CN113120944A - Preparation method of spinel type transition metal oxide and application of spinel type transition metal oxide in degrading antibiotics - Google Patents

Preparation method of spinel type transition metal oxide and application of spinel type transition metal oxide in degrading antibiotics Download PDF

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CN113120944A
CN113120944A CN202010024839.4A CN202010024839A CN113120944A CN 113120944 A CN113120944 A CN 113120944A CN 202010024839 A CN202010024839 A CN 202010024839A CN 113120944 A CN113120944 A CN 113120944A
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transition metal
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吕国诚
田林涛
刘亿浩
廖立兵
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China University of Geosciences Beijing
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Abstract

The invention relates to a preparation method of spinel-type transition metal oxide and application thereof in degrading antibiotics, wherein cobalt oxide is prepared by a hydrothermal-calcination method, iron oxide and manganese oxide are directly synthesized by the hydrothermal method, and zinc and aluminum are respectively doped to prepare the spinel-type transition metal oxide, the transition metal oxide degrades the antibiotics under microwave induction, and the degradation amount of the antibiotics can reach more than 40 mg/g.

Description

Preparation method of spinel type transition metal oxide and application of spinel type transition metal oxide in degrading antibiotics
Technical Field
The invention relates to a preparation method of spinel-type transition metal oxide and application of the spinel-type transition metal oxide in degrading antibiotics, belonging to the field of material chemistry.
Background
In recent years, persistent organic pollutants in water have attracted a great deal of social attention, particularly antibiotic pollution. Antibiotics, a commonly used drug for the treatment of bacterial infections, refer to a class of substances produced by bacteria, molds, or other microbial metabolic processes that have anti-pathogenic or other activities. The antibiotic pollution in the water body of the east China is serious, the discharge density is more than 6 times of that of the water body of the west China, the antibiotic pollution in the water body of the Beijing city is the most serious, and the tetracycline is the highest in content. At present, most of antibiotics taken into the body cannot be completely absorbed, and more than 85 percent of antibiotics are discharged out of the body in the form of original forms or metabolites and pass through sewage or directly enter the environment.
The existing antibiotic treatment technologies at home and abroad mainly comprise a conventional method (flocculation, filtration and the like), an adsorption method, a biodegradation method, a chemical oxidation method and the like. The chemical oxidation method mainly comprises chlorination, Fenton, ozone, photocatalysis and electrochemical oxidation, and is a chemical treatment technology. Although the water-soluble characteristics of the antibiotics can be utilized to achieve good degradation effects on various antibiotics, the antibiotics are not removed selectively, and the use cost and the energy consumption are high. Studies found that penicillin was completely degraded within 2h by chlorination treatment technique and amoxicillin and cefradine were completely degraded within 1min (Navalon S, 2008). By fenton's technique, sulfamethazine is totally removed within 2min, but the toxicity of the resulting product is increased and amoxicillin can be removed within 1min in combination with photocatalysis (Elmolla E, 2009). By using the ozone catalytic oxidation technology, 90% of amoxicillin can be removed after 4min, and 18% of amoxicillin can be mineralized after 20min (Andreozzi R, 2005); the combination of H2O2 can accelerate the degradation of antibiotics, ozone can degrade 97% of erythromycin and tylosin in wastewater within 10min, and erythromycin and tylosin can be completely degraded within 20min (Lin A Y C, 2009). 0.4mg/mg-1 ozone can 100% remove oxytetracycline in 10mg/L-1 simulated water, 1.2mg/mg-1 can remove oxytetracycline in waste mother liquor with the concentration of 92% being 702mg/L-1, and the generation of drug-resistant bacteria and drug-resistant genes in the subsequent biological treatment process can be reduced (Liu M, 2017). Under the photocatalysis technology, 66% of antibiotics can be degraded under the condition that the pH value is 6.0 (Molinari R, 2006); sulfadoxine, sulfathiazole were able to be totally degraded after 30min under UV lamp and 200mg/L-1TiO2, 80% of sulfadiazine was removed and 90% of sulfamethazine was removed (Calza P, 2004). Therefore, it is of great significance to develop new efficient degradation technology for antibiotic contamination.
The microwave is an electromagnetic wave having a frequency of 300MHz to 300GHz (wavelength of 1m to 1 mm). The application of microwave technology to environmental pollution treatment is a new research field which is emerging in recent years, and is favored by researchers due to the characteristics of rapidness, high efficiency, no secondary pollution and the like. Microwaves belong to non-ionizing radiation waves and act mainly by exciting molecular translation. The microwave action does not alter or break the chemical bonds of the molecules, but the molecules can vibrate or rotate by absorbing microwave energy under the action of the microwaves. The microwave energy interacts with the polar part in the substance to be absorbed, and the converted energy enables part of surface sites to be rapidly heated to form a 'hot spot effect', so that the oxidation activity of the material is improved, and the oxidative decomposition of organic pollutants is further enhanced (Zhang L, 2011). At present, the microwave technology is widely applied to the field of organic matters which are difficult to degrade in the treatment environment. Abramovith R A et al (Zhang L, 2011; Sun H J, 2015) utilize microwave technology to treat organic pollutants such as polychlorinated biphenyl and the like in soil, and obtain good effect. The Xitao Liu and the Gang Yu (Lu A H, 2004) utilize microwave-assisted activated carbon to adsorb and degrade 2,4, 5-trichlorobiphenyl in soil, and test results show that the degradation rate of the trichlorobiphenyl can reach 100 percent, and dioxin is not generated. Rural areas and the like (Guan H T, 2015; cheng tao, 2008) adopt activated carbon as a catalyst, microwave irradiation is used for treating high-concentration dioctyl phthalate production wastewater, and the removal rate of COD reaches 86.3%. Therefore, the microwave technology can be widely applied as an efficient antibiotic treatment technology.
Disclosure of Invention
The invention provides a preparation method of spinel-type transition metal oxide, and the spinel-type transition metal oxide is used for degrading antibiotics. Cobalt oxide is prepared by a hydrothermal-calcination method, iron oxide and manganese oxide are directly synthesized by the hydrothermal method, zinc and aluminum are respectively doped to prepare spinel-type transition metal oxide, the transition metal oxide degrades antibiotics under microwave induction, and the degradation amount of the antibiotics can reach more than 40mg/g, so that the invention is completed.
Accordingly, the present invention provides, in a first aspect, a process for preparing a spinel-type transition metal oxide, the process comprising the steps of:
step 1, preparing a precursor compound of transition metal and doped metal;
step 2, dissolving the raw materials in a solvent to prepare a solution;
and 3, carrying out reaction in the reactor to obtain a solid product, and optionally carrying out post-treatment.
In the step 1, the transition metal comprises cobalt, iron and manganese, and the doping metal comprises zinc and aluminum; precursors of the transition metal oxide are salt compounds, such as hydrochlorides of cobalt and iron, preferably hydrated hydrochlorides, and manganates, such as potassium permanganate; precursors of the doping metal are nitrates, such as zinc nitrate, preferably hydrated nitrates, and hydrochlorides, such as aluminum chloride.
In the step 2, the solvent is water, alcohol or a hydroalcoholic solution, and the alcohol is monohydric alcohol or polyhydric alcohol, preferably ethylene glycol; after the raw materials are dissolved in the solvent, optionally stirring, and preferably adding salt substances into the mixture; the salt is preferably ammonium salt, more preferably ammonium carbonate or ammonium bicarbonate, and sodium acetate can also be used.
In step 3, the reaction is carried out in a high-pressure device, preferably a stainless steel high-pressure reactor, and the reaction is heated at the temperature of 120-; the post-treatment includes washing, drying and calcining.
The oxide prepared by the method can be used for degrading antibiotics, and the degradation amount can reach more than 40 mg/g.
Drawings
Fig. 1 shows an XRD pattern of zinc-doped cobalt oxide prepared in example 1;
FIG. 2 shows the XRD pattern of the aluminum-doped cobalt oxide prepared in example 2;
fig. 3 shows an XRD pattern of zinc-doped iron oxide prepared in example 3;
FIG. 4 shows an XRD pattern of aluminum-doped iron oxide prepared in example 4;
FIG. 5 shows the XRD pattern of the new doped manganese oxide prepared in example 5;
FIG. 6 shows an XRD pattern of aluminum-doped manganese oxide prepared in example 6;
FIG. 7 shows the effect of microwave-induced degradation of tetracycline by zinc-doped cobalt oxide prepared in example 1;
FIG. 8 shows the effect of microwave-induced degradation of tetracycline by aluminum-doped cobalt oxide prepared in example 2;
FIG. 9 shows the effect of microwave-induced degradation of tetracycline by zinc-doped iron oxide prepared in example 3;
FIG. 10 shows the effect of microwave-induced degradation of tetracycline by aluminum-doped iron oxide obtained in example 4;
FIG. 11 shows the effect of microwave-induced degradation of tetracycline by the novel doped oxides of manganese prepared in example 5;
fig. 12 shows the effect of removing tetracycline by microwave-induced degradation of aluminum-doped manganese oxide prepared in example 6.
FIG. 13 shows an SEM image of Zn-doped Co oxide prepared in example 1, where Co is present3O4(a),Zn0.2Co2.8O4(b),Zn0.4Co2.6O4(c),Zn0.6Co2.4O4(d),Zn0.8Co2.2O4(e),Zn1Co2O4(f)。
Detailed Description
The features and advantages of the present invention will become more apparent and appreciated from the following detailed description of the invention.
The word "exemplary" is used exclusively herein to mean "serving as an example, embodiment, or illustration. Any embodiment described herein as "exemplary" is not necessarily to be construed as preferred or advantageous over other embodiments.
According to the invention, a spinel-type transition metal oxide, a preparation method thereof and application thereof in the aspect of antibiotic degradation are provided.
The preparation method of the spinel-type transition metal oxide provided by the invention comprises the following steps:
step 1, preparing precursor compounds of transition metals and doped metals.
The transition metals include cobalt, iron, and manganese.
For the transition metal, the oxide precursor thereof is a respective salt compound, for example, cobalt, iron hydrochloride, i.e., cobalt chloride, iron chloride, preferably, respective hydrated hydrochloride, and a manganate salt, such as potassium permanganate.
The doped metals include zinc and aluminum.
For the doping metal, the oxide precursor is a respective salt compound, preferably a nitrate salt, such as zinc nitrate, preferably a respective hydrated nitrate salt, such as zinc nitrate hexahydrate and aluminum nitrate nonahydrate, and a hydrochloride salt, such as aluminum chloride.
And 2, dissolving the raw materials in a solvent to prepare a solution.
The solvent is capable of dissolving the above-mentioned raw materials, for example, water or alcohol, or a hydroalcoholic solution may be used, and the alcohol may be a monohydric alcohol such as methanol, ethanol, butanol, etc., or a polyhydric alcohol such as a dihydric alcohol, preferably ethylene glycol and propylene glycol, more preferably ethylene glycol, or a polyhydric alcohol such as glycerin.
In the preparation of the iron oxide, it is preferable to use a glycol solvent, and the iron oxide is first dissolved in glycol, so that Fe can be effectively prevented3+And (3) hydrolyzing and stirring to uniformly disperse the mixture.
According to a preferred embodiment of the present invention, after dissolving the above raw materials in the solvent, optionally stirring, preferably a salt-like substance, preferably an ammonium salt, more preferably ammonium carbonate or ammonium bicarbonate, and also preferably sodium acetate, such as sodium acetate trihydrate, is added to the mixture, and then stirring is continued.
When preparing the iron oxide, sodium acetate trihydrate is added into the mixture at 50 ℃ to promote the formation of ferric hydroxide gel, and finally the spinel-structured iron oxide is directly synthesized under the hydrothermal condition.
In the case of cobalt oxide preparation, ammonium bicarbonate is preferably used to control morphology. Firstly, carbonate particles are formed by ammonium bicarbonate under hydrothermal conditions, and carbonate clusters are formed after self-assembly to finally form carbonate spheres. Then the carbonate is changed into oxide by calcining.
And 3, carrying out reaction in the reactor to obtain a solid product, and optionally carrying out post-treatment.
According to the present invention, the above stirred solution may be reacted in situ to obtain a fixed product, but is preferably transferred to a high pressure apparatus, preferably a stainless steel autoclave reactor, and heated at high temperature, for example at 120-.
The post-treatment includes washing, drying and calcining.
The washing is preferably a centrifugal washing, 5 times, wherein 3 times with deionized water and 2 times with ethanol.
Drying may be carried out at ambient temperature, preferably at 60 ℃, more preferably in an oven, for example overnight.
The calcination the dried product is calcined at 350 c for 2 hours using a dry gas, preferably air in a furnace.
The product is obtained and can be ground to a powder. The prepared metal oxide can degrade antibiotics under microwave induction, and the degradation amount can reach more than 40 mg/g.
The spinel-type transition metal oxide, the preparation method thereof and the application thereof in the aspect of antibiotic degradation have the following advantages or beneficial effects:
1) and synthesize a series of Zn2+And Al3+Respective isomorphism substituting for M2+(M: Co, Fe, Mn) and M3+Three kinds of spinel-structured transition metal oxides of (M: Co, Fe, Mn). Wherein, the cobalt oxide is successfully prepared by adopting a hydrothermal-calcining method, and the hydrothermal method is adoptedThe method directly synthesizes iron oxide and manganese oxide.
2)、Zn2+And Al3+Respectively successfully doped to M3O4In the crystal lattice of (M: Co, Fe, Mn), neither the crystal system nor the space group is changed. For Co3O4，Zn2+The doping of (A) is not changed in morphology, and is spherical particles with diameters of about 6-7 mu m, Al3+The doping of (a) causes the morphology to become cubic block-shaped particles with side lengths of 7-9 μm. For Fe3O4，Al3+The doping of (A) is not changed in shape, and is spherical particles with the diameter of about 400nm, Zn2+The doping of (2) reduces the diameter to around 100 nm. For Mn3O4，Zn2+The doping of (A) does not change the appearance, and all are octahedral particles with uniform size.
3) And the influence of components and morphology on the microwave-induced oxidative degradation performance is researched by regulating and controlling the spinel oxide structure, and the relation between the components and the microwave-induced degradation mechanism is disclosed.
4) Microwave induced Co3O4、Fe3O4The degradation amount of the degradable tetracycline can reach 47.7mg/g and 47.8mg/g respectively, and Zn is2+Has no influence on the microwave induced degradation effect, and Al3+The microwave degradation rate is reduced, and the balance time is prolonged. Microwave induced Mn3O4The degradation amount of degrading tetracycline can reach 42.81mg/g, Zn2+Reducing degradation rate, reducing degradation amount, prolonging balance time, and adding Al3+Has no influence on the microwave induced degradation effect.
Examples
Examples and information relating to the drugs and instruments used in the comparative examples are listed below:
experimental materials
Figure BDA0002362080830000081
The structure of the transition metal oxide was characterized by an X-ray diffraction analyzer (XRD), from Bruker, model TC-FY-II, with CuKa radiation at 40kV and 100mA, step-by-step scanning at 8 deg./min, step size 0.02 deg.. And performing Rietveld structure refinement on the transition metal oxide by utilizing Topas software, refining the crystal structure and calculating the structural parameters of the crystal structure.
ExamplesExample 1:preparation of cobalt oxide and zinc-doped cobalt oxide
Weighing 6 parts of cobalt chloride hexahydrate and zinc nitrate hexahydrate by an analytical balance according to corresponding stoichiometric ratio, wherein the total substance amount of the cobalt chloride hexahydrate and the zinc nitrate hexahydrate in each part is 3.0mmol, the zinc nitrate hexahydrate comprises 0, 0.2mmol, 0.4mmol, 0.6mmol, 0.80mmol and 1.0mmol respectively, and the balance is cobalt chloride hexahydrate;
the above raw materials were dissolved in a mixed solution of 30mL of ethylene glycol and 10mL of deionized water, and stirred for 30 minutes. Then 30mmol ammonium bicarbonate was added to the mixture and dissolved for 30 minutes with stirring.
The solution was then transferred to a stainless steel autoclave reactor and heated in an oven at 180 ℃ for 24 hours. The resulting solid product was washed 5 times by centrifugation, 3 times by centrifugation with deionized water, 2 times by centrifugation with ethanol, and then dried overnight in an oven at 60 ℃.
Finally, the dried product was calcined at 350 ℃ for 2 hours using air in a furnace and ground to a powder to give the (zinc doped) cobalt oxide ZnxCo(3-x)O4(x is more than or equal to 0 and less than or equal to 1), wherein x is 0, 0.2, 0.4, 0.6, 0.8 and 1.0 respectively, namely Zn2+Isomorphism substitution of Co occupying tetrahedral voids2+Substitution ratios are 0%, 20%, 40%, 60%, 80%, 100%.
The XRD results are shown in FIG. 1, and it can be seen from FIG. 1 that (Zn-doped) cobalt oxide ZnxCo(3-x)O4In accordance with the standard diffractogram of cobaltosic oxide (JCPDS: 42-1476). The space group of cobaltosic oxide is as follows: fd-3m, standard cell parameters are:
Figure BDA0002362080830000091
Z＝8。
through Rietveld structure refinement calculation, the space group of the synthesized cobaltosic oxide is not changed,
Figure BDA0002362080830000092
and after the structure is refined RexpIs 1.687, RwpIs 2.140, RpIs 1.687. When Co is present2+Is covered with Zn2+After all the substitutions, the space group is not changed,
Figure BDA0002362080830000093
and after the structure is refined RexpIs 1.589, RwpIs 2.236, RpIs 1.733. With Zn2+Does not change the space group of the synthesized cobalt oxide due to Zn2+Has an ionic radius greater than that of Co2+And thus the cell parameters gradually increase.
Example 2:preparation of cobalt oxide and aluminum-doped cobalt oxide
Example 1 was repeated, with the difference that zinc nitrate hexahydrate was replaced by aluminium nitrate nonahydrate, giving an (aluminium-doped) cobalt oxide Co(3-x)AlxO4(x is more than or equal to 0 and less than or equal to 2), wherein x is 0, 0.5, 0.9, 1.3, 1.7 and 2.0 respectively, namely Al3+Substitution of isomorphs for Co occupying octahedral voids3+Substitution ratios are 0%, 20%, 40%, 60%, 80%, 100%.
The XRD results are shown in FIG. 2, and it can be seen from FIG. 1 that (aluminum-doped) cobalt oxide Co(3-x)AlxO4In accordance with the standard diffraction pattern of cobaltosic oxide (JCPDS: 42-1476). The space group of cobaltosic oxide is as follows: fd-3m, standard cell parameters are:
Figure BDA0002362080830000101
Z＝8。
when Co is present3+Is covered with Al3+After all the substitutions, the space group is not changed,
Figure BDA0002362080830000102
and after the structure is refined RexpIs 1.508, RwpIs 3.751, RpIs 2.394. With Zn2+Gradually increasing of (2), emptying of synthesized cobalt oxideThe cell population is unchanged, but the cell parameters are gradually increased.
Example 3:preparation of iron oxides and zinc-doped iron oxides
Weighing 6 parts of ferric chloride hexahydrate and zinc nitrate hexahydrate in a corresponding stoichiometric ratio by using an analytical balance, wherein the total amount of substances is 2.4mmol, the zinc nitrate hexahydrate comprises 0, 0.16mmol, 0.32mmol, 0.48mmol, 0.64mmol and 0.8mmol respectively, and the balance is cobalt chloride hexahydrate;
the above raw materials were dissolved in 40mL of ethylene glycol and stirred for 30 minutes. Then 30mmol of sodium acetate trihydrate was added to the mixture and stirred at 50 ℃ for 30 minutes;
the solution was then transferred to a stainless steel autoclave reactor and heated in an oven at 180 ℃ for 12 hours. The resulting solid product was washed 5 times by centrifugation, 3 times by centrifugation with deionized water, 2 times by centrifugation with ethanol, and then dried overnight in an oven at 60 ℃.
Finally, the prepared sample was ground to a powder to obtain the (zinc doped) iron oxide ZnxFe(3-x)O4(x is more than or equal to 0 and less than or equal to 1), wherein x is 0, 0.2, 0.4, 0.6, 0.8 and 1.0 respectively, namely Zn2+Substitution of class homologies for Fe occupying octahedral voids2+Substitution ratios are 0%, 20%, 40%, 60%, 80%, 100%.
The XRD results are shown in FIG. 3, and it can be seen from FIG. 3 that (Zn-doped) iron oxide ZnxFe(3-x)O4In accordance with the standard diffraction pattern (JCPDS: 19-629). The space group of ferroferric oxide is as follows: fd-3m, standard cell parameters are:
Figure BDA0002362080830000103
Z＝8。
through Rietveld structure refinement calculation, the space group of the synthesized ferroferric oxide is not changed,
Figure BDA0002362080830000111
and after the structure is refined RexpIs 3.644, RwpIs 9.905, RpIs 7.444. When Fe2+Is covered with Zn2+After all the substitutions, the space group is not changed,
Figure BDA0002362080830000112
and after the structure is refined RexpIs 8.276, RwpIs 10.557, RpIs 8.240. Among other iron oxides, with Zn2+The space group of the synthesized iron oxide is not changed, but the unit cell parameter is increased.
Example 4:preparation of iron oxide and aluminum-doped cobalt oxide
Example 3 was repeated, with the difference that crystalline aluminum chloride was used instead of zinc nitrate hexahydrate, giving the (aluminum-doped) iron oxide Fe(3-x)AlxO4(x is more than or equal to 0 and less than or equal to 1), wherein x is 0, 0.1, 0.2, 0.3, 0.4 and 0.5 respectively, namely Al3+Isomorphism substitution of Fe occupying tetrahedral (or octahedral) voids3+The substitution ratios are 0%, 10%, 20%, 30%, 40%, 50%.
The XRD results are shown in FIG. 4, and Fe can be seen from FIG. 4(3-x)AlxO4In accordance with the standard diffractogram of ferroferric oxide (JCPDS: 19-629). The space group of ferroferric oxide is as follows: fd-3m, standard cell parameters are:
Figure BDA0002362080830000113
Z＝8。
when Fe3+Is covered with Al3+After all the substitutions, the space group is not changed,
Figure BDA0002362080830000114
and after the structure is refined RexpIs 3.158, RwpIs 8.296, RpIs 6.407. Among other iron oxides, with Al3+The space group of the synthesized iron oxide is not changed, but the unit cell parameter is reduced.
Example 5:preparation of manganese oxide and zinc-doped manganese oxide
Potassium permanganate and zinc nitrate hexahydrate are weighed according to the corresponding stoichiometric ratio by an analytical balance, the total amount of substances is 2.4mmol, wherein the zinc nitrate hexahydrate comprises 0, 0.48mmol, 0.56mmol, 0.64mmol, 0.72mmol and 0.8mmol respectively, and the balance is potassium permanganate;
the above starting material was dissolved in 20mL of deionized water and stirred for 30 minutes. Then adding 5mmol ethanol into the mixture and stirring to dissolve for 30 minutes;
the solution was then transferred to a stainless steel autoclave reactor and heated in an oven at 180 ℃ for 12 hours. The resulting solid product was washed 3 times by centrifugation with deionized water and then dried in an oven at 60 ℃ overnight.
Finally, the prepared sample is ground into powder to obtain the (zinc doped) manganese oxide ZnxMn(3-x)O4(x is more than or equal to 0.6 and less than or equal to 1), wherein x is respectively 0.6, 0.7, 0.8, 0.9 and 1.0, namely Zn2+Substitution of isomorphs for Mn occupying octahedral voids2+The substitution ratios are 60%, 70%, 80%, 90%, 100%.
The XRD results are shown in FIG. 5, and it can be seen from FIG. 5 that (Zn-doped) manganese oxide ZnxMn(3-x)O4In accordance with the standard diffractogram (JCPDS: 24-734). The manganous manganic oxide is a tetragonal system, and the space group is as follows: i41/amd, standard cell parameters:
Figure BDA0002362080830000121
Z＝4。
through Rietveld structure refinement calculation, the space group of the synthesized ferroferric oxide is not changed,
Figure BDA0002362080830000122
and after the structure is refined RexpIs 17.001, RwpIs 20.813, RpIs 13.936. When Mn is present2+Is covered with Zn2+After all the substitutions, the space group is not changed,
Figure BDA0002362080830000123
and after the structure is refined RexpIs 14.506, RwpIs 19.655, RpIs 15.747. Among other oxides of manganeseWith Zn2+The space group of the synthesized manganese oxide is not changed but the unit cell parameter is reduced.
Example 6:preparation of manganese oxide and zinc-doped manganese oxide
Example 5 was repeated, with the difference that crystalline aluminum chloride was used instead of zinc nitrate hexahydrate, to give the (aluminum-doped) manganese oxide Mn(3-x)AlxO4(x is more than or equal to 0.5 and less than or equal to 0.9), wherein x is respectively 0.5, 0.6, 0.7, 0.8 and 0.9, namely Al3+Substitution of isomorphs for Mn occupying octahedral voids3+The substitution ratios are 50%, 60%, 70%, 80%, 90%.
The XRD results are shown in FIG. 6, and it can be seen from FIG. 6 that Mn is(3-x)AlxO4In accordance with the standard diffractogram of manganomanganic oxide (JCPDS: 24-734). The space group of the manganous manganic oxide is as follows: i41/amd, standard cell parameters:
Figure BDA0002362080830000124
Z＝4。
when Mn is present3+Is covered with Al3+After all the substitutions, the space group is not changed,
Figure BDA0002362080830000131
but due to the influence of AlOOH impurities, R is obtained after the structure is refinedexpIs 14.945, RwpIs 27.483, RpIs 20.945. Among other oxides of manganese, with Al3+The space group of the synthesized manganese oxide is not changed but the unit cell parameter is reduced.
Examples of the experiments
Microwave absorption characteristics
A network analyzer is adopted to represent the microwave absorption characteristic of the transition metal oxide, the manufacturer is Agilent, the model is N5244A, the dielectric loss and the magnetic loss are calculated, the microwave loss mechanism of the transition metal oxide is discussed by representing and calculating the spin magnetic moment, and the relationship between the spin magnetic moment and the microwave absorption performance and the microwave induced degradation is further disclosed.
Microwave induced degradation
The microwave oven device is adopted to explore the effect of the transition metal oxide on the tetracycline microwave-induced degradation. An ultraviolet-visible spectrophotometer is adopted to represent the effect of degrading tetracycline by three transition metal oxides, a manufacturer is Beijing Sundapu apparatus technology company Limited, the model is TU-1901, the spectral bandwidth is 2nm, the response time is 0.2s, the wavelength range is 500nm-700nm, the interval is 1nm in the scanning speed, and the absorbance display range is 0.2-0.8.
Zn obtained in example 1xCo(3-x)O4The removal effect of microwave-induced degradation of tetracycline is shown in fig. 7. As can be seen from FIG. 7, Co3O4The physical adsorption value of the zinc oxide to tetracycline is 2.2mg/g at 30min, and Zn is combinedxCo(3-x)O4The appearance of the adsorbent has no obvious change, and the physical adsorption quantity is basically kept consistent. Compared with single microwave induced degradation of tetracycline, the degradation amount is 36.8mg/g at 30 min. After adding ZnxCo(3-x)O4Then, the degradation rate is obviously accelerated, the degradation balance can be achieved within 15min, and the degradation amount can reach 47.7 mg/g. With Zn2+The content is increased, the degradation rate and the degradation amount are basically kept consistent.
Co obtained in example 2(3-x)AlxO4The removal effect of microwave-induced degradation of tetracycline is shown in fig. 8. As can be seen from FIG. 8, Co3O4The physical adsorption value of the tetracycline at 30min is 2.2 mg/g. The same comparison shows that the degradation amount of tetracycline induced by microwave alone is 36.8mg/g at 30 min. After adding Co(3-x)AlxO4After, compare Co3O4The degradation rate is obviously slowed down, the degradation balance can be achieved only after 20min, but the degradation amount is basically kept consistent. With Al3+The content is increased, the degradation rate is obviously slowed down, and the degradation amount at 15min is also lower, which indicates that Co3+Plays an obvious role in the process of degrading tetracycline by microwave induction.
Zn obtained in example 3xFe(3-x)O4The removal effect of microwave-induced degradation of tetracycline is shown in fig. 9. As can be seen from the view in figure 9,Fe3O4the physical adsorption value of the zinc oxide to tetracycline is 4.4mg/g at 30min, and Zn is combinedxFe(3-x)O4The appearance of the oxide has no obvious change, and the physical adsorption quantity is basically kept consistent. Compared with single microwave induced degradation of tetracycline, the degradation amount is 35.96mg/g at 30 min. After adding ZnxFe(3-x)O4Then, the degradation rate is obviously accelerated, the degradation balance can be achieved within 20min, and the degradation amount can reach 47.8 mg/g.
Fe obtained in example 4(3-x)AlxO4The removal effect of microwave-induced degradation of tetracycline is shown in fig. 10. As can be seen from FIG. 10, after addition of Fe(3-x)AlxO4After, phase ratio of Fe3O4The degradation rate is obviously slowed down, the degradation balance can be achieved only within 30min, and the degradation amount is also reduced.
Zn obtained in example 5xMn(3-x)O4The removal effect of microwave-induced degradation of tetracycline is shown in fig. 11. As can be seen from FIG. 11, Mn3O4The physical adsorption value of the zinc oxide to tetracycline is 2.38mg/g at 30min, and Zn is combinedxMn(3-x)O4The appearance of the adsorbent has no obvious change, and the physical adsorption quantity is basically kept consistent. Compared with single microwave induced degradation of tetracycline, the degradation amount is 35.81mg/g at 30 min. After adding Mn3O4After the oxide catalyst is used, the degradation rate is obviously accelerated, and the maximum degradation amount, namely 42.81mg/g, can be reached within 30 min.
Mn obtained in example 6(3-x)AlxO4The removal effect of microwave-induced degradation of tetracycline is shown in fig. 12. As can be seen from FIG. 12, Mn is added(3-x)AlxO4Then, the degradation rate is obviously accelerated, and the maximum degradation amount of the product can reach 42.81mg/g within 30 min.
SEM testing and analysis
The morphology of the transition metal oxide was characterized by Scanning Electron Microscopy (SEM), with the manufacturer being JEOL, model JSM-IT300, a scanning voltage of 20kV, and a magnification of 5000.
Obtained in example 1ZnxCo(3-x)O4The sample was analyzed for morphology, and its SEM is shown in FIG. 13. FIG. 13 results show that different Zn2+The appearance of the sample with the doping proportion is not obviously changed, and the sample is spherical particles with uniform size, the diameter is about 6-7 mu m, and the sample is assembled by small blocky particles with different side lengths of 400-900 nm. On one hand, the contact area with the tetracycline is increased, the tetracycline is favorably adsorbed, and the rate of degrading the tetracycline by microwave induction is increased; on the other hand, with Zn2+The content is increased, the appearance is not obviously changed, and the interference of other factors can be eliminated.
The invention has been described in detail with reference to specific embodiments and illustrative examples, but the description is not intended to be construed in a limiting sense. Those skilled in the art will appreciate that various equivalent substitutions, modifications or improvements may be made to the technical solution of the present invention and its embodiments without departing from the spirit and scope of the present invention, which fall within the scope of the present invention. The scope of the invention is defined by the appended claims.

Claims (10)

1. A method for preparing a spinel-type transition metal oxide, comprising the steps of:
step 1, preparing a precursor compound of transition metal and doped metal;
step 2, dissolving the raw materials in a solvent to prepare a solution;
and 3, carrying out reaction in the reactor to obtain a solid product, and optionally carrying out post-treatment.
2. The method of claim 1, wherein in step 1, the transition metal comprises cobalt, iron, and manganese, and the dopant metal comprises zinc and aluminum.
3. The method according to claim 1, wherein in step 1, the precursor of the transition metal oxide is a salt compound, such as cobalt, iron hydrochloride, preferably hydrate hydrochloride, and manganate, such as potassium permanganate.
4. The method according to claim 1, characterized in that in step 1, the precursor of the doping metal is a nitrate, such as zinc nitrate, preferably a hydrated nitrate, and a hydrochloride, such as aluminum chloride.
5. The process according to any one of claims 1 to 4, wherein in step 2, the solvent is water, an alcohol or a hydroalcoholic solution, and the alcohol is a monohydric or polyhydric alcohol, preferably ethylene glycol.
6. The method according to any one of claims 1 to 5, wherein in step 2, after the raw material is dissolved in the solvent, optionally with stirring, the mixture is preferably added with a salt.
7. A method according to claim 6, wherein the salt is preferably an ammonium salt, more preferably ammonium carbonate or ammonium bicarbonate, and sodium acetate may also be used.
8. Process according to one of claims 1 to 7, characterized in that in step 3 the reaction is carried out in a high-pressure apparatus, preferably a stainless steel autoclave reactor, and is heated at 120-.
9. The method according to one of claims 1 to 8, characterized in that in step 3, the post-treatment comprises washing, drying and calcination.
10. Use of the oxide obtained according to the process of one of claims 1 to 9 for the degradation of antibiotics in amounts up to 40mg/g or more.
CN202010024839.4A 2020-01-10 2020-01-10 Preparation method of spinel type transition metal oxide and application of spinel type transition metal oxide in degrading antibiotics Pending CN113120944A (en)

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JUN LIU ET AL.: ""Facile synthesis of stoichiometric zinc ferrite nanocrystal clusters with superparamagnetism and high magnetization"", 《MATERIALS RESEARCH BULLETIN》 *
XIN LIU ET AL.: ""Structural, Magnetic, and Thermodynamic Evolutions of Zn-Doped Fe3O4 Nanoparticles Synthesized Using a One-Step Solvothermal Method"", 《THE JOURNAL OF PHYSICAL CHEMISTRY C》 *
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113877599A (en) * 2021-09-27 2022-01-04 中国地质大学（武汉） Cobalt-manganese spinel material and preparation method and application thereof
CN113877599B (en) * 2021-09-27 2024-02-09 中国地质大学（武汉） Cobalt manganese spinel material and preparation method and application thereof

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