CN110548519A - porous nano cobalt-doped zinc manganate spinel catalyst and preparation method and application thereof - Google Patents
porous nano cobalt-doped zinc manganate spinel catalyst and preparation method and application thereof Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 30
- 229910052596 spinel Inorganic materials 0.000 title claims abstract description 29
- 239000011029 spinel Substances 0.000 title claims abstract description 29
- XRFJZINEJXCFNW-UHFFFAOYSA-N [Zn+2].[O-][Mn]([O-])(=O)=O Chemical compound [Zn+2].[O-][Mn]([O-])(=O)=O XRFJZINEJXCFNW-UHFFFAOYSA-N 0.000 title claims abstract description 17
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims abstract description 30
- 238000010438 heat treatment Methods 0.000 claims abstract description 17
- 239000011259 mixed solution Substances 0.000 claims abstract description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229940011182 cobalt acetate Drugs 0.000 claims abstract description 11
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims abstract description 11
- 229940071125 manganese acetate Drugs 0.000 claims abstract description 11
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 claims abstract description 11
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 9
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000000137 annealing Methods 0.000 claims abstract description 9
- 239000008367 deionised water Substances 0.000 claims abstract description 9
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 9
- 229910017604 nitric acid Inorganic materials 0.000 claims abstract description 9
- 239000004246 zinc acetate Substances 0.000 claims abstract description 9
- 238000001035 drying Methods 0.000 claims abstract description 8
- 238000003756 stirring Methods 0.000 claims abstract description 7
- 229960004106 citric acid Drugs 0.000 claims abstract description 5
- 238000000227 grinding Methods 0.000 claims abstract description 5
- 229960000314 zinc acetate Drugs 0.000 claims abstract description 5
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 24
- 238000006731 degradation reaction Methods 0.000 claims description 9
- 230000015556 catabolic process Effects 0.000 claims description 7
- 230000004913 activation Effects 0.000 claims description 3
- FHHJDRFHHWUPDG-UHFFFAOYSA-L peroxysulfate(2-) Chemical compound [O-]OS([O-])(=O)=O FHHJDRFHHWUPDG-UHFFFAOYSA-L 0.000 claims description 3
- 230000003647 oxidation Effects 0.000 abstract description 8
- 238000007254 oxidation reaction Methods 0.000 abstract description 8
- 239000011572 manganese Substances 0.000 description 11
- 239000000243 solution Substances 0.000 description 9
- 238000000034 method Methods 0.000 description 8
- 239000000463 material Substances 0.000 description 7
- 239000002086 nanomaterial Substances 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 5
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 4
- 238000009303 advanced oxidation process reaction Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000011701 zinc Substances 0.000 description 3
- 101100464695 Drosophila melanogaster aop gene Proteins 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- 239000000356 contaminant Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
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- 229910052748 manganese Inorganic materials 0.000 description 2
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- 238000012986 modification Methods 0.000 description 2
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- 229910052725 zinc Inorganic materials 0.000 description 2
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
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- 150000002500 ions Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
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- 239000012528 membrane Substances 0.000 description 1
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- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000011941 photocatalyst Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
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- 230000000171 quenching effect Effects 0.000 description 1
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- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 229910021642 ultra pure water Inorganic materials 0.000 description 1
- 239000012498 ultrapure water Substances 0.000 description 1
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Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/005—Spinels
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/889—Manganese, technetium or rhenium
- B01J23/8892—Manganese
-
- 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
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
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- 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
- C02F2101/34—Organic compounds containing oxygen
- C02F2101/345—Phenols
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/02—Specific form of oxidant
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/02—Specific form of oxidant
- C02F2305/023—Reactive oxygen species, singlet oxygen, OH radical
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- 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
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/30—Wastewater or sewage treatment systems using renewable energies
- Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy
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- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
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Abstract
the invention belongs to the technical field of advanced oxidation, and discloses a porous nano cobalt-doped zinc manganate (ZnCoMnO 4) spinel catalyst and a preparation method and application thereof, wherein the catalyst is prepared by dissolving zinc acetate, manganese acetate, cobalt acetate and citric acid in deionized water and nitric acid to obtain a mixed solution, heating the mixed solution to 80-100 ℃ under the condition of stirring to prepare gel, drying the gel at 150-190 ℃, grinding the obtained dried gel, and heating the ground dried gel to 550-650 ℃ in the air for annealing.
Description
Technical Field
The invention belongs to the technical field of advanced oxidation, and particularly relates to a porous nano cobalt-doped zinc manganate (ZnCoMnO 4) spinel catalyst, and a preparation method and application thereof.
background
With the rapid development of economy, phenolic organic matters are widely applied to industries such as petrochemical industry, medicine, synthetic fiber and the like, and a large amount of phenolic wastewater is generated. The phenol organic matters have strong toxicity and are difficult to be directly biologically treated, and at present, the common treatment methods comprise an adsorption method, a membrane treatment method, a chemical precipitation method and advanced oxidation technologies (AOPs).
Advanced oxidation technologies (OH-AOPs) based on induction of hydroxyl radicals (OH-) have often been investigated for degradation of even organic contaminants in water, because OH-driven oxidation is very rapid and almost non-selective OH-AOPs including UV/O 3/H 2 O 2, O 3/H 2 O 2, Fenton reaction etc. in recent years, AOPs induced by sulfate radicals (SO 4 - ·) have received increasing attention 483SO 6 has a significantly higher reduction potential of 2.6V, slightly lower than OH- (2.9V). furthermore, it shows a non-selective oxidation mode and can rapidly decompose most of the organic contaminants in water, sulfate is converted to non-toxic sulfate after oxidation, without any secondary treatment.
Disclosure of Invention
In order to solve the defects in the prior art, the invention aims at providing the ZnCoMnO 4 spinel catalyst with the porous nano structure, which has the porous structure and the good chemical and physical stability as a catalytic material, and can activate peroxymonosulfate to generate SO 4 - · and OH, SO that phenol is effectively degraded, and the cycle experiment shows that the ZnCoMnO 4 spinel catalyst has good reusability.
Another object of the present invention is to provide a method for preparing the above ZnCoMnO 4 spinel catalyst having a porous nanostructure.
The invention also aims to provide application of the layered porous ZnCoMnO 4 spinel catalyst.
The purpose of the invention is realized by the following technical scheme:
A porous nanometer cobalt-doped zinc manganate spinel catalyst is prepared by dissolving zinc acetate, manganese acetate, cobalt acetate and citric acid in deionized water and nitric acid to obtain a mixed solution A; heating the mixed solution A to 80-100 ℃ under the condition of stirring to obtain gel; and drying the gel at 150-190 ℃, grinding the obtained dry gel, and heating to 550-650 ℃ in air for annealing to obtain the gel.
preferably, the ratio of the moles of zinc acetate, the total moles of manganese acetate and cobalt acetate, the moles of citric acid, the volume of deionized water and the volume of nitric acid in the mixed solution a is 2.5 mmol: 5 mmol: (12-16) mmol: 30 ml: (1.5-2.5) ml.
preferably, the molar ratio of the manganese acetate to the cobalt acetate is (0.5-0.9): (0.1-0.5).
The preparation method of the porous nano cobalt-doped zinc manganate spinel catalyst comprises the following specific steps:
S1, dissolving zinc acetate, manganese acetate, cobalt acetate and citric acid in deionized water and nitric acid to obtain a mixed solution A;
s2, heating the mixed solution A to 80-100 ℃ under the stirring condition to obtain gel;
s3, drying the gel at 150-190 ℃, grinding the obtained dry gel, heating the ground dry gel to 550-650 ℃ in the air, and annealing to obtain the porous nano ZnCoMnO 4 spinel catalyst.
Preferably, the heating time in the step S2 is 4-8 h.
Preferably, the drying time in the step S3 is 8-16 h; the annealing time is 5-7 h.
Preferably, the temperature rise rate in step S3 is 8-12 ℃/min.
The porous nano cobalt-doped zinc manganate spinel catalyst is applied to activating peroxymonosulfate to degrade phenol.
The invention adopts a simple sol-gel spontaneous combustion method to prepare pure ZnCoMnO 4 spinel powder with a porous nano structure, the nano material has a large specific surface area, a large number of active sites can be provided, the catalytic efficiency is improved, Mn and Zn ions in the material can effectively inhibit the precipitation of Co, the stability of the material is greatly improved, and the environmental risk is reduced.
The mechanism of transition metal activation of PMS is as follows:
S2O8 2-+Me2+→SO4 -·+SO4 2-+Me3+
HSO5 -+Me2+→SO4 -·+OH-+Me3+
SO4 -·+OH-→SO4 2-+OH·
Compared with the prior art, the invention has the following beneficial effects:
1. The invention synthesizes the ZnCoMnO 4 spinel composite photocatalyst with a porous nano structure for the first time, and the nano material has larger specific surface area.
2. The catalyst synthesized by the method has good physical and chemical stability and shows good reusability.
3. The invention has simple synthesis process, good catalytic performance and basic conditions for practical application.
Drawings
Fig. 1 is SEM and TEM photographs of ZnCoMnO 4 in example 1.
FIG. 2 is an XPS plot of ZnCoMnO 4 in example 1;
FIG. 3 is an EPR diagram of the PMS system of comparative example 1 and the ZnCoMnO 4 + PMS system of example 1;
FIG. 4 is a graph of the efficiency of phenol degradation in the PMS system of comparative example 1 and the ZnCoMnO 4 + PMS system of example 1;
FIG. 5 is a graph of the cycle efficiency for phenol degradation using ZnCoMnO 4 of example 1.
Detailed Description
The following examples are presented to further illustrate the present invention and should not be construed as limiting the invention. Unless otherwise specified, the technical means used in the examples are conventional means well known to those skilled in the art. Reagents, methods and apparatus used in the present invention are conventional in the art unless otherwise indicated.
example 1
Dissolving 1.2.5mmol of zinc acetate, 2.5mmol of manganese acetate, 2.5mmol of cobalt acetate and 12mmol of citric acid in 30ml of deionized water and 2.5ml of nitric acid to obtain a mixed solution;
2. Continuously stirring the mixed solution, heating to 90 ℃, and keeping the temperature for 8 hours to obtain viscous gel;
3. the gel was put in an oven at 170 ℃ for 8 hours to remove the remaining water, the dried gel was thoroughly ground and annealed at 550 ℃ for 7 hours in air (heating rate: 10 ℃ C. min -1) to give ZnCoMnO 4 spinel powder.
FIG. 1 is SEM and TEM photographs of a ZnCoMnO 4 spinel material in this example, it can be seen from FIG. 1 that the surface of the ZnCoMnO 4 spinel material exhibits a porous structure, which is agglomerated from 50-100nm nanoparticles, the porous structure may be due to combustion of citric acid as a raw material during the annealing stage producing a large amount of CO 2, and the pores are formed when the gas is released from the solid.the porous structure of the catalyst is due to the presence of surface grains, which allows the catalyst to have a large specific surface area, which provides more reaction sites, while enhancing the catalytic activity of the material.FIG. 2 is a XPS diagram of ZnCoMnO 4 in this example, the chemical composition of ZnCoMnO 4 is provided by X-ray photoelectron spectroscopy (XPS). The (a) in FIG. 2 shows a typical broad scan XPS spectra, illustrating the presence of Zn, Co, Mn and O in the material.2 (b) shows a high resolution Zn 2p spectrum, the two main peaks with binding energy values of 8 and 6 eV, which are 2+ eV, and the Mn 5842 and Mn 4642 are shown by the respective Mn 4624 and Mn 4642 peaks of the Mn 641.9 and Mn 4624 and Mn 4642 c spectra of the Mn 465 and Mn 641.9 as well as shown in the above 97,32,32,32,32,32,32,32,48,48,48,48,48,32,48,48,32.
Example 2
Dissolving 1.2.5mmol of zinc acetate, 4.5mmol of manganese acetate, 0.5mmol of cobalt acetate and 16mmol of citric acid in 30ml of deionized water and 1.5ml of nitric acid to obtain a mixed solution;
4. continuously stirring the mixed solution, heating to 90 ℃, and keeping the temperature for 8 hours to obtain viscous gel;
5. The gel was put in an oven at 170 ℃ for 16 hours to remove the remaining water, and the dried gel was thoroughly ground and annealed at 650 ℃ for 5 hours in air (heating rate: 10 ℃ C. min -1) to give ZnCoMnO 4 spinel powder.
Application example 1
4The phenol degradation reaction was carried out in a 600mL reactor in which 15-25mg/L of phenol solution was continuously stirred at 400-.
the ZnCoMnO 4 catalyst prepared in example 1 was applied to ZnCoMnO 4 + PMS system and tested for performance fig. 3 is a EPR graph of PMS system (solution of PMS and phenol) and ZnCoMnO 4 + PMS system (solution of PMS, catalyst and phenol) it can be seen that SO 4 - · and OH · signals in solution are weak only when PMS is present and that SO 4 - · and OH · signals are greatly enhanced after activation of ZnCoMnO 4 nanomaterial, indicating that SO 4 - · and OH · concentration in solution are increased fig. 4 is a graph of efficiency of phenol degradation in PMS system and ZnCoMnO 4 + PMS system as can be seen from fig. 4. phenol is not substantially degraded in PMS system, when PMS is activated by adding ZnCoMnO 4, a large amount of SO 4 - · and OH · are generated in system, SO that phenol is rapidly decomposed and after 45 minutes of reaction, phenol removal rate reaches 97.8%, fig. 5 is ZnCoMnO 4, zncomno. 5 shows that the degradation of phenol is reduced by cycle of ZnCoMnO 4, which shows that there is good performance due to the cycle of PMS 3688.
Comparative example 1
the phenol degradation reaction was carried out in a 600mL reactor with 15-25mg/L phenol solution being continuously stirred at 400-500 rpm. The reactor was held in place by a holder and immersed in a water bath equipped with a temperature controller. Unless otherwise stated, the reaction temperature was maintained at 25 ℃. 2g/L PMS was added to the solution to initiate catalytic oxidation. After the reaction started, 1mL of the solution was taken at the specified time and then injected into an HPLC vial and mixed with 0.5mL of a quenching agent in methanol. The concentration of the phenol solution was analyzed on hplc (shimadzu hplc) using a UV detector at a detection wavelength of 270 nm. The organics were separated using a C18 column (2.7. mu.L, 100X 2.1 mm). The mobile phase was a mixture of ultrapure water and acetonitrile (9: 1, v/v), the flow rate was 0.5mL/min, and the injection volume was 10. mu.L.
The data are compiled to give a phenol degradation rate table from table 1, it is seen that the removal rate of phenol by the ZnCoMnO 4 + PMS system (97.8%) is significantly improved compared to the PMS system alone (1.46%).
TABLE 1 removal rate of catalytically degraded phenol after 45min reaction in application example 1 and comparative example 1 systems
| Catalyst and process for preparing same | PMS | ZnCoMnO4+PMS |
| Phenol removal rate (%) | 1.46％ | 97.8％ |
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations and simplifications are intended to be included in the scope of the present invention.
Claims (10)
1. A porous nanometer cobalt-doped zinc manganate spinel catalyst is characterized in that zinc acetate, manganese acetate, cobalt acetate and citric acid are dissolved in deionized water and nitric acid to obtain a mixed solution; heating the mixed solution to 80-100 ℃ under the condition of stirring to obtain gel; and drying the gel at 150-190 ℃, grinding the obtained dry gel, and heating to 550-650 ℃ in air for annealing to obtain the gel.
2. The porous nano cobalt-doped zinc manganate spinel catalyst of claim 1, wherein the molar ratio of zinc acetate, total molar of manganese acetate and cobalt acetate, molar of citric acid, volume of deionized water and volume of nitric acid in said mixed solution is 2.5 mmol: 5 mmol: (12-16) mmol: 30 ml: (1.5-2.5) ml.
3. The porous nano cobalt-doped zinc manganate spinel catalyst of claim 2, wherein the molar ratio of manganese acetate to cobalt acetate is (0.5-0.9): (0.1-0.5).
4. The porous nano cobalt-doped zinc manganate spinel catalyst of claim 1, wherein the heating time is 4-8 h, the drying time is 8-16 h, and the annealing time is 5-7 h.
5. The preparation method of the porous nano cobalt-doped zinc manganate spinel catalyst according to any of claims 1-4, characterized by comprising the following specific steps:
S1, dissolving zinc acetate, manganese acetate, cobalt acetate and citric acid in deionized water and nitric acid to obtain a mixed solution;
S2, heating the mixed solution to 80-100 ℃ under the stirring condition to obtain gel;
S3, drying the gel at 150-190 ℃, grinding the obtained dry gel, heating the ground dry gel to 550-650 ℃ in the air, and annealing to obtain the porous nano ZnCoMnO 4 spinel catalyst.
6. The preparation method of the porous nano cobalt-doped zinc manganate spinel catalyst of claim 5, wherein the heating time in step S2 is 4-8 h.
7. The preparation method of the porous nano cobalt-doped zinc manganate spinel catalyst of claim 5, wherein the drying time in step S3 is 8-16 h.
8. the preparation method of the porous nano cobalt-doped zinc manganate spinel catalyst of claim 5, wherein the annealing time in step S3 is 5-7 h.
9. The preparation method of the porous nano cobalt-doped zinc manganate spinel catalyst of claim 5, wherein the temperature raising rate in step S3 is 8-12 ℃/min.
10. Use of the porous nanocobalt-doped zinc manganate spinel catalyst of any of claims 1-4 in the activation of peroxymonosulfate for the degradation of phenol.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201910727144.XA CN110548519B (en) | 2019-08-07 | 2019-08-07 | Porous nano cobalt-doped zinc manganate spinel catalyst and preparation method and application thereof |
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| CN201910727144.XA CN110548519B (en) | 2019-08-07 | 2019-08-07 | Porous nano cobalt-doped zinc manganate spinel catalyst and preparation method and application thereof |
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| Publication Number | Publication Date |
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| CN110548519A true CN110548519A (en) | 2019-12-10 |
| CN110548519B CN110548519B (en) | 2022-07-12 |
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