 heterogeneous catalysis Methods 0.000 description 2
- 230000036571 hydration Effects 0.000 description 2
- 238000006703 hydration reaction Methods 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 239000002957 persistent organic pollutant Substances 0.000 description 2
- 230000027756 respiratory electron transport chain Effects 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- JWOZORSLWHFOEI-UHFFFAOYSA-N [O--].[O--].[Mg++].[Mn++] Chemical compound [O--].[O--].[Mg++].[Mn++] JWOZORSLWHFOEI-UHFFFAOYSA-N 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 239000012018 catalyst precursor Substances 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 239000002778 food additive Substances 0.000 description 1
- 235000013373 food additive Nutrition 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000007172 homogeneous catalysis Methods 0.000 description 1
- 239000005556 hormone Substances 0.000 description 1
- 229940088597 hormone Drugs 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 229910001425 magnesium ion Inorganic materials 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000008239 natural water Substances 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000006276 transfer reaction Methods 0.000 description 1
- 229910001428 transition metal ion Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 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
-
- 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—
-
- 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
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/78—Treatment of water, waste water, or sewage by oxidation with ozone
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
Abstract
The invention discloses a monatomic nitrogen-doped magnesium-manganese binary oxide catalyst, which is applied to catalyzing ozone oxidation to remove acetic acid. The invention utilizes the characteristic that the electronegativity of nitrogen is lower than that of oxygen to carry out monatomic doping to strengthen the catalytic ozone activity of the magnesium-manganese binary oxide catalyst, and simultaneously, the doping of nitrogen reduces the number of alkaline site lattice oxygen of the magnesium-manganese binary oxide so as to improve the stability of the magnesium-manganese binary oxide in water.
Description
(I) the technical field
The invention relates to the field of preparation of doped catalysts, in particular to a preparation method of a single-atom doped magnesium-manganese binary oxide catalyst and a treatment method for catalyzing ozone to treat acetic acid by using the same.
(II) background of the invention
With the development and progress of the analysis and detection technology, emerging organic pollutants such as medicines, personal care products, pesticides, hormones, food additives and the like are detected in natural water. Most of emerging pollutants can not be degraded biochemicallyAnd poses potential harm to human health. The advanced oxidation technology can generate oxygen-containing free radicals with strong oxidation capability, and can directly mineralize organic matters in wastewater or improve the biodegradability of organic pollutants. The ozone advanced oxidation technology is one of the most promising methods for treating organic degradation-resistant wastewater at present. Solid base MgO has the advantages of homogeneous and heterogeneous catalysis ozone, in the reaction process of catalyzing ozone by MgO, the pH value of the solution can be obviously raised to be alkaline, so that the ozone decomposition is promoted to generate oxygen-containing free radicals, and experiments prove that MgO has surface active sites to catalyze the ozone decomposition to generate the oxygen-containing free radicals. However, the hydration of MgO can affect the stability of MgO-catalyzed ozone. Reaction of MgO with water produces Mg (OH) which is sparingly soluble in water and has a catalytic ozone activity lower than that of MgO 2 . It was found that the catalytic ozone activity of solid bases is directly proportional to their alkaline strength, whereas their alkaline strength is inversely proportional to stability. In addition, researches find that the double-metal oxide magnesium manganese formed by the alkaline earth metal Mg and the transition metal Mn overcomes the contradiction between the activity and the stability of solid base catalytic ozone, and provides an acid-base concerted catalytic ozone reaction mechanism. The introduction of transition metal element Mn properly reduces the basic strength of the catalyst, and simultaneously transition metal ions (Mn) with low valence state in acid site-crystal lattice 2+ 、Mn 3+ ) An electron transfer reaction with ozone with the aid of a basic site-protonated hydroxyl group produces an oxygen-containing radical. Magnesium manganese oxide thus has a higher catalytic ozone activity and stability than MgO.
The alkaline strength of the magnesium-manganese metal binary oxide is properly reduced, and although the activity of an alkaline site is influenced, the hydration of the catalyst can be reduced, and the stability of the catalyst is improved; meanwhile, the electron transfer capacity of the acid site of the magnesium-manganese metal binary oxide is enhanced, the activity lost by the alkaline site is compensated, the maintenance is maintained, and even the overall activity of the catalyst is improved, so that the alkaline strength of the catalyst is properly reduced, and the catalytic ozone activity of the acid site is enhanced, which is a design idea for further improving the catalytic ozone activity and stability of the magnesium-manganese metal binary oxide. Therefore, the non-metal element with electronegativity less than that of oxygen is doped into the magnesium-transition metal binary oxide, and feasibility is provided for further improving the catalytic ozone activity and stability of the magnesium-manganese metal binary oxide.
In conclusion, the preparation of the nonmetal monatomic doped magnesium-manganese metal binary oxide and the research on the catalytic ozone performance have important meanings. The following problems also exist in the current research:
(1) the influence rule of non-metal doping atoms on the acid-base chemical properties of the magnesium-manganese metal binary oxide is lacked.
(2) The study on the activity and stability rule of the acid-base concerted catalysis ozone of the magnesium-manganese metal binary oxide by the non-metal doping atoms is vacant.
Based on the research background and thought, aiming at the problem of optimizing the acid-base synergistic activity and stability of the ozone water treatment catalyst magnesium-manganese metal binary oxide, the project adopts single element nitrogen doping to regulate and control the acid-base property of the magnesium-manganese metal binary oxide, and the acid-base synergistic catalytic ozone activity and stability of the catalyst are improved. The influence rule of the monatomic nitrogen doping on the activity and stability of the acid-base concerted catalysis ozone of the magnesium-manganese metal binary oxide is researched. By implementing the project, the design and synthesis of the high-efficiency stable ozone water treatment catalyst can be realized, the optimization mechanism of acid-base concerted catalysis ozone of magnesium-manganese metal binary oxide is constructed, and the development and application of heterogeneous catalysis ozone technology are promoted.
Disclosure of the invention
Aiming at the stability problem of the catalyst, the invention aims to prepare a monatomic nitrogen-doped magnesium-manganese binary oxide catalyst and apply the monatomic nitrogen-doped magnesium-manganese binary oxide catalyst to catalytic ozonation for removing acetic acid.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides an N-doped manganese-magnesium binary oxide, which is prepared as follows:
dissolving magnesium nitrate and manganese nitrate in secondary distilled water, dropwise adding NaOH solution, stirring and reacting for 1h-3h (preferably 2h) at 70-120 ℃ (preferably 90 ℃), cooling and centrifuging the obtained reaction liquid, taking the lower-layer precipitate, washing with water until the pH of the washing liquid is less than 9, drying in vacuum, grinding to obtain a carrier, dropwise adding a water solution of a nitrogen source, fully mixing, standing for 5h-15h (preferably 12h), and calcining for 1h-3h (preferably 2h) at 200-800 ℃ (preferably 500 ℃), so as to obtain the N-doped manganese-magnesium binary oxide;
the mass ratio of the magnesium nitrate to the manganese nitrate is 1-2:1 (preferably 1: 1); the ratio of the amount of NaOH contained in the NaOH solution to the total amount of magnesium nitrate and manganese nitrate is 6-12: 1 (preferably 10.5: 1); the volume of the water solution of the nitrogen source is equal to the saturated water absorption capacity of the carrier; the nitrogen source contained in the nitrogen source aqueous solution is urea or cyanamide (preferably urea); the mass of the nitrogen source is 3-28% (preferably 19%) of the mass of the support, based on its theoretical nitrogen content.
Further, the volume of the secondarily distilled water is 0.5 to 1.0L/mol (preferably 0.75L/mol) in terms of the sum of the amounts of the magnesium nitrate and the manganese nitrate.
Further, the concentration of the NaOH solution is 4 to 8mol/L (preferably 6 mol/L).
Preferably, the carrier has a particle size of 0.0385-0.05mm, and can be obtained by sieving with 300-mesh and 400-mesh sieves in sequence.
The invention also provides application of the N-doped manganese-magnesium binary oxide as a catalyst in catalyzing ozone to degrade acetic acid in an acetic acid-containing solution.
The application specifically comprises the following steps: and adding the N-doped manganese-magnesium binary oxide into the acetic acid-containing solution, placing the obtained mixture into a reactor, and introducing ozone from the bottom of the reactor for degradation.
Preferably the pH of the acetic acid containing solution is between 5 and 9, preferably the pH is 5. Of course, there are some effects at other pH's. The concentration of the acetic acid-containing solution is 20mg/L, and the volume of the acetic acid-containing solution is 2.5L/g based on the mass of the N-doped manganese-magnesium binary oxide.
Specifically, in the embodiment of the invention, the ozone is introduced into the reactor in the form of a mixed gas of ozone and oxygen, the flow rate of the mixed gas is 0.5L/min, and the concentration of the ozone in the mixed gas is 40 mg/L.
The acetic acid-containing solution can be regarded as acetic acid-containing wastewater, and the effect of the catalyst for catalyzing and degrading the acetic acid in different wastewater is analyzed through the acetic acid-containing solution with different pH values.
The doping source is mainly selected from a nitrogen source suitable for an isometric impregnation method, if the nitrogen source with poor water solubility is used, the isometric impregnation effect cannot be achieved during impregnation, and Mg ions are dissolved out due to excessive impregnation. The solvent used in the invention is deionized water, and if a corresponding organic solvent is used, the organic solvent contains other elements such as carbon and the like, which has influence on a doping system and subsequent degradation systems.
The invention also relates to application of the nitrogen-doped magnesium-manganese binary oxide solid catalyst in catalyzing ozone oxidation to remove acetic acid and actual wastewater. The catalyst of the present invention can raise the elimination rate of acetic acid.
When the monatomic nitrogen-doped magnesium-manganese binary oxide solid catalyst is used for catalyzing acetic acid in ozone oxidation water, the process conditions are specifically as follows: adjusting the pH value of 250mL of acetic acid aqueous solution containing 20mg/L to 5,7 and 9, adding 400mg/L of monatomic nitrogen-doped magnesium-manganese binary oxide solid catalyst, introducing ozone to degrade the acetic acid, wherein the adding amount of the ozone is 40mg/L, and the flow rate of the ozone and the oxygen is 0.5L/min.
Compared with the prior art, the monatomic nitrogen-doped magnesium-manganese binary oxide solid catalyst is prepared by adding the monatomic nitrogen-doped magnesium-manganese binary oxide solid catalyst into O 3 In the acetic acid solution treatment, the following beneficial effects are achieved:
(1) the characteristic that the electronegativity of nitrogen is lower than that of oxygen is utilized to carry out single atom doping to strengthen the catalytic ozone activity of the magnesium-manganese binary oxide catalyst, and meanwhile, the doping of nitrogen reduces the number of alkaline site lattice oxygen of the magnesium-manganese binary oxide so as to improve the stability of the magnesium-manganese binary oxide in water.
(2) The monatomic nitrogen-doped magnesium-manganese binary metal oxide solid catalyst can be used for treating water samples with different pH values.
(IV) detailed description of the preferred embodiments
The invention will be further described with reference to specific examples, but the scope of the invention is not limited thereto.
In the following examples, MgMnO containing 3% of N in an amount of 1:1 based on the amount of Mg and Mn y The symbol of-N is MgMnO y -N 3 MgMnO with N doping amount of 7% y The symbol of-N is MgMnO y -N 7 MgMnO with N doping amount of 12% y The symbol of-N is MgMnO y -N 12 MgMnO with N doping amount of 19% y The symbol of-N is MgMnO y -N 19 MgMnO with N doping amount of 28% y The symbol of-N is MgMnO y -N 28 (ii) a MgMnO containing 5% of C with a 1:1 ratio of Mg and Mn y the-C mark is MgMnO y -C 5 MgMnO with C doping amount of 10% y the-C mark is MgMnO y -C 10 MgMnO with C doping amount of 15% y The symbol of-C is MgMnO y -C 15 。
And calculating the concentration of the nitrogen source or the C source solution according to the N/C doping amount. (calculation formula: doping ratio-mass of N contained in Nitrogen Source/mass of catalyst precursor)
Ozone in the following examples was prepared in an ozone generator using oxygen as a raw material, and mixed gas of ozone and oxygen was introduced when acetic acid was degraded.
Example 1: preparation of N (urea) -doped catalyst
(1) 15.38g of Mg (NO) are weighed 3 ) 2 ·6H 2 O solid and 21.47g of Mn (NO) 3 ) 2 The solution was mixed and dissolved in 90mL of redistilled water (0.06 mol of each of Mg and Mn species);
(2) 210mL of NaOH solution (6mol/L) is added into the solution dropwise;
(3) stirring the solution obtained in the step (2) in a temperature-controlled magnetic stirrer at 90 ℃ for 2 hours in an oil bath manner;
(4) cooling and centrifuging the solution obtained in the step (3) to obtain a lower-layer precipitate, washing the lower-layer precipitate with water, centrifuging the lower-layer precipitate again, and repeating the washing and the centrifuging until the pH value of the supernatant is less than 9;
(5) putting the precipitate collected in the step (4) into a vacuum drying oven, and drying for 12h at the temperature of 80 ℃;
(6) grinding the substance obtained in the step (5) into powder, screening to obtain 0.0385-0.05mm of catalyst powder, dropwise adding deionized water into 1g of catalyst powder, and uniformly stirring until the volume of the solution just infiltrates the carrier, so that no excess water exists on the surface of the infiltrated catalyst, and measuring the volume of the solution to be 0.8mL, which is the saturated water absorption capacity of the catalyst powder.
(7) Calculating the amount of urea required by doping according to the doping proportion of 3%, 7%, 12%, 19% and 28% N, respectively weighing 1g of catalyst powder, respectively putting the catalyst powder into 0.8mL of deionized water solution with the concentration of 0.8mL of 0.0804g/mL, 0.1875g/mL, 0.3214g/mL, 0.5088g/mL and 0.7500g/mL of urea aqueous solution, mutually mixing and standing for 12 hours;
(8) putting the substance obtained in the step (7) into a muffle furnace to calcine for 2 hours at 500 ℃ to obtain MgMnO y ，MgMnO y -N 3 ，MgMnO y -N 7 ，MgMnO y -N 12 ，MgMnO y -N 19 ，MgMnO y -N 28 Catalyst (urea is a nitrogen source).
Preparing 250mL of 20mg/L acetic acid solution, adjusting the pH value to 5, and adding MgMnO y ，MgMnO y -N 3 ，MgMnO y -N 7 ，MgMnO y -N 12 ，MgMnO y -N 19 ，MgMnO y -N 28 The catalyst (urea is nitrogen source) is added in an amount of 0.1g, and then the catalyst is added into a columnar reactor, and ozone is introduced into the bottom of the reactor.
The amount of ozone added was 40mg/L (ozone concentration in the mixed gas), and the flow rate of ozone and oxygen was 0.5L/min. The experiment is started, and samples are taken for detection at 0min,3min,6min and 9min respectively.
The detection method comprises the following steps: acetic acid was purified by thermo fisher Dionex Ultimate3000 high performance liquid chromatography.
The effect after 9min of water sample treatment with pH5 is as shown in Table 1:
TABLE 1
Example 2: preparation of N (urea) doped catalyst
(1) 15.38g of Mg (NO) are weighed 3 ) 2 ·6H 2 O solids and 21.47g Mn (NO) 3 ) 2 The solution was mixed and dissolved in 90mL of redistilled water (the amounts of Mg and Mn substances were 0.06mol each);
(2) 210mL of NaOH solution (6mol/L) is added into the solution dropwise;
(3) stirring the solution obtained in the step (2) in a temperature-controlled magnetic stirrer at 90 ℃ for 2 hours in an oil bath manner;
(4) cooling and centrifuging the solution obtained in the step (3) to obtain a lower-layer precipitate, washing and centrifuging the lower-layer precipitate, and repeating the washing and the centrifuging until the pH value of the supernatant of the centrifugation is less than 9;
(5) putting the precipitate collected in the step (4) into a vacuum drying oven, and drying for 12h at the temperature of 80 ℃;
(6) grinding the substance obtained in the step (5) into powder, screening to obtain 0.0385mm-0.05mm of catalyst powder, dropwise adding deionized water into 1g of catalyst powder, and uniformly stirring until the volume of the solution just soaks the carrier, so that no excess water exists on the surface of the soaked catalyst, and measuring the volume of the solution to be 0.8mL, wherein the volume is the saturated water absorption capacity of the catalyst powder.
(7) Calculating the amount of urea required by doping according to the doping proportion of 3%, 7%, 12%, 19% and 28%, respectively weighing 1g of catalyst powder, respectively putting the catalyst powder into 0.8mL of deionized water solution with the concentration of 0.8mL of 0.0804g/mL, 0.1875g/mL, 0.3214g/mL, 0.5088g/mL and 0.7500g/mL of urea aqueous solution, mixing the urea aqueous solution and the urea aqueous solution, and standing for 12 hours;
(8) putting the substance obtained in the step (7) into a muffle furnace to calcine for 2 hours at 500 ℃ to obtain MgMnO y ，MgMnO y -N 3 ，MgMnO y -N 7 ，MgMnO y -N 12 ，MgMnO y -N 19 ，MgMnO y -N 28 Catalyst (urea is a nitrogen source).
Preparing 250mL of 20mg/L acetic acid solution, adjusting the pH value to 7, and adding MgMnO y ，MgMnO y -N 3 ，MgMnO y -N 7 ，MgMnO y -N 12 ，MgMnO y -N 19 ，MgMnO y -N 28 The catalyst (urea is nitrogen source) is added in an amount of 0.1g, and then the catalyst is added into a columnar reactor, and ozone is introduced into the bottom of the reactor.
The amount of ozone added was 40mg/L (ozone concentration in the mixed gas), and the flow rate of ozone and oxygen was 0.5L/min. The experiment is started, and samples are taken for detection at 0min,3min,6min and 9min respectively.
The detection method comprises the following steps: acetic acid was purified by thermo fisher Dionex Ultimate3000 high performance liquid chromatography.
The effect after 9min of water sample treatment with pH7 is shown in Table 2:
TABLE 2
Example 3: preparation of N (urea) doped catalyst
(1) 15.38g of Mg (NO) are weighed 3 ) 2 ·6H 2 O solid and 21.47g of Mn (NO) 3 ) 2 The solution was mixed and dissolved in 90mL of redistilled water (0.06 mol of each of Mg and Mn species);
(2) 210mL of NaOH solution (6mol/L) is added into the solution dropwise;
(3) stirring the solution obtained in the step (2) in a temperature-controlled magnetic stirrer at 90 ℃ for 2 hours in an oil bath manner;
(4) cooling and centrifuging the solution obtained in the step (3) to obtain a lower-layer precipitate, washing the lower-layer precipitate with water, centrifuging the lower-layer precipitate again, and repeating the washing and the centrifuging until the pH value of the supernatant is less than 9;
(5) putting the precipitate collected in the step (4) into a vacuum drying oven, and drying for 12h at the temperature of 80 ℃;
(6) grinding the substance obtained in the step (5) into powder, screening to obtain 0.0385mm-0.05mm of catalyst powder, dropwise adding deionized water into 1g of catalyst powder, and uniformly stirring until the volume of the solution just soaks the carrier, so that no excess water exists on the surface of the soaked catalyst, and measuring the volume of the solution to be 0.8mL, wherein the volume is the saturated water absorption capacity of the catalyst powder.
(7) Calculating the amount of urea required by doping according to the doping proportion of 3%, 7%, 12%, 19% and 28%, respectively weighing 1g of catalyst powder, respectively putting the catalyst powder into 0.8mL of deionized water solution, wherein the concentration of 0.8mL is 0.0804g/mL, 0.1875g/mL, 0.3214g/mL, 0.5088g/mL and 0.7500g/mL of urea aqueous solution, mutually mixing and standing for 12 hours;
(8) putting the substance obtained in the step (7) into a muffle furnace to calcine for 2 hours at 500 ℃ to obtain MgMnO y ，MgMnO y -N 3 ，MgMnO y -N 7 ，MgMnO y -N 12 ，MgMnO y -N 19 ，MgMnO y -N 28 Catalyst (urea is a nitrogen source).
Preparing 250mL of acetic acid solution containing 20mg/L, adjusting the pH to 9, and adding MgMnO y ，MgMnO y -N 3 ，MgMnO y -N 7 ，MgMnO y -N 12 ，MgMnO y -N 19 ，MgMnO y -N 28 The catalyst (urea is nitrogen source) is added in an amount of 0.1g, and then the catalyst is added into a columnar reactor, and ozone is introduced into the bottom of the reactor.
The amount of ozone added was 40mg/L (ozone concentration in the mixed gas), and the flow rate of ozone and oxygen was 0.5L/min. The experiment is started, and samples are taken for detection at 0min,3min,6min and 9min respectively.
The detection method comprises the following steps: acetic acid was purified by thermo fisher Dionex Ultimate3000 high performance liquid chromatography.
The effect of water sample treatment at pH9 for 9min is shown in Table 3:
TABLE 3
Example 4: preparation of N (cyanamide) doped catalyst
(1) 15.38g of Mg (NO) are weighed 3 ) 2 ·6H 2 O solids and 21.47g Mn (NO) 3 ) 2 The solution was mixed and dissolved in 90mL of redistilled water (0.06 mol of each of Mg and Mn species);
(2) 210mL of NaOH solution (6mol/L) is added into the solution dropwise;
(3) stirring the solution obtained in the step (2) in a temperature-controlled magnetic stirrer at 90 ℃ for 2 hours in an oil bath manner;
(4) cooling and centrifuging the solution obtained in the step (3) to obtain a lower-layer precipitate, washing the lower-layer precipitate with water, centrifuging the lower-layer precipitate again, and repeating the washing and the centrifuging until the pH value of the supernatant is less than 9;
(5) putting the precipitate collected in the step (4) into a vacuum drying oven, and drying for 12h at the temperature of 80 ℃;
(6) grinding the substance obtained in the step (5) into powder, screening to obtain 0.0385-0.05mm of catalyst powder, dropwise adding deionized water into 1g of catalyst powder, and uniformly stirring until the volume of the solution just infiltrates the carrier, so that no excess water exists on the surface of the infiltrated catalyst, and measuring the volume of the solution to be 0.8mL, which is the saturated water absorption capacity of the catalyst powder.
(7) Calculating the amount of cyanamide required by doping according to the doping proportion of 3%, 7%, 12%, 19% and 28%, respectively weighing 1g of catalyst powder, respectively putting the catalyst powder into 0.8mL of deionized water solution, 0.8mL of cyanamide aqueous solution with the concentration of 0.0563g/mL, 0.1313g/mL, 0.2250g/mL, 0.3563g/mL and 0.5250g/mL, mutually mixing and standing for 12 hours;
(8) putting the substance obtained in the step (7) into a muffle furnace to calcine for 2 hours at 500 ℃ to obtain MgMnO y ，MgMnO y -N 3 ，MgMnO y -N 7 ，MgMnO y -N 12 ，MgMnO y -N 19 ，MgMnO y -N 28 Catalyst (cyanamide as nitrogen source).
Preparing 250mL of 20mg/L acetic acid solution, adjusting the pH value to 5, and adding MgMnO y ，MgMnO y -N 3 ，MgMnO y -N 7 ，MgMnO y -N 12 ，MgMnO y -N 19 ，MgMnO y -N 28 The catalyst (cyanamide is nitrogen source) is added in an amount of 0.1g, and then the catalyst is added into a columnar reactor, and ozone is introduced into the bottom of the reactor.
The amount of ozone added was 40mg/L (ozone concentration in the mixed gas), and the flow rate of ozone and oxygen was 0.5L/min. The experiment is started, and samples are taken for detection at 0min,3min,6min and 9min respectively.
The detection method comprises the following steps: acetic acid was purified by thermo fisher Dionex Ultimate3000 high performance liquid chromatography.
The effect of water sample treatment at pH5 for 9min is shown in Table 4:
TABLE 4
Example 5: preparation of N (cyanamide) doped catalyst
(1) 15.38g of Mg (NO) are weighed 3 ) 2 ·6H 2 O solid and 21.47g of Mn (NO) 3 ) 2 The solution was mixed and dissolved in 90mL of redistilled water (0.06 mol of each of Mg and Mn species);
(2) 210mL of NaOH solution (6mol/L) is added into the solution dropwise;
(3) stirring the solution obtained in the step (2) in a temperature-controlled magnetic stirrer at 90 ℃ for 2 hours in an oil bath manner;
(4) cooling and centrifuging the solution obtained in the step (3) to obtain a lower-layer precipitate, washing the lower-layer precipitate with water, centrifuging the lower-layer precipitate again, and repeating the washing and the centrifuging until the pH value of the supernatant is less than 9;
(5) putting the precipitate collected in the step (4) into a vacuum drying oven, and drying for 12h at the temperature of 80 ℃;
(6) grinding the substance obtained in the step (5) into powder, screening to obtain 0.0385mm-0.05mm of catalyst powder, dropwise adding deionized water into 1g of catalyst powder, and uniformly stirring until the volume of the solution just soaks the carrier, so that no excess water exists on the surface of the soaked catalyst, and measuring the volume of the solution to be 0.8mL, wherein the volume is the saturated water absorption capacity of the catalyst powder.
(7) Calculating the amount of cyanamide required by doping according to the doping proportion of 3%, 7%, 12%, 19% and 28%, respectively weighing 1g of catalyst powder, respectively putting the catalyst powder into 0.8mL of deionized water solution, 0.8mL of cyanamide aqueous solution with the concentration of 0.0563g/mL, 0.1313g/mL, 0.2250g/mL, 0.3563g/mL and 0.5250g/mL, mutually mixing and standing for 12 hours;
(8) obtained in step (7)Calcining the substance in a muffle furnace at 500 ℃ for 2 hours to obtain MgMnO y ，MgMnO y -N 3 ，MgMnO y -N 7 ，MgMnO y -N 12 ，MgMnO y -N 19 ，MgMnO y -N 28 Catalyst (cyanamide as nitrogen source).
Preparing 250mL of 20mg/L acetic acid solution, adjusting the pH value to 7, and adding MgMnO y ，MgMnO y -N 3 ，MgMnO y -N 7 ，MgMnO y -N 12 ，MgMnO y -N 19 ，MgMnO y -N 28 The catalyst (cyanamide is nitrogen source) is added in an amount of 0.1g, and then the catalyst is added into a columnar reactor, and ozone is introduced into the bottom of the reactor.
The amount of ozone added was 40mg/L (ozone concentration in the mixed gas), and the flow rate of ozone and oxygen was 0.5L/min. The experiment is started, and samples are taken for detection at 0min,3min,6min and 9min respectively.
The detection method comprises the following steps: acetic acid was purified by thermo fisher Dionex Ultimate3000 high performance liquid chromatography.
The effect after 9min of water sample treatment with pH7 is as shown in Table 5:
TABLE 5
Example 6: preparation of N (cyanamide) doped catalyst
(1) 15.38g of Mg (NO) are weighed 3 ) 2 ·6H 2 O solid and 21.47g of Mn (NO) 3 ) 2 The solution was mixed and dissolved in 90mL of redistilled water (0.06 mol of each of Mg and Mn species);
(2) 210mL of NaOH solution (6mol/L) is added into the solution dropwise;
(3) stirring the solution obtained in the step (2) in a temperature-controlled magnetic stirrer at 90 ℃ for 2 hours in an oil bath;
(4) cooling and centrifuging the solution obtained in the step (3) to obtain a lower-layer precipitate, washing the lower-layer precipitate with water, centrifuging the lower-layer precipitate again, and repeating the washing and the centrifuging until the pH value of the supernatant is less than 9;
(5) putting the precipitate collected in the step (4) into a vacuum drying oven, and drying for 12h at the temperature of 80 ℃;
(6) grinding the substance obtained in the step (5) into powder, screening to obtain 0.0385-0.05mm of catalyst powder, dropwise adding deionized water into 1g of catalyst powder, and uniformly stirring until the volume of the solution just infiltrates the carrier, so that no excess water exists on the surface of the infiltrated catalyst, and measuring the volume of the solution to be 0.8mL, which is the saturated water absorption capacity of the catalyst powder.
(7) Calculating the amount of cyanamide required by doping according to the doping proportion of 3%, 7%, 12%, 19% and 28%, respectively weighing 1g of catalyst powder, respectively putting the catalyst powder into 0.8mL of deionized water solution, 0.8mL of cyanamide aqueous solution with the concentration of 0.0563g/mL, 0.1313g/mL, 0.2250g/mL, 0.3563g/mL and 0.5250g/mL, mutually mixing and standing for 12 hours;
(8) putting the substance obtained in the step (7) into a muffle furnace to calcine for 2 hours at 500 ℃ to obtain MgMnO y ，MgMnO y -N 3 ，MgMnO y -N 7 ，MgMnO y -N 12 ，MgMnO y -N 19 ，MgMnO y -N 28 Catalyst (cyanamide as nitrogen source).
Preparing 250mL of 20mg/L acetic acid solution, adjusting the pH value to 9, and adding MgMnO y ，MgMnO y -N 3 ，MgMnO y -N 7 ，MgMnO y -N 12 ，MgMnO y -N 19 ，MgMnO y -N 28 The catalyst (cyanamide is nitrogen source) is added in an amount of 0.1g, and then the catalyst is added into a columnar reactor, and ozone is introduced into the bottom of the reactor.
The amount of ozone added was 40mg/L (ozone concentration in the mixed gas), and the flow rate of ozone and oxygen was 0.5L/min. The experiment is started, and samples are taken for detection at 0min,3min,6min and 9min respectively.
The detection method comprises the following steps: acetic acid was purified by high performance liquid chromatography using a ThermoFisher Dionex Ultimate 3000.
The effect after 9min of water sample treatment at pH9 is as shown in Table 6:
TABLE 6
Example 7: preparation of C (glucose) -doped catalyst
(1) 15.38g of Mg (NO) are weighed 3 ) 2 ·6H 2 O solid and 21.47g of Mn (NO) 3 ) 2 The solution was mixed and dissolved in 90mL of redistilled water (0.06 mol of each of Mg and Mn species);
(2) 210mL of NaOH solution (6mol/L) is added into the solution dropwise;
(3) stirring the solution obtained in the step (2) in a temperature-controlled magnetic stirrer at 90 ℃ for 2 hours in an oil bath manner;
(4) cooling and centrifuging the solution obtained in the step (3) to obtain a lower-layer precipitate, washing the lower-layer precipitate with water, centrifuging the lower-layer precipitate again, and repeating the washing and the centrifuging until the pH value of the supernatant is less than 9;
(5) putting the precipitate collected in the step (4) into a vacuum drying oven, and drying for 12h at the temperature of 80 ℃;
(6) grinding the substance obtained in the step (5) into powder, screening to obtain 0.0385-0.05mm of catalyst powder, dropwise adding deionized water into 1g of catalyst powder, and uniformly stirring until the volume of the solution just infiltrates the carrier, so that no excess water exists on the surface of the infiltrated catalyst, and measuring the volume of the solution to be 0.8mL, which is the saturated water absorption capacity of the catalyst powder.
(7) Calculating the amount of glucose required by doping according to the doping proportion of 5%, 10% and 15% C, respectively weighing 1g of catalyst powder, respectively putting the catalyst powder into 0.8mL of deionized water solution, 0.8mL of glucose aqueous solution with the concentration of 0.04g/mL and 0.085g/mL, mutually mixing and standing for 12 hours;
(8) putting the substance obtained in the step (7) into a muffle furnace to calcine for 2 hours at 500 ℃ to obtain MgMnO y ，MgMnO y -C 5 、MgMnO y -C 10 ，MgMnO y -C 15 Catalyst (glucose as carbon source).
Preparing 250mL of 20mg/L acetic acid solution, adjusting the pH value to 5, and adding MgMnO y -C、MgMnO y -C 5 、MgMnO y -C 10 ，MgMnO y -C 15 The catalyst (glucose as carbon source) was added in an amount of 0.1g, and then the mixture was placed in a column reactor, into the bottom of which ozone was introduced.
The amount of ozone added was 40mg/L (ozone concentration in the mixed gas), and the flow rate of ozone and oxygen was 0.5L/min. The experiment is started, and samples are taken for detection at 0min,3min,6min and 9min respectively.
The detection method comprises the following steps: acetic acid was purified by thermo fisher Dionex Ultimate3000 high performance liquid chromatography.
The effect after 9min of water sample treatment at pH5 is as shown in Table 7:
TABLE 7
Example 8: preparation of C (glucose) -doped catalyst
(1) 15.38g of Mg (NO) are weighed 3 ) 2 ·6H 2 O solids and 21.47g Mn (NO) 3 ) 2 The solution was mixed and dissolved in 90mL of redistilled water (0.06 mol of each of Mg and Mn species);
(2) 210mL of NaOH solution (6mol/L) is added into the solution dropwise;
(3) stirring the solution obtained in the step (2) in a temperature-controlled magnetic stirrer at 90 ℃ for 2 hours in an oil bath manner;
(4) cooling and centrifuging the solution obtained in the step (3) to obtain a lower-layer precipitate, washing the lower-layer precipitate with water, centrifuging the lower-layer precipitate again, and repeating the washing and the centrifuging until the pH value of the supernatant is less than 9;
(5) putting the precipitate collected in the step (4) into a vacuum drying oven, and drying for 12h at the temperature of 80 ℃;
(6) grinding the substance obtained in the step (5) into powder, screening to obtain 0.0385mm-0.05mm of catalyst powder, dropwise adding deionized water into 1g of catalyst powder, and uniformly stirring until the volume of the solution just soaks the carrier, so that no excess water exists on the surface of the soaked catalyst, and measuring the volume of the solution to be 0.8mL, wherein the volume is the saturated water absorption capacity of the catalyst powder.
(7) Calculating the amount of glucose required by doping according to the doping proportion of 5%, 10% and 15% C, respectively weighing 1g of catalyst powder, respectively putting the catalyst powder into 0.8mL of deionized water solution, 0.8mL of glucose aqueous solution with the concentration of 0.04g/mL and 0.085g/mL, mutually mixing and standing for 12 hours;
(8) putting the substance obtained in the step (7) into a muffle furnace to calcine for 2 hours at 500 ℃ to obtain MgMnO y ，MgMnO y -C 5 、MgMnO y -C 10 ，MgMnO y -C 15 Catalyst (glucose as carbon source).
Preparing 250mL of 20mg/L acetic acid solution, adjusting the pH value to 7, and adding MgMnO y -C、MgMnO y -C 5 、MgMnO y -C 10 ，MgMnO y -C 15 The catalyst (glucose as carbon source) was added in an amount of 0.1g, and then the mixture was placed in a column reactor, into the bottom of which ozone was introduced.
The amount of ozone added was 40mg/L (ozone concentration in the mixed gas), and the flow rate of ozone and oxygen was 0.5L/min. The experiment is started, and samples are taken for detection at 0min,3min,6min and 9min respectively.
The detection method comprises the following steps: acetic acid was purified by thermo fisher Dionex Ultimate3000 high performance liquid chromatography.
The effect of water sample treatment at pH7 for 9min is shown in Table 8:
TABLE 8
Example 9: preparation of C (glucose) -doped catalyst
(1) 15.38g of Mg (NO) are weighed 3 ) 2 ·6H 2 O solid and 21.47g of Mn (NO) 3 ) 2 The solution was mixed and dissolved in 90mL of redistilled water (the amounts of Mg and Mn substances were 0.06mol each);
(2) 210mL of NaOH solution (6mol/L) is added into the solution dropwise;
(3) stirring the solution obtained in the step (2) in a temperature-controlled magnetic stirrer at 90 ℃ for 2 hours in an oil bath manner;
(4) cooling and centrifuging the solution obtained in the step (3) to obtain a lower-layer precipitate, washing the lower-layer precipitate with water, centrifuging the lower-layer precipitate again, and repeating the washing and the centrifuging until the pH value of the supernatant is less than 9;
(5) putting the precipitate collected in the step (4) into a vacuum drying oven, and drying for 12h at the temperature of 80 ℃;
(6) grinding the substance obtained in the step (5) into powder, screening to obtain 0.0385-0.05mm of catalyst powder, dropwise adding deionized water into 1g of catalyst powder, and uniformly stirring until the volume of the solution just infiltrates the carrier, so that no excess water exists on the surface of the infiltrated catalyst, and measuring the volume of the solution to be 0.8mL, which is the saturated water absorption capacity of the catalyst powder.
(7) Calculating the amount of glucose required by doping according to the doping proportion of 5%, 10% and 15% C, respectively weighing 1g of catalyst powder, respectively putting the catalyst powder into 0.8mL of deionized water solution, 0.8mL of glucose aqueous solution with the concentration of 0.04g/mL and 0.085g/mL, mutually mixing and standing for 12 h;
(8) putting the substance obtained in the step (7) into a muffle furnace to calcine for 2 hours at 500 ℃ to obtain MgMnO y ，MgMnO y -C 5 、MgMnO y -C 10 ，MgMnO y -C 15 Catalyst (glucose as carbon source).
Preparing 250mL of 20mg/L acetic acid solution, adjusting the pH value to 9, and adding MgMnO y -C、MgMnO y -C 5 、MgMnO y -C 10 ，MgMnO y -C 15 The catalyst (glucose as carbon source) was added in an amount of 0.1g, and then the mixture was placed in a column reactor, into the bottom of which ozone was introduced.
The amount of ozone added was 40mg/L (ozone concentration in the mixed gas), and the flow rate of ozone and oxygen was 0.5L/min. The experiment is started, and samples are taken for detection at 0min,3min,6min and 9min respectively.
The detection method comprises the following steps: acetic acid was purified by thermo fisher Dionex Ultimate3000 high performance liquid chromatography.
The effect after 9min of water sample treatment at pH9 is as shown in Table 9:
TABLE 9
From the above C-doped examples (examples 7 to 9), it is understood that the carbon-doped catalyst prepared by using glucose as the C source is O when the pH is 5,7 acetic acid is treated 3 /MgMnO y -C 5 Has better effect than O 3 /MgMnO y The catalytic efficiency of (2) is high. With increasing pH, O 3 /MgMnO y -C 5 And O 3 /MgMnO y The difference in catalytic efficiency becomes gradually smaller, and even when acetic acid having a pH of 9 is treated, the C doping has a very weak influence on the catalytic effect. From the above N-doped examples (examples 1 to 6), it can be seen that when acetic acid having pH values of 5,7 and 9 is treated, all of them are O 3 /MgMnO y -N 12 The catalyst has better effect, and O is generated along with the increase of pH 3 /MgMnO y -N 12 And O 3 /MgMnO y The catalytic efficiency gap of (2) is gradually reduced, and in addition, urea is used as O of an N source 3 /MgMnO y -N 12 O with dicyandiamide as N source 3 /MgMnO y -N 12 And O with glucose as C source 3 /MgMnO y -C 5 The catalytic ozonation of acetic acid is more effective. The N-doped catalyst with urea as an N source can be used for water quality conditions with different pH values, has a good effect of catalyzing and oxidizing acetic acid, and can achieve the best effect of degrading acetic acid.
Claims (10)
1. An N-doped manganese-magnesium binary oxide, characterized in that the N-doped manganese-magnesium binary oxide is prepared as follows:
dissolving magnesium nitrate and manganese nitrate in secondary distilled water, dropwise adding a NaOH solution, stirring and reacting at 70-120 ℃ for 1-3 h, cooling and centrifuging the obtained reaction liquid, taking the lower-layer precipitate, washing until the pH of a washing liquid is less than 9, drying in vacuum, grinding to obtain a carrier, dropwise adding a nitrogen source aqueous solution, fully mixing, standing for 5-15 h, and calcining at 200-800 ℃ for 1-3 h to obtain the N-doped manganese-magnesium binary oxide;
the mass ratio of the magnesium nitrate to the manganese nitrate is 1-2: 1; the ratio of the amount of NaOH contained in the NaOH solution to the total amount of magnesium nitrate and manganese nitrate is 6-12: 1; the volume of the water solution of the nitrogen source is equal to the saturated water absorption capacity of the carrier; the nitrogen source contained in the aqueous solution of the nitrogen source is urea or cyanamide; the mass of the nitrogen source is 3-28% of the mass of the carrier based on the theoretical nitrogen content.
2. The N-doped manganese-magnesium binary oxide of claim 1, wherein: the volume of the secondary distilled water is 0.5-1.0L/mol based on the sum of the amounts of the magnesium nitrate and the manganese nitrate.
3. The N-doped manganese-magnesium binary oxide of claim 1, wherein: the concentration of the NaOH solution is 4-8 mol/L.
4. The N-doped manganese-magnesium binary oxide of claim 1, wherein: the mass ratio of the magnesium nitrate to the manganese nitrate is 1: 1.
5. The N-doped manganese-magnesium binary oxide of claim 1, wherein: the nitrogen source in the aqueous solution of the nitrogen source is urea.
6. The N-doped manganese-magnesium binary oxide of claim 1, wherein: the mass of the nitrogen source is 19% of the mass of the carrier in terms of the theoretical nitrogen content.
7. The use of an N-doped manganese-magnesium binary oxide according to claim 1 as a catalyst for the catalytic ozonation of acetic acid in an acetic acid-containing solution.
8. The use according to claim 7, characterized in that the use is: adding the N-doped manganese-magnesium binary oxide into the acetic acid-containing solution, placing the obtained mixture into a reactor, and introducing ozone from the bottom of the reactor for degradation.
9. The use of claim 8, wherein: the pH of the acetic acid-containing solution is 5-9; the concentration of the acetic acid-containing solution is 20mg/L, and the volume of the acetic acid-containing solution is 2.5L/g based on the mass of the N-doped manganese-magnesium binary oxide.
10. The use of claim 8, wherein: the ozone is introduced into the reactor in the form of a mixed gas of ozone and oxygen, the flow rate of the mixed gas is 0.5L/min, and the concentration of the ozone in the mixed gas is 40 mg/L.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210522344.3A CN114931963A (en) | 2022-05-13 | 2022-05-13 | N-doped manganese-magnesium binary oxide and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210522344.3A CN114931963A (en) | 2022-05-13 | 2022-05-13 | N-doped manganese-magnesium binary oxide and preparation method and application thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN114931963A true CN114931963A (en) | 2022-08-23 |
Family
ID=82864092
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210522344.3A Pending CN114931963A (en) | 2022-05-13 | 2022-05-13 | N-doped manganese-magnesium binary oxide and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114931963A (en) |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103964412A (en) * | 2013-01-30 | 2014-08-06 | 北京化工大学 | Preparation method of nitrogen-doped porous-structure carbon material |
| CN113797924A (en) * | 2021-09-28 | 2021-12-17 | 杭州诚洁环保有限公司 | Single-atom carbon-doped magnesium-manganese binary oxide and preparation method and application thereof |
-
2022
- 2022-05-13 CN CN202210522344.3A patent/CN114931963A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103964412A (en) * | 2013-01-30 | 2014-08-06 | 北京化工大学 | Preparation method of nitrogen-doped porous-structure carbon material |
| CN113797924A (en) * | 2021-09-28 | 2021-12-17 | 杭州诚洁环保有限公司 | Single-atom carbon-doped magnesium-manganese binary oxide and preparation method and application thereof |
Non-Patent Citations (2)
| Title |
|---|
| WEIYE WANG等: "Development of an MFC-powered BEF system with novel Fe–Mn–Mg/CF composite cathode to degrade refractory pollutants", 《JOURNAL OF CLEANER PRODUCTION》, vol. 326, no. 129348, 13 October 2021 (2021-10-13), pages 1 - 15, XP086852256, DOI: 10.1016/j.jclepro.2021.129348 * |
| 郭琳 等: "基于催化臭氧氧化水溶液中氨氮的Mg/Mn 催化剂制备研究", 《有色金属工程》, vol. 8, no. 3, 30 June 2018 (2018-06-30), pages 128 - 132 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105174416B (en) | A kind of method that persulfate degraded dichloro quinolinic acid organic pollution is catalyzed based on carried active carbon | |
| CN106807376B (en) | Magnetic nano composite catalyst and preparation method and application thereof | |
| CN112264064B (en) | Preparation method of copper single-atom carbon-based catalyst and application of copper single-atom carbon-based catalyst in degradation of phenolic organic pollutants | |
| CN110420655A (en) | A kind of graphitic carbon package iron-nitrogen-carbon solid phase fenton catalyst preparation method and applications | |
| CN108212158B (en) | Fenton catalyst and preparation method and application thereof | |
| CN113877579B (en) | Preparation method and application of catalyst for degrading endocrine disruptors | |
| CN113856725B (en) | g-C 3 N 4 /Fe/MoS 2 Ternary flower-like heterojunction material and preparation method and application thereof | |
| CN115779955B (en) | Lignin carbon-loaded Fe-N single-atom catalyst | |
| CN109772402B (en) | Fenton-like reaction catalyst, preparation method, method for degrading organic sewage and application of Fenton-like reaction catalyst | |
| CN112517042B (en) | Nitrogen-doped Fenton-like catalyst and preparation method and application thereof | |
| CN112919576A (en) | Method for removing antibiotics in wastewater by using biochar loaded bimetal to promote ionizing irradiation | |
| CN111659453B (en) | Catalyst for visible light-ozone synergistic catalysis and preparation method thereof | |
| CN111804300B (en) | Ozone oxidation catalyst for advanced treatment of organic wastewater and preparation method thereof | |
| CN114931963A (en) | N-doped manganese-magnesium binary oxide and preparation method and application thereof | |
| WO2024077867A1 (en) | Preparation of supported catalyst for fenton fluidized bed and method for treating industrial water | |
| CN105032463A (en) | CsPMo/g-C3N4-Bi2O3 photocatalyst and preparation method therefor and application thereof in phenolic wastewater treatment | |
| CN115400782B (en) | Copper-modified porous hollow spherical graphite phase carbon nitride and preparation method and application thereof | |
| CN113893882B (en) | Copper oxide catalyst based on metal organic ligand and preparation method and application thereof | |
| CN114618592A (en) | Preparation method of efficient heterogeneous Fenton catalyst and application of efficient heterogeneous Fenton catalyst in printing and dyeing wastewater treatment | |
| CN113797924A (en) | Single-atom carbon-doped magnesium-manganese binary oxide and preparation method and application thereof | |
| CN115254153B (en) | Manganese sulfide doped ferric oxychloride, and preparation method and application thereof | |
| CN115245834B (en) | Efficient neutral heterogeneous Fenton catalyst FeOF and preparation method and application thereof | |
| CN115646525B (en) | Iron-nitrogen co-doped biochar, preparation method thereof and application thereof in wastewater treatment | |
| CN111167506B (en) | Sr2FeO4/SBA-15 composite catalyst material and preparation method thereof | |
| CN117680181A (en) | Ultra-high-load single-atom copper catalyst and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |