CN110548519B - 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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- 229910052596 spinel Inorganic materials 0.000 title claims abstract description 23
- 239000011029 spinel Substances 0.000 title claims abstract description 23
- 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 9
- 238000002360 preparation method Methods 0.000 title claims abstract description 7
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract description 30
- 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 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 16
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- 229940011182 cobalt acetate Drugs 0.000 claims abstract description 10
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims abstract description 10
- 229940071125 manganese acetate Drugs 0.000 claims abstract description 10
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 claims abstract description 10
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 8
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000008367 deionised water Substances 0.000 claims abstract description 8
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 8
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- 239000004246 zinc acetate Substances 0.000 claims abstract description 8
- 238000000137 annealing Methods 0.000 claims abstract description 6
- 238000001035 drying Methods 0.000 claims abstract description 6
- 230000003213 activating effect Effects 0.000 claims abstract description 4
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- 238000000034 method Methods 0.000 claims description 11
- 238000006731 degradation reaction Methods 0.000 claims description 7
- 230000015556 catabolic process Effects 0.000 claims description 5
- FHHJDRFHHWUPDG-UHFFFAOYSA-L peroxysulfate(2-) Chemical compound [O-]OS([O-])(=O)=O FHHJDRFHHWUPDG-UHFFFAOYSA-L 0.000 claims description 4
- 239000000463 material Substances 0.000 abstract description 11
- 230000003647 oxidation Effects 0.000 abstract description 9
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- 238000002474 experimental method Methods 0.000 abstract description 3
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- 239000000243 solution Substances 0.000 description 12
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- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 6
- 238000009303 advanced oxidation process reaction Methods 0.000 description 6
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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
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- B01J35/60—
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- B01J35/61—
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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
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/34—Organic compounds containing oxygen
- C02F2101/345—Phenols
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/02—Specific form of oxidant
-
- 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
-
- 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
Abstract
The invention belongs to the technical field of advanced oxidation and discloses porous nano cobalt-doped zinc manganate (ZnCoMnO)4) Spinel catalyst, preparation method and application thereof. 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; 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. The catalyst has a porous structure and a catalytic material with good chemical and physical stability, and can activate persulfate to generate SO4 ‑·And OH to effectively degrade phenol, and the cycle experiment shows that ZnCoMnO4The spinel catalyst has good reutilization property, and can be applied to the field of degrading phenol by activating persulfate.
Description
Technical Field
The invention belongs to the technical field of advanced oxidation, and particularly relates to porous nano cobalt-doped zinc manganate (ZnCoMnO)4) Spinel catalyst, 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 techniques (OH-AOPs) based on the induction of hydroxyl radicals (OH-) are often investigated for the degradation of even organic contaminants in water, because OH-driven oxidation is very rapid and almost non-selective. OH-AOPs include UV/O3，UV/H2O2，O3/H2O2Fenton reaction, etc. In recent years, however, the radical (SO) is derived from sulfate radicals4 -·) Induced AOPs are of increasing interest. SO (SO)4 -·Has a significantly high reduction potential of 2.6V, which is slightly lower than OH (2.9V). In addition, it exhibits a non-selective oxidation mode and can rapidly decompose most organic pollutants in water. The sulfate can be converted into nontoxic sulfate after oxidation, and no secondary treatment is needed. Thus, sulfate-based AOPs (SR-AOPs) are environmentally friendly. Permonosulfate (PMS) is generally used as SO4 -·But the source of the sulfate ion (S) is stable due to PMS, and the sulfate ion is generated after dissolving in water under the condition of normal temperature2O8 2-) The reaction rate is slow, and organic pollutants are difficult to degrade. Therefore, PMS needs to be activated by heating, catalyst or UV. The transition metal catalyst can activate PMS at normal temperature, and is widely used, wherein Co is2+The activation efficiency is the best, but the toxicity is strong, and the application of Co materials is limited. Thus, in the water treatment process, an efficient and stable catalyst is prepared to produce OH and SO4 -·Is important.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention mainly aims to provide ZnCoMnO with a porous nano structure4A spinel catalyst. The catalyst has a porous structure and a catalytic material with good chemical and physical stability, and can activate peroxymonosulfate to generate SO4 -·And OH to effectively degrade phenol, and the cycle experiment shows that ZnCoMnO4The spinel catalyst has good reusability.
It is another object of the present invention to provide the above ZnCoMnO having a porous nanostructure4A preparation method of a spinel catalyst.
It is a further object of the present invention to provide ZnCoMnO having the layered porous structure as described above4The application of 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 ZnCoMnO4A 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 with a porous nano structure4Spinel powder. The sodium isThe rice material has a large specific surface area, can provide a large number of active sites, and improves the catalytic efficiency. And Mn and Zn ions in the material can effectively inhibit the precipitation of Co, so that 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 ZnCoMnO with a porous nano structure for the first time4The spinel composite photocatalyst has a large 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 shows ZnCoMnO of example 14SEM and TEM photographs.
FIG. 2 shows ZnCoMnO of example 14XPS plots of (c);
FIG. 3 shows PMS system in comparative example 1 and ZnCoMnO in example 14+ EPR diagram of PMS system;
FIG. 4 shows PMS system in comparative example 1 and ZnCoMnO in example 14+ phenol degradation efficiency map in PMS system;
FIG. 5 shows ZnCoMnO of application example 14Graph of the cycle efficiency of degrading phenol.
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 obtain ZnCoMnO4Spinel powder.
FIG. 1 shows ZnCoMnO of the present example4SEM and TEM photographs of spinel materials. As can be seen from FIG. 1, ZnCoMnO4The surface of the spinel material exhibits a porous structure, which is agglomerated from 50-100nm nanoparticles. The porous structure may be due to the combustion of citric acid as a raw material during the annealing stage to produce a large amount of CO2Pores are formed when the gas is released from the solid. The porous structure of the catalyst is due to the existence of surface grains, so that the catalyst has larger specific surface area, more reaction sites can be provided, and the catalytic activity of the material is enhanced. FIG. 2 shows ZnCoMnO in this example4An XPS map of (A); ZnCoMnO4The chemical composition of (a) is provided by X-ray photoelectron spectroscopy (XPS). A typical broad scan XPS spectrum is shown in figure 2 (a), illustrating the presence of Zn, Co, Mn and O in the material. FIG. 2 (b) shows high-resolution Zn2pThe two main peaks have the binding energy values of 1020.9 eV and 1044.0eV respectively, which are Zn2+Are respectively attributed to Zn 2p3/2And Zn 2p1/2. FIG. 2(c) shows Mn2p3/2And Mn2p1/2Spectra with peaks of 641.9eV and 653.5eV, respectively, assigned to Mn3+Status. Co2pThe spectrum is shown in FIG. 2(d), Co2p3/2And Co2p1/2Two main units ofPeaks at 780.2eV and 795.3eV, apparently Co3+Species of the species. From the above data, ZnCoMnO4The catalyst was successfully synthesized.
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 placed in an oven at 170 ℃ for 16 hours to remove the remaining water, the dried gel was thoroughly ground and annealed in air at 650 ℃ for 5 hours (heating rate: 10 ℃ C. min)-1) To obtain ZnCoMnO4Spinel powder.
Application 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 ℃. Firstly, 0.15-0.25g/L of ZnCoMnO is added4The catalyst was mixed with the phenol solution for 30 minutes to reach adsorption/desorption equilibrium. 2g/LPMS was then 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.
ZnCoMnO obtained in example 14Application of catalyst to ZnCoMnO4+ PMS system, and test its performance. FIG. 3 shows PMS system (solution of PMS and phenol) and ZnCoMnO4EPR profile of + PMS system (PMS, catalyst and phenol solution). It can be seen that SO is present in solution only in the presence of PMS4 -·And OH. the signal is weak, passing through ZnCoMnO4After activation of the nanomaterial, SO4 -·And OH. the signal is greatly enhanced, saidSO in Ming liquor4 -·And the OH concentration increases. FIG. 4 shows a PMS system and ZnCoMnO4+ phenol degradation efficiency plot in PMS system. As can be seen from FIG. 4, in the PMS system, phenol is not substantially degraded; when ZnCoMnO is added4After PMS is activated, a large amount of SO is generated in the system4 -·And OH to rapidly decompose phenol, and after reacting for 45 minutes, the removal rate of phenol reaches 97.8 percent. FIG. 5 shows ZnCoMnO4The circulation efficiency of the system for degrading phenol is shown. As can be seen from FIG. 5, after 4 cycles of the experiment, ZnCoMnO was obtained4The + PMS system still has 88.3 percent of removal rate on phenol, which indicates that ZnCoMnO is4The spinel has good reusability, which is attributed to the existence of Mn and Zn ions, and the precipitation of Co is reduced, so that the material still has good catalytic performance.
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 were compiled to give a phenol degradation rate table. As can be seen from Table 1, ZnCoMnO was compared to PMS alone system (1.46%)4The removal rate of the phenol by the + PMS system (97.8%) is obviously improved.
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 (3)
1. A preparation method of a porous nano cobalt-doped zinc manganate spinel catalyst for activating peroxymonosulfate to degrade phenol is characterized by comprising the following specific steps of:
s1, dissolving zinc acetate, manganese acetate, cobalt acetate and citric acid in deionized water and nitric acid to obtain a mixed solution; the volume ratio of the zinc acetate, the total mole of manganese acetate and cobalt acetate, the citric acid, the deionized water and the nitric acid in the mixed solution is 2.5 mmol: 5mmol, (12-16) mmol: 30ml, (1.5-2.5) ml; the molar ratio of the manganese acetate to the cobalt acetate is (0.5-0.9) to (0.1-0.5);
s2, heating the mixed solution to a temperature of
Heating for 4-8 h to obtain gel;
s3, gel is added in
Drying, grinding the obtained dry gel, and heating in air to
Annealing for 5-7 h to obtain the porous nano ZnCoMnO4A spinel catalyst.
2. The method for preparing the porous nano cobalt-doped zinc manganate spinel catalyst for activating peroxymonosulfate degradation phenol as claimed in claim 1, wherein the drying time in step S3 is
3. The method as claimed in claim 1, wherein the temperature is raised at a rate of 3
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Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102082270A (en) * | 2010-12-03 | 2011-06-01 | 南开大学 | Manganese spinel nano material as well as preparation method and application of manganese spinel nano material |
| CN103030208A (en) * | 2013-01-08 | 2013-04-10 | 哈尔滨工业大学 | Application of spinel ferrite catalyst and method for urging persulfate to generate free radicals to catalytically degrade organic matters |
| CN103861597A (en) * | 2012-12-18 | 2014-06-18 | 中国科学院大连化学物理研究所 | Supported spinel compound and preparation and application thereof |
| CN106111144A (en) * | 2016-06-15 | 2016-11-16 | 广东工业大学 | A kind of complex function reforming hydrogen-production catalyst and its preparation method and application |
| CN106132997A (en) * | 2014-03-11 | 2016-11-16 | 纳幕尔杜邦公司 | Poly-α 1,3 glucosan as the oxidation of detergent builders |
| CN106140173A (en) * | 2015-04-14 | 2016-11-23 | 中国科学院大连化学物理研究所 | A kind of ferrite/metal oxide materials and its preparation method and application |
| CN108421545A (en) * | 2018-03-08 | 2018-08-21 | 清华大学 | Manganese dioxide composite material and its preparation method and application |
| CN109794280A (en) * | 2019-02-28 | 2019-05-24 | 山东大学 | A kind of magnetic Nano g-C3N4/MnFe2O4The preparation method of catalyst |
| JP2019125480A (en) * | 2018-01-16 | 2019-07-25 | 大阪瓦斯株式会社 | Cell-to-cell connection member, cell for solid oxide type fuel battery, solid oxide type fuel battery, sofc mono-generation system, and sofc co-generation system |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US10707025B2 (en) * | 2017-10-04 | 2020-07-07 | Nanotek Instruments Group, Llc | Internal hybrid electrochemical energy storage cell having both high power and high energy density |
-
2019
- 2019-08-07 CN CN201910727144.XA patent/CN110548519B/en active Active
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102082270A (en) * | 2010-12-03 | 2011-06-01 | 南开大学 | Manganese spinel nano material as well as preparation method and application of manganese spinel nano material |
| CN103861597A (en) * | 2012-12-18 | 2014-06-18 | 中国科学院大连化学物理研究所 | Supported spinel compound and preparation and application thereof |
| CN103030208A (en) * | 2013-01-08 | 2013-04-10 | 哈尔滨工业大学 | Application of spinel ferrite catalyst and method for urging persulfate to generate free radicals to catalytically degrade organic matters |
| CN106132997A (en) * | 2014-03-11 | 2016-11-16 | 纳幕尔杜邦公司 | Poly-α 1,3 glucosan as the oxidation of detergent builders |
| CN106140173A (en) * | 2015-04-14 | 2016-11-23 | 中国科学院大连化学物理研究所 | A kind of ferrite/metal oxide materials and its preparation method and application |
| CN106111144A (en) * | 2016-06-15 | 2016-11-16 | 广东工业大学 | A kind of complex function reforming hydrogen-production catalyst and its preparation method and application |
| JP2019125480A (en) * | 2018-01-16 | 2019-07-25 | 大阪瓦斯株式会社 | Cell-to-cell connection member, cell for solid oxide type fuel battery, solid oxide type fuel battery, sofc mono-generation system, and sofc co-generation system |
| CN108421545A (en) * | 2018-03-08 | 2018-08-21 | 清华大学 | Manganese dioxide composite material and its preparation method and application |
| CN109794280A (en) * | 2019-02-28 | 2019-05-24 | 山东大学 | A kind of magnetic Nano g-C3N4/MnFe2O4The preparation method of catalyst |
Non-Patent Citations (3)
| Title |
|---|
| "Synthesis and Photocatalytic Properties of Co-Doped Zn1-xCoxMn2O Hollow Nanospheres";Long Ma et al;《Journal of Nanomaterials》;20190509;第1-9页 * |
| "尖晶石型复合氧化物的制备、表征及光催化活性研究";张燕青;《中国优秀博硕士学位论文全文数据库(硕士)工程科技Ⅰ辑》;20071215(第06期);第10页第2.2节，第24页引言 * |
| "锌尖晶石ZnMn2O4(M=Cr，Mn，Fe)纳米晶的制备及其在可见光下对染料的光催化降解";姜妍彦等;《硅酸盐学报》;20071115;第35卷(第11期);第1440页1.1节 * |
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