CN115463661A - Zinc oxide loaded nickel lanthanum cobaltate and preparation method and application thereof - Google Patents
Zinc oxide loaded nickel lanthanum cobaltate and preparation method and application thereof Download PDFInfo
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- CN115463661A CN115463661A CN202211152425.5A CN202211152425A CN115463661A CN 115463661 A CN115463661 A CN 115463661A CN 202211152425 A CN202211152425 A CN 202211152425A CN 115463661 A CN115463661 A CN 115463661A
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- lanthanum
- zinc oxide
- cobaltate
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- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 title claims abstract description 128
- 239000011787 zinc oxide Substances 0.000 title claims abstract description 64
- DOARWPHSJVUWFT-UHFFFAOYSA-N lanthanum nickel Chemical compound [Ni].[La] DOARWPHSJVUWFT-UHFFFAOYSA-N 0.000 title claims abstract description 43
- 238000002360 preparation method Methods 0.000 title abstract description 8
- GSDSWSVVBLHKDQ-UHFFFAOYSA-N 9-fluoro-3-methyl-10-(4-methylpiperazin-1-yl)-7-oxo-2,3-dihydro-7H-[1,4]oxazino[2,3,4-ij]quinoline-6-carboxylic acid Chemical compound FC1=CC(C(C(C(O)=O)=C2)=O)=C3N2C(C)COC3=C1N1CCN(C)CC1 GSDSWSVVBLHKDQ-UHFFFAOYSA-N 0.000 claims abstract description 40
- 229960001699 ofloxacin Drugs 0.000 claims abstract description 40
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 20
- 150000001875 compounds Chemical class 0.000 claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 15
- 238000001035 drying Methods 0.000 claims abstract description 14
- 239000011259 mixed solution Substances 0.000 claims abstract description 13
- 238000001354 calcination Methods 0.000 claims abstract description 12
- 239000002105 nanoparticle Substances 0.000 claims abstract description 12
- 239000002243 precursor Substances 0.000 claims abstract description 11
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 10
- 229910052746 lanthanum Inorganic materials 0.000 claims abstract description 9
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 8
- 239000010941 cobalt Substances 0.000 claims abstract description 8
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000003756 stirring Methods 0.000 claims abstract description 7
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 6
- 239000002994 raw material Substances 0.000 claims abstract description 5
- 238000000227 grinding Methods 0.000 claims abstract description 4
- 230000002195 synergetic effect Effects 0.000 claims abstract description 4
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 239000007864 aqueous solution Substances 0.000 claims description 6
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 4
- 230000000593 degrading effect Effects 0.000 claims description 4
- 229910052725 zinc Inorganic materials 0.000 claims description 4
- 239000011701 zinc Substances 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- SHWZFQPXYGHRKT-FDGPNNRMSA-N (z)-4-hydroxypent-3-en-2-one;nickel Chemical compound [Ni].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O SHWZFQPXYGHRKT-FDGPNNRMSA-N 0.000 claims description 2
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 2
- OPDRIGFSUGVDKR-UHFFFAOYSA-N cobalt lanthanum nickel Chemical compound [Co].[Ni].[La] OPDRIGFSUGVDKR-UHFFFAOYSA-N 0.000 claims description 2
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 2
- FJDJVBXSSLDNJB-LNTINUHCSA-N cobalt;(z)-4-hydroxypent-3-en-2-one Chemical compound [Co].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O FJDJVBXSSLDNJB-LNTINUHCSA-N 0.000 claims description 2
- 239000008139 complexing agent Substances 0.000 claims description 2
- 238000003837 high-temperature calcination Methods 0.000 claims description 2
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 claims description 2
- ICAKDTKJOYSXGC-UHFFFAOYSA-K lanthanum(iii) chloride Chemical compound Cl[La](Cl)Cl ICAKDTKJOYSXGC-UHFFFAOYSA-K 0.000 claims description 2
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 abstract description 8
- 238000002386 leaching Methods 0.000 abstract description 4
- 231100000331 toxic Toxicity 0.000 abstract description 4
- 230000002588 toxic effect Effects 0.000 abstract description 4
- 230000015556 catabolic process Effects 0.000 description 22
- 238000006731 degradation reaction Methods 0.000 description 22
- 238000001514 detection method Methods 0.000 description 8
- 239000007787 solid Substances 0.000 description 7
- 230000003213 activating effect Effects 0.000 description 5
- VMTPSMDWKJCNNA-UHFFFAOYSA-N cobalt lanthanum oxonickel Chemical compound [Ni]=O.[Co].[La] VMTPSMDWKJCNNA-UHFFFAOYSA-N 0.000 description 5
- 238000002474 experimental method Methods 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 239000003242 anti bacterial agent Substances 0.000 description 4
- 229940088710 antibiotic agent Drugs 0.000 description 4
- 229910052573 porcelain Inorganic materials 0.000 description 4
- 238000001878 scanning electron micrograph Methods 0.000 description 4
- 238000009303 advanced oxidation process reaction Methods 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 239000003814 drug Substances 0.000 description 3
- 239000003344 environmental pollutant Substances 0.000 description 3
- -1 hydroxyl radicals Chemical class 0.000 description 3
- 231100000719 pollutant Toxicity 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- MPMSMUBQXQALQI-UHFFFAOYSA-N cobalt phthalocyanine Chemical compound [Co+2].C12=CC=CC=C2C(N=C2[N-]C(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2[N-]1 MPMSMUBQXQALQI-UHFFFAOYSA-N 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 229940079593 drug Drugs 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000010842 industrial wastewater Substances 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000004570 mortar (masonry) Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000003642 reactive oxygen metabolite Substances 0.000 description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 239000003741 agents affecting lipid metabolism Substances 0.000 description 1
- 229940121363 anti-inflammatory agent Drugs 0.000 description 1
- 239000002260 anti-inflammatory agent Substances 0.000 description 1
- 238000006065 biodegradation reaction Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- QGUAJWGNOXCYJF-UHFFFAOYSA-N cobalt dinitrate hexahydrate Chemical compound O.O.O.O.O.O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QGUAJWGNOXCYJF-UHFFFAOYSA-N 0.000 description 1
- 229910052963 cobaltite Inorganic materials 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000012084 conversion product Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000010791 domestic waste Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000002638 heterogeneous catalyst Substances 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000000077 insect repellent Substances 0.000 description 1
- GJKFIJKSBFYMQK-UHFFFAOYSA-N lanthanum(3+);trinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O GJKFIJKSBFYMQK-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000002906 medical waste Substances 0.000 description 1
- 239000002207 metabolite Substances 0.000 description 1
- AOPCKOPZYFFEDA-UHFFFAOYSA-N nickel(2+);dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O AOPCKOPZYFFEDA-UHFFFAOYSA-N 0.000 description 1
- FHHJDRFHHWUPDG-UHFFFAOYSA-L peroxysulfate(2-) Chemical compound [O-]OS([O-])(=O)=O FHHJDRFHHWUPDG-UHFFFAOYSA-L 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 239000003306 quinoline derived antiinfective agent Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
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- 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
- B01J23/83—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 rare earths or actinides
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
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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
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- C02F1/00—Treatment of water, waste water, or sewage
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- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
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Abstract
The invention discloses zinc oxide loaded nickel lanthanum cobaltate, and a preparation method and application thereof, and belongs to the technical field of catalysts. The preparation method comprises the following steps: taking a nickel-containing compound, a cobalt-containing compound and a lanthanum-containing compound as raw materials, magnetically stirring at 20-60 ℃ to obtain a nickel-lanthanum cobaltate precursor mixed solution, adding zinc oxide nanoparticles into the nickel-lanthanum cobaltate precursor mixed solution, magnetically stirring at 65-95 ℃ to obtain zinc oxide-loaded nickel-lanthanum cobaltate gel, and sequentially drying, grinding and calcining the zinc oxide-loaded nickel-lanthanum cobaltate gel at high temperature to obtain the zinc oxide-loaded nickel-lanthanum cobaltate. The invention has the advantages that: the method has simple and convenient process, easy operation and cheap and easily obtained raw materials; the prepared zinc oxide loaded nickel-lanthanum cobaltate active component is not easy to agglomerate, free of toxic metal ion leaching, good in stability and capable of forming a synergistic system with PMS to efficiently catalyze and degrade ofloxacin.
Description
Technical Field
The invention relates to a compound, a preparation method and application thereof, in particular to zinc oxide loaded nickel lanthanum cobaltate, a preparation method thereof and application of the zinc oxide loaded nickel lanthanum cobaltate as a catalyst and a PMS (permanent magnet system) formed synergistic system in ofloxacin degradation, belonging to the technical field of catalysts.
Background
In recent years, pharmaceuticals and Personal Care Products (PPCPs) have received increasing attention as emerging aquatic pollutants because they may pose threats to humans and aquatic ecosystems. PPCPs comprise a number of chemical classes, for example: antibiotics, anti-inflammatory agents, lipid regulating agents, and the like; personal care product ingredients such as insect repellents, preservatives, and metabolites or conversion products thereof. Among the drugs, antibiotics are one of the most widely used classes, ofloxacin being a fluoroquinolone antibiotic that is frequently detected in the environment, entering the environment mainly through domestic, hospital and industrial waste waters, and to a lesser extent through discharge from the production site and improper disposal of the drugs. Since ofloxacin has the characteristics of difficult biodegradation, wide application range, difficult removal by a conventional method and the like, the problem of removing ofloxacin by currently developing a reliable and popularizing technology is urgently needed to be solved in the environmental field.
Advanced Oxidation Processes (AOPs) are a new water treatment technology proposed in 1987 that relies on the in situ generation of highly Reactive Oxygen Species (ROS) to degrade recalcitrant contaminants such as hydroxyl radicals: (OH: (R)) · OH), sulfate radical (SO) 4 ·- ) And singlet oxygen ( 1 O 2 ). Based on SO 4 ·- The AOPs have higher oxidation potential, longer half-life and wider pH application range. As a catalyst which is widely researched, the transition metal oxide can effectively activate Peroxymonosulfate (PMS) to remove pollutants.
Perovskite oxides have abundant physicochemical properties and flexible structures, and they are one of the most promising heterogeneous catalysts for activating PMS. However, the original perovskite oxide has inherent defects of easy agglomeration (the specific surface area is reduced, the contact area with PMS is reduced), toxic metal ion leaching (secondary pollution to the environment) and the like, and the application of the perovskite oxide in actual water treatment is limited.
The zinc oxide has the advantages of good stability, low price, easy obtaining and the like, and can be used as a potential carrier of the perovskite oxide.
In conclusion, the zinc oxide-supported perovskite metal oxide has great potential in the aspects of activating antibiotics in PMS (permanent magnet system) degradation water and the like, and the zinc oxide-supported perovskite metal oxide as an efficient catalyst in the advanced oxidation technology must have great application value in the industrial wastewater treatment in the future.
Disclosure of Invention
The invention aims to provide a catalyst which has the advantages of difficult agglomeration of active components, no leaching of toxic metal ions, good stability and capability of forming a synergistic system with PMS to efficiently catalyze and degrade ofloxacin, and a method for preparing the catalyst, which has the advantages of cheap and easily-obtained raw materials, simple operation and easy implementation.
In order to achieve the above purpose, the invention adopts the following technical scheme:
a method for preparing zinc oxide loaded nickel lanthanum cobaltate is characterized by comprising the following steps:
(1) Taking a nickel-containing compound, a cobalt-containing compound and a lanthanum-containing compound as raw materials, wherein the mass ratio of lanthanum, nickel and cobalt is 5:3:2, using citric acid as a complexing agent, wherein the mass ratio of the citric acid to the total metal ion substances is 1-1.5: 1, taking water, ethanol or an ethanol aqueous solution as a solvent, and magnetically stirring for 1-3 hours at 20-60 ℃ to prepare a cobalt-substituted partial nickel site nickel-cobalt lanthanum precursor mixed solution;
(2) Adding zinc oxide nanoparticles into the mixed solution of the lanthanum nickel cobaltate precursor prepared in the step (1), wherein the mass ratio of the zinc oxide nanoparticles to the predicted lanthanum nickel cobaltate is 5:1, magnetically stirring for 1-5 hours at 65-95 ℃ to prepare zinc oxide-loaded nickel-lanthanum cobaltate gel;
(3) And (3) sequentially drying, grinding and calcining the zinc oxide-loaded lanthanum nickel cobaltate gel prepared in the step (2) at a high temperature to obtain the zinc oxide-loaded lanthanum nickel cobaltate.
Preferably, in step (1), the nickel-containing compound includes: nickel nitrate and nickel acetylacetonate; the cobalt-containing compound includes: cobalt nitrate and cobalt acetylacetonate; the lanthanum-containing compound includes: lanthanum nitrate and lanthanum chloride.
Preferably, in the step (3), drying is carried out in an oven, the drying temperature is 50-100 ℃, and the drying time is 6-15 h; the high-temperature calcination is carried out in a tubular furnace in the air atmosphere, the calcination temperature is 700-900 ℃, and the calcination time is 4-6 h.
A zinc oxide-supported lanthanum nickel cobaltate prepared by any one of the methods described above.
The invention has the advantages that:
(1) According to the method for preparing the zinc oxide loaded lanthanum nickel cobaltate, zinc oxide is added into a mixed solution of a lanthanum nickel cobaltate precursor to form mixed-state gel, and the mixed-state gel is dried and then calcined at high temperature to form the zinc oxide loaded lanthanum nickel cobaltate;
(2) The zinc oxide loaded lanthanum nickel cobaltate prepared by the method provided by the invention has good stability, and the lanthanum nickel cobaltate is uniformly dispersed on the zinc oxide and is not easy to agglomerate, so that the active site of the lanthanum nickel cobaltate is in contact with PMS in a larger area, namely, the capability of activating PMS is enhanced, and finally the higher activity of catalytic degradation of antibiotics is realized;
(3) The zinc oxide loaded nickel lanthanum cobaltate prepared by the method provided by the invention can effectively inhibit leaching of toxic metal ions nickel and cobalt, and avoids secondary pollution to the environment;
(4) When the zinc oxide loaded lanthanum cobaltous nickelate prepared by the invention is used for activating ofloxacin in PMS degraded water, the removal rate of the ofloxacin reaches 97-98%, and the zinc oxide loaded lanthanum cobaltous nickelate still has high catalytic activity after repeated degradation for 5 times.
Drawings
FIG. 1 shows LaNi prepared in example 1 0.6 Co 0.4 O 3 XRD patterns before and after ZnO catalytic reaction;
FIG. 2 shows LaNi prepared in example 1 0.6 Co 0.4 O 3 The ZnO is repeatedly used in a degradation graph of activating PMS to degrade ofloxacin;
FIG. 3 shows LaNi prepared in example 1 0.6 Co 0.4 O 3 SEM picture of (1);
fig. 4 is an SEM image of zinc oxide nanoparticles used in the present invention;
FIG. 5 shows LaNi prepared in example 1 0.6 Co 0.4 O 3 SEM image of/ZnO.
Detailed Description
The present invention will be described in detail with reference to the following embodiments.
Example 1
1.300g (3.0 mmol) of lanthanum nitrate hexahydrate, 0.524g (1.8 mmol) of nickel nitrate hexahydrate and 0.349g (1.2 mmol) of cobalt nitrate hexahydrate are weighed, the three solids are completely dissolved in 10ml of water and 20ml of ethanol, and the mixture is magnetically stirred at room temperature for 15min to obtain a light green mixed solution. 1.261g (6.6 mmol) of citric acid is weighed, slowly added into the light green mixed solution, and magnetically stirred for 2 hours at room temperature to obtain a lanthanum nickel cobaltate precursor mixed solution, and 0.7371g (3.0 mmol) of lanthanum nickel cobaltate is expected to be obtained.
3.686g of zinc oxide nanoparticles are weighed, the zinc oxide nanoparticles are added into the mixed solution of the lanthanum nickel cobalt oxide precursor obtained by the previous preparation, and the mass ratio of the zinc oxide nanoparticles to the predicted lanthanum nickel cobalt oxide is 5: magnetically stirring the mixture for 3 hours at the temperature of 1,90 ℃ to obtain zinc oxide loaded nickel lanthanum cobaltate gel.
And (3) putting the zinc oxide-loaded nickel lanthanum cobaltate gel into an oven, and drying for 12h at the temperature of 60 ℃ to obtain a white solid. The white solid was ground to a powder with an agate mortar. Putting the powder into a porcelain boat, putting the porcelain boat into a tube furnace, heating the tube furnace to 700 ℃ at the speed of 5 ℃/min in the air atmosphere, calcining for 4h, naturally cooling to room temperature after calcining is finished, and obtaining white solid particles, namely zinc oxide loaded nickel lanthanum cobaltite, which is recorded as LaNi 0.6 Co 0.4 O 3 /ZnO。
0.2g of LaNi 0.6 Co 0.4 O 3 adding/ZnO and 0.5g PMS into 100ml ofloxacin aqueous solution with the concentration of 20ml/L, and oscillating for 30min at room temperature in a swinging way. The detection proves that the degradation rate of the ofloxacin is 97.90%.
LaNi 0.6 Co 0.4 O 3 XRD patterns before and after the/ZnO catalytic reaction are shown in figure 1.
As can be seen from FIG. 1, laNi before and after the catalytic reaction 0.6 Co 0.4 O 3 The characteristic peak of/ZnO is not changed, which shows that LaNi 0.6 Co 0.4 O 3 The structure of the/ZnO is not changed, and the stability of the catalyst is proved.
And centrifugally collecting the reacted zinc oxide loaded nickel-lanthanum cobaltate, repeatedly recovering the zinc oxide loaded nickel-lanthanum cobaltate for 5 times of an ofloxacin degradation experiment, washing the recovered zinc oxide loaded nickel-lanthanum cobaltate with clear water after each pollutant treatment, and drying. Through detection, when the ofloxacin is degraded for the 2 nd time, the degradation rate of the ofloxacin is 96.27 percent; when the ofloxacin is degraded for the 3 rd time, the degradation rate of the ofloxacin is 97.07 percent; when the ofloxacin is degraded for the 4 th time, the degradation rate of the ofloxacin is 96.38 percent; when the ofloxacin is degraded for the 5 th time, the degradation rate of the ofloxacin is 96.49 percent.
And (3) plotting degradation data obtained in each degradation experiment by taking the sampling time as the abscissa and the degradation rate of the ofloxacin as the ordinate to obtain the LaNi 0.6 Co 0.4 O 3 The degradation profile of/ZnO on ofloxacin is shown in FIG. 2.
As can be seen from FIG. 2, laNi 0.6 Co 0.4 O 3 After ZnO is repeatedly recycled, the ofloxacin can be rapidly degraded in a short time, and the degradation rate of the ofloxacin is kept above 96%.
Preparing a lanthanum nickel cobalt oxide precursor mixed solution by adopting the same method as the previous method, then putting the lanthanum nickel cobalt oxide precursor mixed solution into an oven, drying for 12 hours at 60 ℃ to obtain a solid, grinding the solid into powder by using an agate mortar, putting the powder into a porcelain boat, putting the porcelain boat into a tubular furnace, heating the tubular furnace to 700 ℃ at the speed of 5 ℃/min in the air atmosphere, calcining for 4 hours, naturally cooling to room temperature after the calcination is finished to obtain solid particles, namely lanthanum nickel cobalt oxide, which is marked as LaNi 0.6 Co 0.4 O 3 . The LaNi 0.6 Co 0.4 O 3 See fig. 3. As can be seen from FIG. 3, laNi 0.6 Co 0.4 O 3 Exhibit an agglomerated state.
The SEM image of the zinc oxide nanoparticles used in the present invention is shown in fig. 4. As can be seen from fig. 4, the zinc oxide is nanoparticles of about 300 nm.
Example 1 preparation of LaNi 0.6 Co 0.4 O 3 SEM image of/ZnO is shown in FIG. 5. As can be seen from FIG. 5, laNi 0.6 Co 0.4 O 3 Uniformly dispersed on the zinc oxide nano-particles.
Example 2
This example differs from example 1 only in that: the amounts of reactants and solvent in each step were all magnified by a factor of 3. The rest is the same as the embodiment 1, and the description is omitted.
0.6g of LaNi 0.6 Co 0.4 O 3 adding/ZnO and 1.5g PMS into 100ml ofloxacin aqueous solution with the concentration of 20ml/L, and shaking at room temperatureOscillating for 30min. The detection proves that the degradation rate of the ofloxacin is 97.51 percent.
Centrifugally collecting reacted LaNi 0.6 Co 0.4 O 3 and/ZnO, repeatedly recycled for 5 times of the experiment for degrading ofloxacin. Through detection, when the ofloxacin is degraded for the 5 th time, the degradation rate of the ofloxacin is 96.53 percent.
Example 3
This example only differs from example 1 in that: when preparing zinc oxide-loaded nickel lanthanum cobaltate gel, reducing the reaction temperature to 70 ℃; when the zinc oxide supported nickel-lanthanum cobaltate gel is dried, the drying temperature is increased to 70 ℃, and the drying time is shortened to 10 hours. The rest is the same as the embodiment 1, and the description is omitted.
0.2g of LaNi 0.6 Co 0.4 O 3 adding/ZnO and 0.5g PMS into 100ml ofloxacin aqueous solution with the concentration of 20ml/L, and oscillating for 30min at room temperature in a swinging way. The detection proves that the degradation rate of the ofloxacin is 97.51 percent.
Centrifugally collecting reacted LaNi 0.6 Co 0.4 O 3 and/ZnO, repeatedly recycled for 5 times of the experiment for degrading ofloxacin. Through detection, when the ofloxacin is degraded for the 5 th time, the degradation rate of the ofloxacin is 96.01 percent.
Example 4
This example differs from example 1 only in that: when the powder was calcined, the calcination temperature was raised to 750 ℃. The rest is the same as the embodiment 1, and the description is omitted.
0.2g of LaNi 0.6 Co 0.4 O 3 adding/ZnO and 0.5g PMS into 100ml ofloxacin aqueous solution with the concentration of 20ml/L, and oscillating for 30min at room temperature in a swinging way. Through detection, the degradation rate of the ofloxacin is 95.99 percent.
Centrifugally collecting reacted LaNi 0.6 Co 0.4 O 3 and/ZnO, repeatedly recycled for 5 times of the experiment for degrading ofloxacin. Through detection, when the ofloxacin is degraded for the 5 th time, the degradation rate of the ofloxacin is 96.99 percent.
It should be noted that the above examples of the present invention are only examples for clearly illustrating the present invention, and are not intended to limit the embodiments of the present invention. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. Not all embodiments are exhaustive. Obvious changes or modifications of the invention are within the scope of the invention.
Claims (6)
1. A method for preparing zinc oxide loaded nickel lanthanum cobaltate is characterized by comprising the following steps:
(1) Taking a nickel-containing compound, a cobalt-containing compound and a lanthanum-containing compound as raw materials, wherein the mass ratio of lanthanum, nickel and cobalt is 5:3:2, using citric acid as a complexing agent, wherein the quantity ratio of the citric acid to total metal ion substances is (1-1.5): 1, taking water, ethanol or an ethanol aqueous solution as a solvent, and magnetically stirring for 1-3 hours at 20-60 ℃ to prepare a cobalt-substituted partial nickel site nickel-cobalt lanthanum precursor mixed solution;
(2) Adding zinc oxide nanoparticles into the mixed solution of the lanthanum nickel cobaltate precursor prepared in the step (1), wherein the mass ratio of the zinc oxide nanoparticles to the predicted lanthanum nickel cobaltate is 5:1, magnetically stirring for 1-5 hours at 65-95 ℃ to prepare zinc oxide loaded nickel lanthanum cobaltate gel;
(3) And (3) sequentially drying, grinding and calcining the zinc oxide-loaded lanthanum nickel cobaltate gel prepared in the step (2) at a high temperature to obtain the zinc oxide-loaded lanthanum nickel cobaltate.
2. The method of claim 1, wherein in step (1), the nickel-containing compound comprises: nickel nitrate and nickel acetylacetonate; the cobalt-containing compound includes: cobalt nitrate and cobalt acetylacetonate; the lanthanum-containing compound includes: lanthanum nitrate and lanthanum chloride.
3. The method according to claim 1, wherein in step (3), the drying is carried out in an oven at a drying temperature of 50 to 100 ℃ for a drying time of 6 to 15 hours.
4. The method according to claim 1, wherein in the step (3), the high-temperature calcination is performed in a tube furnace under an air atmosphere, the calcination temperature is 700 to 900 ℃, and the calcination time is 4 to 6 hours.
5. A zinc oxide-supported lanthanum nickel cobaltate prepared by the method of any one of claims 1 to 4.
6. The use of the zinc oxide supported lanthanum nickel cobaltate and PMS as a synergistic system for degrading ofloxacin as claimed in claim 5.
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